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Sample records for benzophenone

  1. Palladium catalysed asymmetric alkylation of benzophenone Schiff ...

    Indian Academy of Sciences (India)

    Asymmetric alkyl substitution of various benzophenone Schiff base substrates under biphasic conditions proceeded using optically active Palladium(II) complexes. The corresponding products were obtained in high yields but with moderate enantiomeric excess (ee). Addition of specific ionic liquids to the reaction medium ...

  2. Dermal uptake of benzophenone-3 from clothing

    DEFF Research Database (Denmark)

    Morrison, Glenn; Bekö, Gabriel; Weschler, Charles J.

    2017-01-01

    Benzophenone-3 (aka BP-3, oxybenzone) is added to sunscreens, plastics and some coatings to filter UV radiation. A suspected endocrine disruptor, BP-3 has been widely detected and ot only in summertime, where a more intended use of sunscreen might be expected in the urine of Danish children (Fred...

  3. Antioxidant benzophenones and xanthones from the root bark of ...

    African Journals Online (AJOL)

    Antioxidant benzophenones and xanthones from the root bark of Garcinia smeathmannii. Alain Meli Lannang, Justin Komguem, Fernande Ngounou Ngninzeko, Jean Gustave Tangmouo, David Lontsi, Asma Ajaz, Muhammad Iqbal Choudhary, Beiban Luc Sondengam, Atta -ur-Rahman ...

  4. [Anti-arrhythmic action of some amidinohydrazone substituted benzophenones. 1. Synthesis of new amidinohydrazone and N-phenylamidinohydrazone substituted benzophenones].

    Science.gov (United States)

    Richter, P H; Kasbohm, K; Besch, A; Hagen, A

    1992-10-01

    The title compounds are synthesized as a rule by condensation of substituted benzophenones and derivatives of aminoguanidine in the presence of up to 2.5 moles of an anorganic acid. They can be obtained alternatively via corresponding hydrazones, thiosemicarbazones or methylthiothiocarbonylhydrazones.

  5. Natural polyprenylated benzophenones: keto-enol tautomerism and stereochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Martins, Felipe T.; Cruz Junior, Jose W.; Doriguetto, Antonio C. [Universidade Federal de Alfenas, MG (Brazil). Dept. de Ciencias Exatas. Lab. de Cristalografia]. E-mail: doriguetto@unifal-mg.edu.br; Derogis, Priscilla B.M.C.; Santos, Marcelo H. dos; Veloso, Marcia P. [Universidade Federal de Alfenas, MG (Brazil). Dept. de Ciencias Exatas. Lab. de Fitoquimica e Quimica Medicinal; Ellena, Javier [Universidade de Sao Paulo, Sao Carlos, SP (Brazil). Inst. de Fisica

    2007-07-01

    The keto-enol tautomerism and stereochemistry study of a HIV-inhibitory natural benzophenone, (1R,5R,7R,8S)-(+)-3-(10-(3,4-dihydroxyphenyl)-10-hydroxymethylene) -8-methyl-1,5,7-tris(3-methyl-2-butenyl)-8-(4-methyl-3-pentenyl)-bicyclo [3.3.1]nonane-2,4,9-trione (a), isolated from Garcinia brasiliensis seeds is presented. The crystal structure of (a), which is also know as guttiferona A, was determined by X-ray diffraction and its intra and inter-molecular geometries discussed and compared with two analogue natural benzophenones: clusianone and epiclusianone. In (a), the hydroxyl H atom from enolizable 2,4,10-trione moiety is linked in the oxygen atom bonded to 10-(3,4-dihydroxyphenyl)methylene group, in opposition to the related natural benzophenones, where this analogue H-atom is placed in different O-atoms from bicyclo[3.3.1]nonane ring system. Such behaviour can be explained by the presence of aromatic OH6 group in (a) that origins a further delocalized resonance path along of 3,4-dihydroxyphenyl- C10-OH2 group. In addition, the (a) stereochemistry around C7 atom is compared with known structures of clusianone and epiclusianone and the influence from configuration in this chiral Catom to structural features found in the enolizable system is proposed. (author)

  6. Presence of benzophenones commonly used as UV filters and absorbers in paired maternal and fetal samples

    DEFF Research Database (Denmark)

    Krause, M; Frederiksen, H; Sundberg, K

    2018-01-01

    cordocentesis: and cord blood (n=23) obtained at delivery, both with paired maternal samples of serum and urine collected simultaneously, were used. All biological samples were analyzed by TurboFlow-liquid chromatography - tandem mass spectrometry for seven different benzophenones. RESULTS: Benzophenone-1 (BP-1...... of these compounds in order for better assessment of the risk to the developing fetus....

  7. CHARACTERIZATION AND ANTIPARASITIC ACTIVITY OF BENZOPHENONE THIOSEMICARBAZONES ON Trypanosoma brucei brucei

    Directory of Open Access Journals (Sweden)

    Georges C. Accrombessi

    2011-02-01

    Full Text Available The structure of four synthesized thiosemicarbazones, substituted or not, of benzophenone has been confirmed by spectrometrical analysis IR, NMR 1H and 13C. Their anti-trypanosomal activities were evaluated on Trypanosoma brucei brucei. Among these compounds, benzophenone 4 phenyl-3-thiosemicarbazone 4 has the highest activity with the half-inhibitory concentration (IC50 = 8.48 micromolar (µM. Benzophenone 4-methyl-3-thiosemicarbazone 3 and benzophenone thiosemicarbazone 1 showed moderate anti-trypanosomal activity with IC50 values equal to 23.27 µM and 67.17 µM respectively. Benzophenone 2 methyl-3-thiosemicarbazone 2 showed no activity up to IC50 = 371.74 µM.

  8. Derivative spectrophotometric analysis of benzophenone (as an impurity) in phenytoin.

    Science.gov (United States)

    Walash, Mohamed Ibrahim; Rizk, Mohamed Salem; Sheribah, Zeinab Awad; Salim, Mohamed Mansour

    2011-12-12

    Three simple and rapid spectrophotometric methods were developed for detection and trace determination of benzophenone (the main impurity) in phenytoin bulk powder and pharmaceutical formulations. The first method, zero-crossing first derivative spectrophotometry, depends on measuring the first derivative trough values at 257.6 nm for benzophenone. The second method, zero-crossing third derivative spectrophotometry, depends on measuring the third derivative peak values at 263.2 nm. The third method, ratio first derivative spectrophotometry, depends on measuring the peak amplitudes of the first derivative of the ratio spectra (the spectra of benzophenone divided by the spectrum of 5.0 μg/mL phenytoin solution) at 272 nm. The calibration graphs were linear over the range of 1-10 μg/mL. The detection limits of the first and the third derivative methods were found to be 0.04 μg/mL and 0.11 μg/mL and the quantitation limits were 0.13 μg/mL and 0.34 μg/mL, respectively, while for the ratio derivative method, the detection limit was 0.06 μg/mL and the quantitation limit was 0.18 μg/mL. The proposed methods were applied successfully to the assay of the studied drug in phenytoin bulk powder and certain pharmaceutical preparations. The results were statistically compared to those obtained using a polarographic method and were found to be in good agreement.

  9. Derivative spectrophotometric analysis of benzophenone (as an impurity in phenytoin

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    Walash Mohamed

    2011-12-01

    Full Text Available Abstract Three simple and rapid spectrophotometric methods were developed for detection and trace determination of benzophenone (the main impurity in phenytoin bulk powder and pharmaceutical formulations. The first method, zero-crossing first derivative spectrophotometry, depends on measuring the first derivative trough values at 257.6 nm for benzophenone. The second method, zero-crossing third derivative spectrophotometry, depends on measuring the third derivative peak values at 263.2 nm. The third method, ratio first derivative spectrophotometry, depends on measuring the peak amplitudes of the first derivative of the ratio spectra (the spectra of benzophenone divided by the spectrum of 5.0 μg/mL phenytoin solution at 272 nm. The calibration graphs were linear over the range of 1-10 μg/mL. The detection limits of the first and the third derivative methods were found to be 0.04 μg/mL and 0.11 μg/mL and the quantitation limits were 0.13 μg/mL and 0.34 μg/mL, respectively, while for the ratio derivative method, the detection limit was 0.06 μg/mL and the quantitation limit was 0.18 μg/mL. The proposed methods were applied successfully to the assay of the studied drug in phenytoin bulk powder and certain pharmaceutical preparations. The results were statistically compared to those obtained using a polarographic method and were found to be in good agreement.

  10. Unidirectional seeded single crystal growth from solution of benzophenone

    Science.gov (United States)

    Sankaranarayanan, K.; Ramasamy, P.

    2005-07-01

    A novel crystal growth method has been established for the growth of single crystal with selective orientation at room temperature. Using volatile solvent, the saturated solution containing the material to be crystallized was taken in an ampoule and allowed to crystallize by slow solvent evaporation assisted with a ring heater. The orientation of the growing crystal was imposed by means of a seed fixed at the bottom of the ampoule. By selecting a suitable ring heater voltage and by controlling the ring heater voltage, nucleation and the growth rate of the crystal were controlled more effectively. By employing this novel method, benzophenone single crystal ingots of diameters 10 and 20 mm and length more than 50 mm were successfully grown using xylene as solvent. The ease in scaling up of diameter from 10 to 20 mm shows the vital advantage of this technique. It was possible to achieve solute-crystal conversion efficiency of 100 percent. The grown benzophenone crystal was characterized by FTIR, TG and DTA, powder X-ray diffraction, X-ray rocking curve, optical transmission study and powder SHG measurement. The results show that the crystal quality is at least as good as the quality of the crystal grown by other known methods. Also, microbial growth was naturally avoided in this method, as the fresh solution is constantly made available for the growing crystal.

  11. Surface Photochemistry: Benzophenone as a Probe for the Study of Modified Cellulose Fibres

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    L. F. Vieira Ferreira

    2007-01-01

    Full Text Available This work reports the use of benzophenone, a very well characterized probe, to study new hosts (i.e., modified celluloses grafted with alkyl chains bearing 12 carbon atoms by surface esterification. Laser-induced room temperature luminescence of air-equilibrated or argon-purged solid powdered samples of benzophenone adsorbed onto the two modified celluloses, which will be named C12-1500 and C12-1700, revealed the existence of a vibrationally structured phosphorescence emission of benzophenone in the case where ethanol was used for sample preparation, while a nonstructured emission of benzophenone exists when water was used instead of ethanol. The decay times of the benzophenone emission vary greatly with the solvent used for sample preparation and do not change with the alkylation degree in the range of 1500–1700 micromoles of alkyl chains per gram of cellulose. When water was used as a solvent for sample preparation, the shortest lifetime for the benzophenone emission was observed; this result is similar to the case of benzophenone adsorbed onto the “normal” microcrystalline cellulose surface, with this latter case previously reported by Vieira Ferreira et al. in 1995. This is due to the more efficient hydrogen abstraction reaction from the glycoside rings of cellulose when compared with hydrogen abstraction from the alkyl chains of the modified celluloses. Triplet-triplet transient absorption of benzophenone was obtained in both cases and is the predominant absorption immediately after laser pulse, while benzophenone ketyl radical formation occurs in a microsecond time scale both for normal and modified celluloses.

  12. Optical modulation spectroscopy: a study of the self-reaction of benzophenone oxide

    Energy Technology Data Exchange (ETDEWEB)

    Girard, M.; Griller, D.

    1986-12-18

    The bimolecular self-reaction of benzophenone oxide was investigated by optical modulation spectroscopy and by product studies. The transient decayed to give benzophenone and oxygen and the rate constants for its disappearance, 2k, are described by the expression log (2k) = (9.1 +/- 0.2) - (1.8 +/- 0.3)/theta where theta = 2.30RT kcal mol/sup -1/. The significance of these parameters is discussed in terms of the orientational requirements for self-reaction. Benzophenone oxide was found to react with octanal with a rate constant 2.0 x 10/sup 4/ M/sup -1/ s/sup -1/.

  13. New benzophenone and quercetin galloyl glycosides from Psidium guajava L.

    Science.gov (United States)

    Matsuzaki, Keiichi; Ishii, Rie; Kobiyama, Kaori

    2010-01-01

    New benzophenone and flavonol galloyl glycosides were isolated from an 80% MeOH extract of Psidium guajava L. (Myrtaceae) together with five known quercetin glycosides. The structures of the novel glycosides were elucidated to be 2,4,6-trihydroxybenzophenone 4-O-(6″-O-galloyl)-β-d-glucopyranoside (1, guavinoside A), 2,4,6-trihydroxy-3,5-dimethylbenzophenone 4-O-(6″-O-galloyl)-β-d-glucopyranoside (2, guavinoside B), and quercetin 3-O-(5″-O-galloyl)-α-l-arabinofuranoside (3, guavinoside C) by NMR, MS, UV, and IR spectroscopies. Isolated phenolic glycosides showed significant inhibitory activities against histamine release from rat peritoneal mast cells, and nitric oxide production from a murine macrophage-like cell line, RAW 264.7. PMID:20354804

  14. A new antibacterial benzophenone glycoside from Psidium guajava (Linn.) leaves.

    Science.gov (United States)

    Ukwueze, Stanley E; Osadebe, Patience O; Okoye, Festus B C

    2015-01-01

    Bioactivity-guided fractionation of methanol extract from the leaves of Psidium guajava L. (Myrtaceae) yielded a new benzophenone glycoside, Guajaphenone A (2) together with two known compounds, Garcimangosone D (1) and Guaijaverin (3). Their structures were elucidated by analysis of spectroscopic data including 1D and 2D NMR and electrospray ionisation mass spectrometry (ESI-MS). The isolated compounds were screened against standard strains of Gram-positive and Gram-negative bacteria using broth dilution assay method, and the MIC values determined and compared with reference antibiotic ceftriaxone. They were found to have significant antibacterial activities against Escherichia coli and Staphylococcus aureus with all of them showing better activities against S. aureus, but displaying weaker activities, in comparison to ceftriaxone. However, despite reduced effect of these compounds against the organisms, this work opens the perspective to use these molecules as 'leads' for the design of novel and selective drug candidates for some tropical infectious diseases.

  15. FAAS determination of thallium after preconcentration using nitroso-S and TDBA onto benzophenone

    OpenAIRE

    Mohammad Ali Taher; Sayed Ziae Mohammadi Mobarakeh; Fatameh Saber Mahani

    2005-01-01

    Thallium is quantitatively retained by 2-nitroso-1-naphthol-4-sulfonic acid (nitroso-S) and tetradecyldimethylbenzylammonium chloride (TDBA) onto benzophenone in the pH range 10.0-11.5 from large volumes of aqueous solutions of various samples. After filtration, each solid mass consisting of thallium complex and benzophenone is dissolved with 5 mL of dimethylformamide and the metal was determined by flame atomic absorption spectrophotometry (FAAS). Eight replicate determinations of 10.0 μg...

  16. The potential health benefit of polyisoprenylated benzophenones from Garcinia and related genera: ethnobotanical and therapeutic importance.

    Science.gov (United States)

    Kumar, Satyanshu; Sharma, Shelly; Chattopadhyay, Sunil Kumar

    2013-09-01

    The diversity present in biological activities and the medicinal significance of natural products provide a renewed interest in the use of natural compounds and, more importantly, their role as a basis for drug development. Advancements in the field of natural product chemistry provide valuable information on Garcinia fruits which revealed the presence of biologically important secondary metabolites named as polyisoprenylated benzophenones (PIBs). They are mainly present in the genus Garcinia (Guttiferae) which occupies a prominent position in the history of natural products. Compared to the long history of medicinal uses and widespread research on Garcinia, the study of polyisoprenylated benzophenones was relatively limited. During recent years, these PIBs have been recognized as interesting and valuable biologically active secondary metabolites as many of the isolated polyisoprenylated benzophenones exhibited significant cytotoxic activity in in vitro and in vivo assay. During past decades, some promising advances had been achieved in understanding the chemistry and pharmacology of polyisoprenylated benzophenones. However, there has been not any systematic review on the ethnobotanical importance, chemistry, isolation techniques, structure activity relationships and the biological activities of polyisoprenylated benzophenones. In this review, the biological activity of different structures of polyisoprenylated benzophenones isolated from genus Clusia, Garcinia, Vismia, Allanblackia, Moronobea, Symphonia, Hypericum, Tovomita, Tovomiptosis and Ochrocarpus have been described. Therefore, the goal of this review article would be a valuable reference for the natural product chemists and biologists working on these PIBs. Furthermore, the review article on polyisoprenylated benzophenones would also be useful from the drug discovery point of view as cytotoxic agents in near future. This review focuses our understanding about the specific biological effects of Garcinia

  17. Photolysis of incorporated benzophenone derivatives inside compressed lipid monolayers

    Directory of Open Access Journals (Sweden)

    DEJAN Z. MARKOVIC

    2001-05-01

    Full Text Available The goal of this work was to study the possibility of the occurrence of radical-type lipid peroxidation of the lipid constituents on biomembranes, in compressed monolayers, having lipoidal benzophenone photosensitizers incorporated. The triplets of the photosensitizer abstract allylic and doubly-allylic hydrogen atoms from anticonjugated moities of the lipid molecules. The results simultaneously confirmed the occurrence of H-abstraction (and so the initiation of the peroxidizing chain mechanism, and the absence of the formation of lipid peroxides. The reason lies in "cage effect": the highly restricted spacial area of compressed lipid monolayers limits the mobility of the created radicals (lipid radicals and ketyl radicals and leads to their recombination, thus preventing the propagation step of the chain mechanism. With certain reservations it may be concluded that these results have a clear implication on real biomembranes: the structure of which is one of themain factors preventing the spread of the chain reaction, and the formation of lipid peroxides.

  18. Presence of benzophenones commonly used as UV filters and absorbers in paired maternal and fetal samples.

    Science.gov (United States)

    Krause, M; Frederiksen, H; Sundberg, K; Jørgensen, F S; Jensen, L N; Nørgaard, P; Jørgensen, C; Ertberg, P; Juul, A; Drzewiecki, K T; Skakkebaek, N E; Andersson, A M

    2018-01-01

    Previous studies have demonstrated widespread exposure of humans to certain benzophenones commonly used as UV filters or UV absorbers; some of which have been demonstrated to have endocrine disrupting abilities. To examine whether benzophenones present in pregnant women pass through the placental barrier to amniotic fluid and further to the fetal blood circulation. A prospective study of 200 pregnant women with simultaneously collected paired samples of amniotic fluid and maternal serum and urine. In addition, unique samples of human fetal blood (n=4) obtained during cordocentesis: and cord blood (n=23) obtained at delivery, both with paired maternal samples of serum and urine collected simultaneously, were used. All biological samples were analyzed by TurboFlow-liquid chromatography - tandem mass spectrometry for seven different benzophenones. Benzophenone-1 (BP-1), benzophenone-3 (BP-3), 4-methyl-benzophenone (4-MBP), and 4-hydroxy-benzophenone (4-HBP) were all detectable in amniotic fluid and cord blood samples and except 4-HBP also in fetal blood; albeit at a low frequency. BP-1 and BP-3 were measured at ~10-times lower concentrations in fetal and cord blood compared to maternal serum and 1000-times lower concentration compared to maternal urine levels. Therefore BP-1 and BP-3 were only detectable in the fetal circulation in cases of high maternal exposure indicating some protection by the placental barrier. 4-MBP seems to pass into fetal and cord blood more freely with a median 1:3 ratio between cord blood and maternal serum levels. Only for BP-3, which the women seemed to be most exposed to, did the measured concentrations in maternal urine and serum correlate to concentrations measured in amniotic fluid. Thus, for BP-3, but not for the other tested benzophenones, maternal urinary levels seem to be a valid proxy for fetal exposure. Detectable levels of several of the investigated benzophenones in human amniotic fluid as well as in fetal and cord blood calls

  19. Determination of personal care products -benzophenones and parabens- in human menstrual blood.

    Science.gov (United States)

    Jiménez-Díaz, I; Iribarne-Durán, L M; Ocón, O; Salamanca, E; Fernández, M F; Olea, N; Barranco, E

    2016-11-01

    Benzophenones and parabens are synthetic chemicals used in many personal care products, foods and pharmaceuticals. Benzophenones are used to protect the skin and materials from the adverse effects of UV-radiation, and parabens are used as preservatives. Despite their widespread occurrence and proven endocrine disrupting activity, relatively little is known about human exposure to these compounds. In the present work, an analytical method based on sample treatment using dispersive liquid-liquid microextraction (DLLME) for the extraction of six benzophenones (benzophenone-1, -2, -3, -6, -8 and 4-hydroxybenzophenone) and four parabens (methyl-, ethyl-, propyl- and butyl- paraben) from human menstrual blood samples, followed by ultrahigh performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) analysis, is proposed and validated. The method was validated using matrix-matched standard calibration followed by a recovery assay with spiked samples. The limits of detection ranged from 0.1 to 0.3ngmL -1 , with recoveries of 93.8% to 108.9%, and precision (evaluated as relative standard deviation) lower than 14% for all selected compounds. This method was successfully applied for the determination of the target compounds in 25 samples of human menstrual blood. Methylparaben and benzophenone-3 were the most frequently detected compounds (96%). Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Urinary concentrations of benzophenone-type ultra violet light filters and reproductive parameters in young men

    DEFF Research Database (Denmark)

    Adoamnei, Evdochia; Mendiola, Jaime; Moñino-García, Miriam

    2018-01-01

    BACKGROUND: Benzophenone (BP)-type ultraviolet (UV) light filters are chemicals frequently added to personal care products, insect repellents, sunscreens, and beverage and food packaging to diminish the harmful effects of UV sunlight on human skin or foodstuffs. BP-type UV filters have shown nega...

  1. A possible glycosidic benzophenone with full substitution on B-ring from Psidium guajava leaves.

    Science.gov (United States)

    Venditti, Alessandro; Ukwueze, Stanley E

    2017-04-01

    Bidimensional NMR analysis may be a useful tool to resolve the structure of chemical compounds also in mixture. This letter would demonstrate how these techniques could be applied e.g. to the reported case on identification of benzophenone glycoside from Psidium guajava. A tentative structure for the secondary component, not yet described, was possibly proposed on the basis of observation and critic review of available 1D and 2D NMR spectra.

  2. Acute Toxicity and Ecological Risk Assessment of Benzophenone-3 (BP-3 and Benzophenone-4 (BP-4 in Ultraviolet (UV-Filters

    Directory of Open Access Journals (Sweden)

    Yang Du

    2017-11-01

    Full Text Available Ultraviolet (UV-absorbing chemicals (UV filters are used in personal care products for the protection of human skin and hair from damage by UV radiation. Although these substances are released into the environment in the production and consumption processes, little is known about their ecotoxicology effects. The acute toxicity and potential ecological risk of UV filters benzophenone-3 (BP-3 and benzophenone-4 (BP-4 on Chlorella vulgaris, Daphnia magna, and Brachydanio rerio were analyzed in the present study. The EC50 values (96 h of BP-3 and BP-4 on C. vulgaris were 2.98 and 201.00 mg/L, respectively. The 48 h-LC50 of BP-3 and BP-4 on D. magna were 1.09 and 47.47 mg/L, respectively. The 96 h-LC50 of BP-3 and BP-4 on B. rerio were 3.89 and 633.00 mg/L, respectively. The toxicity of a mixture of BP-3 and BP-4 on C. vulgaris, D. magna, and B. rerio all showed antagonistic effects. The induced predicted no-effect concentrations of BP-3 and BP-4 by the assessment factor method were 1.80 × 10−3 and 0.47 mg/L, respectively, by assessment factor (AF method, which were both lower than the concentrations detected in the environment at present, verifying that BP-3 and BP-4 remain low-risk chemicals to the aquatic ecosystem.

  3. Acute Toxicity and Ecological Risk Assessment of Benzophenone-3 (BP-3) and Benzophenone-4 (BP-4) in Ultraviolet (UV)-Filters.

    Science.gov (United States)

    Du, Yang; Wang, Wen-Qian; Pei, Zhou-Tao; Ahmad, Fahmi; Xu, Rou-Rou; Zhang, Yi-Min; Sun, Li-Wei

    2017-11-19

    Ultraviolet (UV)-absorbing chemicals (UV filters) are used in personal care products for the protection of human skin and hair from damage by UV radiation. Although these substances are released into the environment in the production and consumption processes, little is known about their ecotoxicology effects. The acute toxicity and potential ecological risk of UV filters benzophenone-3 (BP-3) and benzophenone-4 (BP-4) on Chlorella vulgaris , Daphnia magna , and Brachydanio rerio were analyzed in the present study. The EC 50 values (96 h) of BP-3 and BP-4 on C. vulgaris were 2.98 and 201.00 mg/L, respectively. The 48 h-LC 50 of BP-3 and BP-4 on D. magna were 1.09 and 47.47 mg/L, respectively. The 96 h-LC 50 of BP-3 and BP-4 on B. rerio were 3.89 and 633.00 mg/L, respectively. The toxicity of a mixture of BP-3 and BP-4 on C. vulgaris , D. magna , and B. rerio all showed antagonistic effects. The induced predicted no-effect concentrations of BP-3 and BP-4 by the assessment factor method were 1.80 × 10 -3 and 0.47 mg/L, respectively, by assessment factor (AF) method, which were both lower than the concentrations detected in the environment at present, verifying that BP-3 and BP-4 remain low-risk chemicals to the aquatic ecosystem.

  4. Determination of parabens and benzophenone-type UV filters in human placenta. First description of the existence of benzyl paraben and benzophenone-4.

    Science.gov (United States)

    Valle-Sistac, Jennifer; Molins-Delgado, Daniel; Díaz, Marta; Ibáñez, Lourdes; Barceló, Damià; Silvia Díaz-Cruz, M

    2016-03-01

    UV filters and parabens (PBs) are chemicals used in daily personal care and hygiene products to protect materials and humans from the adverse effects of UV radiation and to preserve the integrity of the formulation, respectively. Several studies highlight their widespread environmental occurrence and endocrine disrupting effects. However, little is known about human exposure to these compounds. The objective of this study was to investigate the exposure of human embryos and foetuses to endocrine disrupting UV filters and PBs. Placentas from volunteer mothers in Barcelona were collected at delivery after informed, written consent by the pregnant women. UV filters and parabens were analysed by liquid chromatography-tandem mass spectrometry. The excellent performance of the method allowed measuring the target compounds in human placental tissue at low ng/g fresh weight level. The detection frequency of the selected compounds was in the range 17-100%. Benzophenone-1, methyl paraben, butyl paraben and benzyl paraben were detected in all samples. The highest measured concentration corresponded to methyl paraben, 11.77ng/g fresh weight. Reported concentrations of benzophenone-4 and benzyl paraben constitute the first evidence about their accumulation in placenta. The results obtained corroborate that foetuses are exposed to a wide diversity of UV filters and PBs via the placenta. Copyright © 2015 Elsevier Ltd. All rights reserved.

  5. Ten-year trends in urinary concentrations of triclosan and benzophenone-3 in the general U.S. population from 2003 to 2012.

    Science.gov (United States)

    Han, Changwoo; Lim, Youn-Hee; Hong, Yun-Chul

    2016-01-01

    Despite their popular use and emerging evidences of adverse health effects, consequent trends in population level triclosan and benzophenone-3 exposure have been poorly evaluated. Therefore, we examined temporal trends of urinary triclosan and benzophenone-3 concentration in the general U.S. population by combining five cycles of National Health and Nutritional Examination Survey (NHANES, 2003-2012) data. We calculated percent changes and the least square geometric means (LSGMs) of urinary triclosan and benzophenone-3 concentration from 10,232 participants by using multivariable regression models. As a result, LSGM concentration of urinary triclosan and benzophenone-3 did not show statistically significant changes over the study period. [Percent change (95% CI): Triclosan, -7.35% (-20.86, 8.47); Benzophenone-3, 7.08% (-27.88, 58.99)] However, we found decreasing trend of urinary triclosan concentration and increasing trend of urinary benzophenone-3 concentration since 2005-2006. Socio-demographic factors which affected urinary concentration of triclosan and benzophenone-3 persisted throughout 10 year study period. Highest income group showed higher level of urinary triclosan and benzophenone-3 concentration. Overall concentration of benzophenone-3 was higher in female than in male, and higher in non-Hispanic Whites than any other races/ethnicities. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Benzophenone Suppression of Quercetin Antioxidant Activity towards Lipids under UV-B Irradiation Regime: Detection by HPLC Chromatography

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    Jelena S. Stanojević

    2013-01-01

    Full Text Available Quercetin, a well-known flavonoid antioxidant, has been employed to control benzophenone-sensitized peroxidation of the lipid mixture in methanol solution, induced by continuous UV-B irradiation. Surprisingly, the detected quercetin antioxidant activity was almost negligible. The presented data suggests that the reason is not in its own UV-B-induced degradation but rather in its interrelationship with benzophenone during UV-B stress. On the other side of this relationship, benzophenone anticipated sensitizing role towards lipids; that is, the initiation of lipid peroxidation has been affected as well. These results, obtained by HPLC chromatography, partly confirm but partly relativize to some extent recent results obtained with the same system by spectrophotometric method.

  7. Beta-carotene suppression of benzophenone-sensitized lipid peroxidation in hexane through additional chain-breaking activities

    Energy Technology Data Exchange (ETDEWEB)

    Cvetkovic, Dragan [Faculty of Technology, 16000 Leskovac (Serbia); Markovic, Dejan, E-mail: dejan_markovic57@yahoo.co [Faculty of Technology, 16000 Leskovac (Serbia)

    2011-01-15

    The aim of this work is to estimate the antioxidant activity of {beta}-carotene in the presence of two different mixtures of phospholipids in hexane solution, under continuous UV-irradiation from three different ranges (UV-A, UV-B, and UV-C). {beta}-Carotene is employed to control lipid peroxidation process generated by UV-irradiation, in the presence and in the absence of selected photosensitizer, benzophenone, by scavenging the involved, created free radicals. The results show that {beta}-carotene undergoes to a substantial, probably structural dependent destruction (bleaching), highly dependent on UV-photons energy input, more expressed in the presence than in the absence of benzophenone. The additional bleaching is synchronized with the further increase in {beta}-carotene antioxidant activity in the presence of benzophenone, implying the same cause: increase in (phospholipids peroxidation) chain-breaking activities.

  8. Phytoremediation of Benzophenone and Bisphenol A by Glycosylation with Immobilized Plant Cells

    Directory of Open Access Journals (Sweden)

    Kei Shimoda

    2009-01-01

    Full Text Available Benzophenone and bisphenol A are environmental pollutions, which have been listed among “chemicals suspected of having endocrine disrupting effects” by the World Wildlife Fund, the National Institute of Environmental Health Sciences in the USA and the Japanese Environment Agency. The cultured cells of Nicotiana tabacum glycosylated benzophenone to three glycosides, 4-O-β-D-glucopyranosylbenzophenone (9%, diphenylmethyl β-D-glucopyranoside (14%, and diphenylmethyl 6-O-(β-D-glucopyranosyl-β-D-glucopyranoside (12% after 48 h incubation. On the other hand, incubation of benzophenone with immobilized cells of N. tabacum in sodium alginate gel gave products in higher yields, i.e. the yields of 4-O-β-D-glucopyranosylbenzophenone, diphenylmethyl β-D-glucopyranoside, and diphenylmethyl 6-O-(β-D-glucopyranosyl-β-D-glucopyranoside were 15, 27, and 22%, respectively. Bisphenol A was converted into three glycosides, 2,2-bis(4-β-D-glucopyranosyloxyphenylpropane (16%, 2-(4-β-D-glucopyranosyloxy-3-hydroxyphenyl-2-(4-β-D-gluco- pyranosyloxyphenyl propane (8%, and 2-(3-β-D-glucopyranosyloxy-4-hydroxyphenyl-2-(4-β-D-glucopyranosyloxyphe nylpropane (5%. Also the use of immobilized N. tabacum cells improved the yield of products; the glycosylation of bisphenol A with immobilized N. tabacum gave 2,2-bis(4-β-D-glucopyranosyloxyphenylpropane (24%, 2-(4-β-D-gluco- pyranosyloxy-3-hydroxyphenyl-2-(4-β-D-glucopyranosyloxyphenyl propane (15%, and 2-(3-β-D-glucopyranosyloxy- 4-hydroxyphenyl-2-(4-β-D-glucopyranosyloxyphenylpropane (11%.

  9. Surface studies on benzophenone doped PDMS microstructures fabricated using KrF excimer laser direct write lithography

    Energy Technology Data Exchange (ETDEWEB)

    Kant, Madhushree Bute; Shinde, Shashikant D. [Department of Physics, University of Pune, Pune 411007 (India); Bodas, Dhananjay [Centre for Nanobioscience, Agharkar Research Institute, Agharkar road, Pune 411004 (India); Patil, K.R. [Center for Materials Characterization, National Chemical Laboratories, Pune 411008 (India); Sathe, V.G. [UGC DAE Inter University Consortium, Indore 452017 (India); Adhi, K.P. [Department of Physics, University of Pune, Pune 411007 (India); Gosavi, S.W., E-mail: swg@physics.unipune.ac.in [Department of Physics, University of Pune, Pune 411007 (India)

    2014-09-30

    Graphical abstract: - Highlights: • Use of KrF Laser micromachining for Lab-On-Chip applications at lower fluence. • Addition of Benzophenone in PDMS enhances its self development sensitivity. • Benzophenone helps efficient energy transfer for equal density of bond scissioning. • Correlation of chemical composition with laser dose and microstructure. • Microstructures with well defined clean sidewalls. - Abstract: This paper discusses microfabrication process for benzophenone doped polydimethylsiloxane (PDMS) using laser lithography. KrF excimer laser of 248 nm with 20 ns pulse width at repetition rate of 1 Hz was used for microfabrication of undoped and benzophenone doped PDMS. The doped-PDMS shows sensitivity below 365 nm, permitting processing under ambient light. The analysis of etch depth revealed that doped PDMS shows self developable sensitivity at lower fluence of ∼250 mJ/cm{sup 2}. The unexposed and exposed surface was studied using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and Scanning electron microscopy (SEM). Spectrocopic analysis indicated increase in C-O, C=O, Si-O{sub 3} and Si-O{sub 4} bonding at the expense of Si-C and Si-O{sub 2} bonds of PDMS. In case of laser exposed doped-PDMS, removal of benzophenone from probe depth of spectroscopy was observed. Whereas the surface morphology of exposed and unexposed doped-PDMS was observed to be same, indicating clean development of PDMS micropatterns. The present study indicates that addition of 3.0 wt.% benzophenone in PDMS enhance self development sensitivity of PDMS. The self developable results on doped-PDMS are quite encouraging for its potential use in point of care Lab-On-Chip applications, for fabricating micropatterns using direct write laser lithography technology.

  10. Surface studies on benzophenone doped PDMS microstructures fabricated using KrF excimer laser direct write lithography

    International Nuclear Information System (INIS)

    Kant, Madhushree Bute; Shinde, Shashikant D.; Bodas, Dhananjay; Patil, K.R.; Sathe, V.G.; Adhi, K.P.; Gosavi, S.W.

    2014-01-01

    Graphical abstract: - Highlights: • Use of KrF Laser micromachining for Lab-On-Chip applications at lower fluence. • Addition of Benzophenone in PDMS enhances its self development sensitivity. • Benzophenone helps efficient energy transfer for equal density of bond scissioning. • Correlation of chemical composition with laser dose and microstructure. • Microstructures with well defined clean sidewalls. - Abstract: This paper discusses microfabrication process for benzophenone doped polydimethylsiloxane (PDMS) using laser lithography. KrF excimer laser of 248 nm with 20 ns pulse width at repetition rate of 1 Hz was used for microfabrication of undoped and benzophenone doped PDMS. The doped-PDMS shows sensitivity below 365 nm, permitting processing under ambient light. The analysis of etch depth revealed that doped PDMS shows self developable sensitivity at lower fluence of ∼250 mJ/cm 2 . The unexposed and exposed surface was studied using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and Scanning electron microscopy (SEM). Spectrocopic analysis indicated increase in C-O, C=O, Si-O 3 and Si-O 4 bonding at the expense of Si-C and Si-O 2 bonds of PDMS. In case of laser exposed doped-PDMS, removal of benzophenone from probe depth of spectroscopy was observed. Whereas the surface morphology of exposed and unexposed doped-PDMS was observed to be same, indicating clean development of PDMS micropatterns. The present study indicates that addition of 3.0 wt.% benzophenone in PDMS enhance self development sensitivity of PDMS. The self developable results on doped-PDMS are quite encouraging for its potential use in point of care Lab-On-Chip applications, for fabricating micropatterns using direct write laser lithography technology

  11. The growth of benzophenone crystals by Sankaranarayanan–Ramasamy (SR) method and slow evaporation solution technique (SEST): A comparative investigation

    International Nuclear Information System (INIS)

    Senthil Pandian, M.; Boopathi, K.; Ramasamy, P.; Bhagavannarayana, G.

    2012-01-01

    Highlights: ► Benzophenone single crystal was grown by Sankaranarayanan–Ramasamy method which has the sizes of 1060 mm length and 55 mm diameter for the first time. ► The conventional and SR-grown benzophenone crystals were characterized and compared using HRXRD, etching, laser damage threshold, microhardness, UV-transmittance, birefringence and dielectric analysis. ► The SR-grown benzophenone crystal has higher LDT, microhardness, transparency, dielectric permittivity, birefringence and lower FWHM, EPD, dielectric loss than the crystal grown by conventional method. ► The probable reason for higher crystalline perfection in SR-grown crystal was discussed. -- Abstract: Longest unidirectional〈1 0 0〉 benzophenone (BP) crystal having dimension of 1060 mm length and 55 mm diameter was grown by Sankaranarayanan–Ramasamy method. The growth rate was measured by monitoring the elevation of the crystal–solution interface at different temperatures. The high resolution X-ray diffraction and etching measurements indicate that the unidirectional grown benzophenone crystal has good crystalline perfection and less density of defects. The optical damage threshold of SEST and SR grown BP crystals has been investigated and found that the SR grown benzophenone crystal has higher laser damage threshold value than the conventional method grown crystal. Microhardness measurement shows that crystals grown by SR method have a higher mechanical stability than the crystals grown by SEST method. Dielectric permittivity and birefringence are high in SR grown crystal compared to SEST grown BP crystal. The UV–vis-NIR results show that SR method grown crystal exhibits 7% higher transmittance as against crystals grown by conventional method.

  12. Effects of the UV filter benzophenone-3 (oxybenzone) at low concentrations in zebrafish (Danio rerio)

    Energy Technology Data Exchange (ETDEWEB)

    Blüthgen, Nancy [University of Applied Sciences Northwestern Switzerland, School of Life Sciences, Gründenstrasse 40, CH‐4132 Muttenz (Switzerland); University of Basel, Division of Molecular and Systems Toxicology, Department of Pharmaceutical Sciences, Klingelbergstrasse 50, CH-4056 Basel (Switzerland); Zucchi, Sara [University of Applied Sciences Northwestern Switzerland, School of Life Sciences, Gründenstrasse 40, CH‐4132 Muttenz (Switzerland); Fent, Karl, E-mail: karl.fent@fhnw.ch [University of Applied Sciences Northwestern Switzerland, School of Life Sciences, Gründenstrasse 40, CH‐4132 Muttenz (Switzerland); Swiss Federal Institute of Technology (ETHZ), Department of Environmental Sciences, CH‐8092 Zürich (Switzerland)

    2012-09-01

    Organic UV filters including benzophenone-3 (BP-3) are widely used to protect humans and materials from damage by UV irradiation. Despite the environmental occurrence of BP-3 in the aquatic environment, little is known about its effects and modes of action. In the present study we assess molecular and physiological effects of BP-3 in adult male zebrafish (Danio rerio) and in eleuthero-embryos by a targeted gene expression approach focusing on the sex hormone system. Fish and embryos are exposed for 14 days and 120 hours post fertilization, respectively, to 2.4–312 μg/L and 8.2–438 μg/L BP-3. Chemical analysis of water and fish demonstrates that BP-3 is partly transformed to benzophenone-1 (BP-1) and both compounds are accumulated in adult fish. Biotransformation to BP-1 is absent in eleuthero-embryos. BP-3 exposure leads to similar alterations of gene expression in both adult fish and eleuthero-embryos. In the brain of adult males esr1, ar and cyp19b are down-regulated at 84 μg/L BP-3. There is no induction of vitellogenin expression by BP-3, both at the transcriptional and protein level. An overall down-regulation of the hsd3b, hsd17b3, hsd11b2 and cyp11b2 transcripts is observed in the testes, suggesting an antiandrogenic activity. No histological changes were observed in the testes after BP-3 treatment. The study leads to the conclusion that low concentrations of BP-3 exhibit similar multiple hormonal activities at the transcription level in two different life stages of zebrafish. Forthcoming studies should show whether this translates to additional physiological effects. Highlights: ► Activity of UV filter benzophenone-3 (BP-3) is assessed in zebrafish. ► BP-3 is partly metabolized to benzophenone-1 by adult fish but not embryos. ► Alterations of gene expression are similar in adult males and embryos. ► Gene expression alterations point to multiple hormonal activity of BP-3.

  13. Ten-year trends in urinary concentrations of triclosan and benzophenone-3 in the general U.S. population from 2003 to 2012

    International Nuclear Information System (INIS)

    Han, Changwoo; Lim, Youn-Hee; Hong, Yun-Chul

    2016-01-01

    Despite their popular use and emerging evidences of adverse health effects, consequent trends in population level triclosan and benzophenone-3 exposure have been poorly evaluated. Therefore, we examined temporal trends of urinary triclosan and benzophenone-3 concentration in the general U.S. population by combining five cycles of National Health and Nutritional Examination Survey (NHANES, 2003–2012) data. We calculated percent changes and the least square geometric means (LSGMs) of urinary triclosan and benzophenone-3 concentration from 10,232 participants by using multivariable regression models. As a result, LSGM concentration of urinary triclosan and benzophenone-3 did not show statistically significant changes over the study period. [Percent change (95% CI): Triclosan, −7.35% (−20.86, 8.47); Benzophenone-3, 7.08% (−27.88, 58.99)] However, we found decreasing trend of urinary triclosan concentration and increasing trend of urinary benzophenone-3 concentration since 2005–2006. Socio-demographic factors which affected urinary concentration of triclosan and benzophenone-3 persisted throughout 10 year study period. Highest income group showed higher level of urinary triclosan and benzophenone-3 concentration. Overall concentration of benzophenone-3 was higher in female than in male, and higher in non-Hispanic Whites than any other races/ethnicities. - Highlights: • We analyzed 2003–2012 NHANES to evaluate temporal trends in triclosan and BP3 exposure levels. • There was decreasing trend of urinary triclosan concentration since 2005–2006. • There was increasing trend of urinary BP3 concentration since 2005–2006. • Urinary triclosan and BP3 concentration of each NHANES cycle varied by socio-demographic factors. - In the analysis of 2003–2012 National Health and Nutrition Examination Surveys data, we found decreasing trend of urinary triclosan concentration and increasing trend of urinary Benzophenone-3 concentration since 2005–2006.

  14. FAAS determination of thallium after preconcentration using nitroso-S and TDBA onto benzophenone

    Directory of Open Access Journals (Sweden)

    Mohammad Ali Taher

    2005-06-01

    Full Text Available Thallium is quantitatively retained by 2-nitroso-1-naphthol-4-sulfonic acid (nitroso-S and tetradecyldimethylbenzylammonium chloride (TDBA onto benzophenone in the pH range 10.0-11.5 from large volumes of aqueous solutions of various samples. After filtration, each solid mass consisting of thallium complex and benzophenone is dissolved with 5 mL of dimethylformamide and the metal was determined by flame atomic absorption spectrophotometry (FAAS. Eight replicate determinations of 10.0 μg/mL of thallium in final dimethylformamide (DMF solution gave a mean absorbance of 0.150 with a relative standard deviation of 1.9%. The sensitivity for 1% absorption was 0.293 μg/mL. The method of extraction and preconcentration is economical, rapid, sensitive, highly selective and satisfactory. The interference of a number of anions and cations has been studied and the optimized conditions developed were utilized for the trace determination of thallium in various samples.

  15. Bisphenols, Benzophenones, and Bisphenol A Diglycidyl Ethers in Textiles and Infant Clothing.

    Science.gov (United States)

    Xue, Jingchuan; Liu, Wenbin; Kannan, Kurunthachalam

    2017-05-02

    Little is known with regard to the occurrence of potentially toxic chemicals in textiles and clothes. In this study, 77 textiles and infant clothing pieces were analyzed for the determination of bisphenols including bisphenol A (BPA) and bisphenol S (BPS), benzophenones, bisphenol A diglycidyl ethers (BADGEs), and novolac glycidyl ethers (NOGEs). BPA and BPS occurred in 82% and 53% of the textile samples, respectively, and at mean concentrations of 366 and 15 ng/g, respectively. Benzophenone-3 (BP3) occurred in 70% of the samples at a mean concentration of 11.3 ng/g. Among 11 BADGEs and NOGEs analyzed, BFDGE was the predominant compound, with a mean concentration of 13.6 ng/g. Concentrations of target chemicals were assessed by fabric type, color, and uses. Socks contained the highest concentrations of BPA (mean: 1810 ng/g) with concentrations as high as 13 300 ng/g in a 97% polyester fabric marketed for infants. Calculated dermal exposure dose to BPA by infants via textiles was as high as 7280 pg/kg BW/d. This is the first study to report the occurrence of, and exposure to, BPA, BPS, BADGEs, and NOGEs in textiles and clothing.

  16. New Metabolites and Bioactive Chlorinated Benzophenone Derivatives Produced by a Marine-Derived Fungus Pestalotiopsis heterocornis

    Directory of Open Access Journals (Sweden)

    Hui Lei

    2017-03-01

    Full Text Available Four new compounds, including two isocoumarins, pestaloisocoumarins A and B (1, 2, one sesquiterpenoid degradation, isopolisin B (4, and one furan derivative, pestalotiol A (5, together with one known isocoumarin, gamahorin (3, and three chlorinated benzophenone derivatives, pestalachloride B (6, pestalachloride E (7 and a mixture of pestalalactone atropisomers (8a/8b, were isolated from a culture of the fungus Pestalotiopsis heterocornis associated with sponge Phakellia fusca. These new chemical structures were established using NMR and MS spectroscopic data, as well as single-crystal X-ray crystallographic analysis and CD Cotton effects. All of the isolated compounds were evaluated for their antimicrobial and cytotoxic activities. Isocoumarins 1–3, showed antibacterial activities against Gram-positive bacteria Staphylococcus aureus and Bacillus subtilis with MIC values ranging from 25 to 100 μg/mL and weak antifungal activities. Chlorinated benzophenone derivatives 6–8 exhibited antibacterial activities against S. aureus and B. subtilis with MIC values ranging from 3.0 to 50 μg/mL and cytotoxicities against four human cancer cell lines with IC50 values of 6.8–87.8 μM.

  17. Benzophenone guttiferone A from Garcinia achachairu Rusby (Clusiaceae presents genotoxic effects in different cells of mice.

    Directory of Open Access Journals (Sweden)

    Peterson Menezes Terrazas

    Full Text Available Benzophenones from natural sources and those of synthetic analogues present several reports of potent biological properties, and Guttiferone A represents a promising medicinal natural compound with analgesic and gastroprotective profiles. Considering that there are no reports that assess the genetic toxicity of Guttiferone A, the present study was undertaken to investigate the genotoxic potential of this benzophenone isolated from seeds of Garcinia achachairu in terms of DNA damage in different cells of Swiss albino mice using the comet assay, and its clastogenic/aneugenic effects in bone marrow cells in vivo by the micronucleus test. Cytotoxicity was assessed by scoring polychromatic (PCE and normochromatic (NCE erythrocytes ratio. Guttiferone A was administered by oral gavage at doses of 15, 30 and 60 mg/kg. The results showed that Guttiferone A produced genotoxic effects in leukocytes, liver, bone marrow, brain and testicle cells and clastogenic/aneugenic effects in bone marrow erythrocytes of mice. The PCE/NCE ratio indicated no cytotoxicity. Since guttiferone A is harmful to the genetic material we suggest caution in its use by humans.

  18. Hepatic oxidative stress biomarker responses in freshwater fish Carassius auratus exposed to four benzophenone UV filters.

    Science.gov (United States)

    Liu, Hui; Sun, Ping; Liu, Hongxia; Yang, Shaogui; Wang, Liansheng; Wang, Zunyao

    2015-09-01

    Benzophenone (BP) type UV filters are widely used in many personal care products to protect human from UV irradiation. Despite the estrogenic potencies to fish and the environmental occurrences of BP derivatives in aquatic systems, little information is available regarding their effects on the antioxidant defense system in fish. In this work, the oxidative stress induced in livers of Carassius auratus was assessed using four biomarkers. The integrated biomarker response (IBR) was applied to assess the overall antioxidant status in fish. Moreover, liver tissues were also studied histologically. The changes in the activities of antioxidant enzymes and glutathione levels suggested that BPs generates oxidative stress in fish. The IBR index revealed that the hepatic oxidative toxicity followed the order BP-1>BP-2>BP-4>BP-3. The histopathological analysis revealed lesions caused by BPs. This investigation provides essential information for assessing the potential ecological risk of BP-type UV filters. Copyright © 2015 Elsevier Inc. All rights reserved.

  19. (Benzophenone imine-κNchlorido(hydridotripyrazolylborato(triphenylphosphineruthenium(II diethyl ether solvate

    Directory of Open Access Journals (Sweden)

    Hung-Chun Tong

    2008-11-01

    Full Text Available The reaction of RuCl(Tp(Ph3P2, where Tp is [(CH3N2]3BH, with benzophenone imine leads to the formation of the title compound, [Ru(C9H10BN6Cl(C13H11N(C18H15P]·C4H10O. The environment about the Ru atom corresponds to a slightly distorted octahedron and the bite angle of the Tp ligand produces an average N—Ru—N angle of 86.3 (9°. The three Ru—N(Tp bond lengths [2.117 (2, 2.079 (2 and 2.084 (2 Å] are slightly longer than the average distance (2.038 Å in other ruthenium–Tp complexes.

  20. Transformation of benzophenone-type UV filters by chlorine: Kinetics, products identification and toxicity assessments

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jian; Ma, Li-yun; Xu, Li, E-mail: xulpharm@mails.tjmu.edu.cn

    2016-07-05

    Highlights: • Chlorination kinetics of three benzophenone-type UV filters (BPs) was studied. • Chlorination of BPs followed second-order reaction. • The transformation products (TPs) of six BPs were identified. • Several transformation pathways were proposed. • Mostly enhanced toxicity of TPs after chlorination was observed. - Abstract: The present study focused on the kinetics, transformation pathways and toxicity of several benzophenone-type ultraviolet filters (BPs) during the water chlorination disinfection process. The transformation kinetics of the studied three BPs was found to be second-order reaction, which was dependent on the concentration of BPs and chlorine. The second-order rate constants increased from 86.7 to 975 M{sup −1} s{sup −1} for oxybenzone, 49.6–261.7 M{sup −1} s{sup −1} for 4-hydroxybenzophenone and 51.7–540 M{sup −1} s{sup −1} for 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid with the increasing pH value from 6 to 8 of the chlorination disinfection condition. Then the transformation products (TPs) of these BPs were identified by HPLC-QTof analysis. Several transformation pathways, including electrophilic substitution, methoxyl substitution, ketone groups oxidation, hydrolysis, decarboxylation and ring cleavage reaction, were speculated to participate in the chlorination transformation process. Finally, according to the toxicity experiment on luminescent bacteria, Photobacterium phosphoreum, enhanced toxicity was observed for almost all the TPs of the studied BPs except for 2,2′-dihydroxy-4,4′-dimethoxybenzophenone; it suggested the formation of TPs with more toxic than the parent compounds during the chlorination process. The present study provided a foundation to understand the transformation of BPs during chlorination disinfection process, and was of great significance to the drinking water safety.

  1. Evaluation of ecotoxicological effects of benzophenone UV filters: Luminescent bacteria toxicity, genotoxicity and hormonal activity.

    Science.gov (United States)

    Zhang, Qiuya; Ma, Xiaoyan; Dzakpasu, Mawuli; Wang, Xiaochang C

    2017-08-01

    The widespread use of organic ultraviolet (UV) filters in personal care products raises concerns about their potentially hazardous effects on human and ecosystem health. In this study, the toxicities of four commonly used benzophenones (BPs) UV filters including benzophenone (BP), 2-Hydroxybenzophenone (2HB), 2-Hydroxy-4-methoxybenzophenone (BP3), and 2-Hydroxy-4-methoxybenzophenone-5-sulfonicacid (BP4) in water were assayed in vitro using Vibrio fischeri, SOS/umu assay, and yeast estrogen screen (YES) assay, as well as in vivo using zebrafish larvae. The results showed that the luminescent bacteria toxicity, expressed as logEC 50 , increased with the lipophilicity (logKow) of BPs UV filters. Especially, since 2HB, BP3 and BP4 had different substituent groups, namely -OH, -OCH 3 and -SO 3 H, respectively, these substituent functional groups had a major contribution to the lipophilicity and acute toxicity of these BPs. Similar tendency was observed for the genotoxicity, expressed as the value of induction ratio=1.5. Moreover, all the target BPs UV filters showed estrogenic activity, but no significant influences of lipophilicity on the estrogenicity were observed, with BP3 having the weakest estrogenic efficiency in vitro. Although BP3 displayed no noticeable adverse effects in any in vitro assays, multiple hormonal activities were observed in zebrafish larvae including estrogenicity, anti-estrogenicity and anti-androgenicity by regulating the expression of target genes. The results indicated potential hazardous effects of BPs UV filters and the importance of the combination of toxicological evaluation methods including in vitro and in vivo assays. Copyright © 2017 Elsevier Inc. All rights reserved.

  2. Skin penetration and photoprotection of topical formulations containing benzophenone-3 solid lipid microparticles prepared by the solvent-free spray-congealing technique.

    Science.gov (United States)

    Martins, Rodrigo Molina; Siqueira, Silvia; Fonseca, Maria José Vieira; Freitas, Luis Alexandre Pedro

    2014-01-01

    Solid-lipid microparticles loaded with high amounts of the sunscreen UV filter benzophenone-3 were prepared by spray congealing with the objective of decreasing its skin penetration and evaluate whether the sunscreen's photoprotection were impaired by the microencapsulation process. The microparticles were produced using the natural lipids carnauba wax or bees wax and three different concentrations of benzophenone-3 (30, 50 and 70%) using spray congealing technique. The microparticles presented properties suitable for topical application, such as spherical morphology, high encapsulation efficiency (95.53-102.2%), average particle sizes between 28.5 and 60.0 µm with polydispersivities from 1.2 to 2.5. In studies of in vitro skin penetration and preliminary stability, formulations of gel cream containing carnauba wax solid lipid microparticles and 70% benzophenone-3 when compared to the formulation added of bees wax solid-lipid microparticles containing 70% benzophenone-3, was stable considering the several parameters evaluated and were able to decrease the penetration of the UV filter into pig skin. Moreover, the formulations containing solid lipid microparticles with 70% benzophenone-3 increased the photoprotective capacity of benzophenone-3 under UV irradiation. The results show that spray-congealed microparticles are interesting solid forms to decrease the penetration solar filters in the skin without compromising their photoprotection.

  3. A novel dispersive solid-phase extraction method using metal-organic framework MIL-101 as the adsorbent for the analysis of benzophenones in toner.

    Science.gov (United States)

    Li, Ning; Zhu, Quanfei; Yang, Yang; Huang, Jianlin; Dang, Xueping; Chen, Huaixia

    2015-01-01

    Metal-organic frameworks (MOFs) have been paid widespread attention in the field of adsorption and separation materials due to its porosity, large specific surface area, unsaturated metal-ligand sites and structural diversity. In this study, the green powder MIL-101 was synthesized and used for the extraction of benzophenone, 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxy-benzophenone from toner samples for the first time. The synthesized MIL-101 was characterized by X-ray diffraction, scanning electron microscopy, thermogravimetry and nitrogen adsorption porosimetry. The MIL-101 was applied as the dispersive solid phase extraction (DSPE) adsorbent for the extraction and preconcentration of benzophenone, 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxy-benzophenone from toner samples. The extraction conditions were investigated. Under the optimized conditions, a DSPE-HPLC method for the determination of benzophenone, 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxy-benzophenone was developed. The method yielded a linear calibration curve in the concentration ranges from 4.0 to 3500 μg L(-1) for the three analytes in toner samples with regression coefficients (r(2)) of 0.9992, 0.9999 and 0.9990, respectively. Limits of detection were 1.2, 1.2 and 0.9 μg L(-1), respectively. Both the intra-day and inter-day precisions (RSDs) were <10%. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. Effect of relative humidity on the migration of benzophenone from paperboard into the food simulant Tenax and modelling hereof

    DEFF Research Database (Denmark)

    Barnkob, Line Lundbæk; Petersen, Jens Højslev

    2013-01-01

    carried out at a constant temperature of 34°C. It was found that the migration of benzophenone after more than 30 days was 4.8 times higher at a relative humidity of 64%-71%, and 7.3 times higher at a relative humidity of >73%, compared with that at a relative humidity of 39%-49%. Diffusion and partition......The aim of this study was to investigate the effect of relative humidity on the migration of benzophenone from paperboard into the food simulant Tenax®. Kinetic migration investigations were carried out with three relative humidities in the interval between 39% and >73%. All investigations were...... coefficients were derived from the results by using a software for modelling migration in multilayer materials. Both the diffusion coefficient and the partition coefficient, between paperboard and Tenax®, decrease with increasing relative humidity. The experimental results were correctly modelled only when...

  5. Direct synthesis of highly substituted 2-cyclohexenones and sterically hindered benzophenones based on a [5C + 1C] annulation.

    Science.gov (United States)

    Fu, Zhenqian; Wang, Mang; Dong, Ying; Liu, Jun; Liu, Qun

    2009-08-21

    The regiospecific [5C + 1C] annulation of readily available alpha-alkenoyl ketene (S,S)-acetals 1 with aryl methyl ketones 2, the less active methylene compounds, has been developed. Upon treatment of 1 with 2 in the presence of t-BuOK in DMF at room temperature, highly substituted 2-cyclohexenones 3 were synthesized in high to excellent diastereoselectivities with high yields. On the basis of this strategy, sterically hindered benzophenones 4 were conveniently prepared via the iodonation-aromatization of 2-cyclohexenones 3 with I(2) in MeONa/MeOH basic medium. Furthermore, benzophenones 4 were also obtained directly from 1 and 2 following a sequential [5 + 1] annulation-iodonation-aromatization procedure in a one-pot operation.

  6. Use of pooled samples to assess human exposure to parabens, benzophenone-3 and triclosan in Queensland, Australia.

    Science.gov (United States)

    Heffernan, A L; Baduel, C; Toms, L M L; Calafat, A M; Ye, X; Hobson, P; Broomhall, S; Mueller, J F

    2015-12-01

    Parabens, benzophenone-3 and triclosan are common ingredients used as preservatives, ultraviolet radiation filters and antimicrobial agents, respectively. Human exposure occurs through consumption of processed food and use of cosmetics and consumer products. The aim of this study was to provide a preliminary characterisation of exposure to selected personal care product chemicals in the general Australian population. De-identified urine specimens stratified by age and sex were obtained from a community-based pathology laboratory and pooled (n=24 pools of 100). Concentrations of free and total (sum of free plus conjugated) species of methyl, ethyl, propyl and butyl paraben, benzophenone-3 and triclosan were quantified using isotope dilution tandem mass spectrometry; with geometric means 232, 33.5, 60.6, 4.32, 61.5 and 87.7ng/mL, respectively. Age was inversely associated with paraben concentration, and females had concentrations approximately two times higher than males. Total paraben and benzophenone-3 concentrations are significantly higher than reported worldwide, and the average triclosan concentration was more than one order of magnitude higher than in many other populations. This study provides the first data on exposure of the general Australian population to a range of common personal care product chemical ingredients, which appears to be prevalent and warrants further investigation. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. Photo catalytic reduction of benzophenone on TiO{sub 2}: Effect of preparation method and reaction conditions

    Energy Technology Data Exchange (ETDEWEB)

    Albiter E, E.; Valenzuela Z, M. A.; Alfaro H, S.; Flores V, S. O.; Rios B, O.; Gonzalez A, V. J.; Cordova R, I., E-mail: mavalenz@ipn.m [IPN, Escuela Superior de Ingenieria Quimica e Industrias Extractivas, Laboratorio de Catalisis y Materiales, Zacatenco, 07738 Mexico D. F. (Mexico)

    2010-07-01

    The photo catalytic reduction of benzophenone was studied focussing on improving the yield to benzhydrol. TiO{sub 2} was synthesized by means of a hydrothermal technique. TiO{sub 2} (Degussa TiO{sub 2}-P25) was used as a reference. Catalysts were characterized by X-ray diffraction and nitrogen physisorption. The photo catalytic reduction was carried out in a batch reactor at 25 C under nitrogen atmosphere, acetonitrile as solvent and isopropanol as electron donor. A 200 W Xe-Hg lamp ({lambda}= 360 nm) was employed as irradiation source. The chemical composition of the reaction system was determined by HPLC. Structural and textural properties of the synthesized TiO{sub 2} depended on the type of acid used during sol formation step. Using HCl, a higher specific surface area and narrower pore size distribution of TiO{sub 2} was obtained in comparison with acetic acid. As expected, the photochemical reduction of benzophenone yielded benzopinacol as main product, whereas, benzhydrol is only produced in presence of TiO{sub 2} (i.e. photo catalytic route). In general, the hydrothermally synthesized catalysts were less active and with a lower yield to benzhydrol. The optimal reaction conditions to highest values of benzhydrol yield (70-80%) were found at 2 g/L (catalyst loading) and 0.5 m M of initial concentration of benzophenone, using commercial TiO{sub 2}-P25. (Author)

  8. Photo catalytic reduction of benzophenone on TiO2: Effect of preparation method and reaction conditions

    International Nuclear Information System (INIS)

    Albiter E, E.; Valenzuela Z, M. A.; Alfaro H, S.; Flores V, S. O.; Rios B, O.; Gonzalez A, V. J.; Cordova R, I.

    2010-01-01

    The photo catalytic reduction of benzophenone was studied focussing on improving the yield to benzhydrol. TiO 2 was synthesized by means of a hydrothermal technique. TiO 2 (Degussa TiO 2 -P25) was used as a reference. Catalysts were characterized by X-ray diffraction and nitrogen physisorption. The photo catalytic reduction was carried out in a batch reactor at 25 C under nitrogen atmosphere, acetonitrile as solvent and isopropanol as electron donor. A 200 W Xe-Hg lamp (λ= 360 nm) was employed as irradiation source. The chemical composition of the reaction system was determined by HPLC. Structural and textural properties of the synthesized TiO 2 depended on the type of acid used during sol formation step. Using HCl, a higher specific surface area and narrower pore size distribution of TiO 2 was obtained in comparison with acetic acid. As expected, the photochemical reduction of benzophenone yielded benzopinacol as main product, whereas, benzhydrol is only produced in presence of TiO 2 (i.e. photo catalytic route). In general, the hydrothermally synthesized catalysts were less active and with a lower yield to benzhydrol. The optimal reaction conditions to highest values of benzhydrol yield (70-80%) were found at 2 g/L (catalyst loading) and 0.5 m M of initial concentration of benzophenone, using commercial TiO 2 -P25. (Author)

  9. Use of pooled samples to assess human exposure to parabens, benzophenone-3 and triclosan in Queensland, Australia

    Science.gov (United States)

    Heffernan, A.L.; Baduel, C.; Toms, L.M.L.; Calafat, A.M.; Ye, X.; Hobson, P.; Broomhall, S.; Mueller, J.F.

    2017-01-01

    Parabens, benzophenone-3 and triclosan are common ingredients used as preservatives, ultraviolet radiation filters and antimicrobial agents, respectively. Human exposure occurs through consumption of processed food and use of cosmetics and consumer products. The aim of this study was to provide a preliminary characterisation of exposure to selected personal care product chemicals in the general Australian population. De-identified urine specimens stratified by age and sex were obtained from a community-based pathology laboratory and pooled (n = 24 pools of 100). Concentrations of free and total (sum of free plus conjugated) species of methyl, ethyl, propyl and butyl paraben, benzophenone-3 and triclosan were quantified using isotope dilution tandem mass spectrometry; with geometric means 232, 33.5, 60.6, 4.32, 61.5 and 87.7 ng/mL, respectively. Age was inversely associated with paraben concentration, and females had concentrations approximately two times higher than males. Total paraben and benzophenone-3 concentrations are significantly higher than reported worldwide, and the average triclosan concentration was more than one order of magnitude higher than in many other populations. This study provides the first data on exposure of the general Australian population to a range of common personal care product chemical ingredients, which appears to be prevalent and warrants further investigation. PMID:26368661

  10. A new method for the determination of benzophenone-UV filters in human serum samples by dispersive liquid-liquid microextraction with liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Vela-Soria, F; Ballesteros, O; Zafra-Gómez, A; Ballesteros, L; Navalón, A

    2014-04-01

    Benzophenone-UV filters (BP-UV filters) are extensively used in cosmetics products to avoid damaging effects of UV radiation. Despite their low toxicity, many research papers indicate that BP-UV filters are weak endocrine disruptors (EDCs). There are clear relationships between BP-UV filters exposure and several health disorders such as carcinogenesis and malformations observed in animals. In the present work, a new sample treatment procedure by dispersive liquid-liquid microextraction (DLLME) is proposed for the extraction of six BPs, namely benzophenone-1 (BP-1), benzophenone-2 (BP-2), benzophenone-3 (BP-3), benzophenone-6 (BP-6), benzophenone-8 (BP-8) and 4-hydroxybenzophenone (4-OH-BP), in human serum samples, followed by ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) analysis. The method involves an enzymatic treatment to quantify the total content (free plus conjugated species) of BP-UV filters in serum. The extraction parameters were accurately optimized using multivariate optimization approach. Benzophenone-d₁₀ (BP-d₁₀) was used as surrogate. Limits of quantification (LOQs) ranged from 0.4 to 0.9 ng mL(-1) and inter-day precision (evaluated as relative standard deviation) ranged from 1.9% to 13.1%. The method was validated using matrix-matched calibration and a recovery assay. Recovery rates for spiked samples ranged from 97% to 106%, and acceptable linearity was obtained up to concentrations of 40 ng mL(-1). The method was applied to the determination of the target compounds in human serum samples from 20 randomly selected anonymous individuals. Copyright © 2013 Elsevier B.V. All rights reserved.

  11. Urinary Concentrations of Triclosan, Benzophenone-3, and Bisphenol A in Taiwanese Children and Adolescents

    Directory of Open Access Journals (Sweden)

    Fu-Kuei Chang

    2017-12-01

    Full Text Available The purpose of this study was to determine the levels of urinary triclosan (TCS, benzophenone-3 (BP-3, and bisphenol A (BPA in 52 children and 71 adolescents. The effects of age and sex on the levels of urinary TCS, BP-3, and BPA were explored, respectively. Results demonstrated the overall detection rates of urinary TCS, BP-3, and BPA were 18.7%, 8.1%, and 49.6%, respectively. The females had higher TCS concentrations than males (p = 0.051. The detection rate of urinary BP-3 in females (12.3% was higher than that in males (0% (p = 0.015. Moreover, the detection rate of urinary BP-3 in adolescents (14.1% was higher than that in children (0% (p = 0.005. For children, no urinary BP-3 was found. There were no differences in detection rates and concentrations of urinary TCS, BP-3, and BPA between males and females, respectively. For adolescents, urinary BP-3 was only found in the females. Urinary TCS levels in females were higher than those in males (p = 0.047. The present study showed that urinary TCS concentrations in females were significantly higher than those in males, respectively. In addition, BP-3 was only detected in urine samples of female adolescents. Sex and age were the important factors influencing urinary TCS and BP-3 concentrations.

  12. Polymer-graphene composites by photocuring of a system containing benzophenone macromer

    Directory of Open Access Journals (Sweden)

    Jitaru Florentina

    2016-01-01

    Full Text Available Formulations incorporating benzophenone oligodimethacrylate (BP-DMA and graphene structures (graphene oxide/GO, reduced graphene oxide/RGO were exposed to UV/vis irradiation or femtosecond laser beam to achieve hybrid composites. All structures were characterized through various methods including 1H NMR and FTIR spectroscopies, optical microscopy, TEM, SEM/EDAX analysis, and DSC/XRD techniques. The photopolymerization of BP-DMA in monomer compositions with and without GO or RGO was investigated by photo-DSC and FTIR methods for determining the polymerization kinetic parameters. The photopolymerization experiments revealed a good photoreactivity of the monomers (degree of conversion: 65-77% after 1 minute exposure to UV/vis irradiation and the addition of graphene (up to 0.5%, whereas the polymerization rate varied between 0.14 and 0.1 s-1. Moreover, two-photon photopolymerization of the formulations in presence/absence of GO or RGO nanosheets (0.1 wt.% generated 2D microstructures by direct laser writing procedure. Also, the morphology and the properties of composites materials were analyzed.

  13. Photochemical reactions of triplet benzophenone and anthraquinone molecules with amines in the gas phase

    International Nuclear Information System (INIS)

    Zalesskaya, G.A.; Sambor, E.G.; Belyi, N.N.

    2004-01-01

    The intermolecular photoinduced reactions between triplet ketone molecules and aliphatic amines and pyridine are studied by the quenching of delayed fluorescence of anthraquinone and benzophenone vapors by diethylamine, dibutylamine, cyclohexylamine, triethylamine, and pyridine. In the temperature range 423-573 K, the delayed fluorescence quenching rate constants k q are estimated from changes in the decay rate constant and the intensity of delayed fluorescence upon increasing pressure of bath gases. It is ascertained that, in the gas phase, the mixtures under study exhibit both a negative and a positive dependence of k q on temperature, which indicates that some photoinduced reactions do not have activation barriers. The rate constant k q is shown to increase with decreasing ionization potential of the electron donors. This points to the importance of interactions with charge transfer in the photoreaction of triplet ketone molecules with aliphatic amines and pyridine in the gas phase. The relationship between k q and the change in the free energy ΔG upon the photoinduced intermolecular electron transfer, which is the primary stage of the photochemical reaction, is studied. It is shown that the dependence k q (ΔG) for the donor-acceptor pairs under study is described well by the Marcus equation, in which the average vibrational energies of the donor and acceptor are taken into account for the estimate of ΔG

  14. Measurement of Urinary Biomarkers of Parabens, Benzophenone-3, and Phthalates in a Belgian Population

    Science.gov (United States)

    Dewalque, Lucas; Pirard, Catherine; Charlier, Corinne

    2014-01-01

    Parabens, benzophenone-3 (BP3), and phthalates are commonly used as antimicrobial conservator, UV-filter, and plasticizer, respectively, and are thought to exhibit endocrine disrupting properties. These endocrine disrupting activities have been recently assumed to lead to cutaneous malignant melanoma. Humans are exposed to these chemicals through different sources such as food, personal care products, or cosmetics. In this study, we measured urinary levels of 4 parabens, BP3, and 7 metabolites of phthalates in samples collected from 261 participants living in and around Liege (Belgium). The analyses were carried out by liquid chromatography tandem mass spectrometry (LC-MS/MS) using isotopic dilution. To the best of our knowledge, this is the first time that the urinary levels of these 3 classes of chemicals are reported for the same general population in Belgium. Most of the parabens, the BP3, and all the phthalate metabolites were detected in 82.8 to 100.0% of the samples. For most of these chemicals, the exposure patterns significantly differ not only between children and adults, but also between males and females, especially with higher concentrations of parabens and phthalate metabolites in female and children subjects, respectively. PMID:24719881

  15. Antiviral activity of GW678248, a novel benzophenone nonnucleoside reverse transcriptase inhibitor.

    Science.gov (United States)

    Ferris, Robert G; Hazen, Richard J; Roberts, Grace B; St Clair, Marty H; Chan, Joseph H; Romines, Karen R; Freeman, George A; Tidwell, Jeffrey H; Schaller, Lee T; Cowan, Jill R; Short, Steven A; Weaver, Kurt L; Selleseth, Dean W; Moniri, Kelly R; Boone, Lawrence R

    2005-10-01

    The compound GW678248 is a novel benzophenone nonnucleoside reverse transcriptase inhibitor (NNRTI). Preclinical assessment of GW678248 indicates that this compound potently inhibits wild-type (WT) and mutant human immunodeficiency virus type 1 (HIV-1) reverse transcriptase in biochemical assays, with 50% inhibitory concentrations (IC(50)s) between 0.8 and 6.8 nM. In HeLa CD4 MAGI cell culture virus replication assays, GW678248 has an IC(50) of E138K, Y181C, Y188C, Y188L, G190A/E, P225H, and P236L and various combinations. An IC(50) of 86 nM was obtained with a mutant virus having V106I, E138K, and P236L mutations that resulted from serial passage of WT virus in the presence of GW678248. The presence of 45 mg/ml human serum albumin plus 1 mg/ml alpha-1 acid glycoprotein increased the IC(50) approximately sevenfold. Cytotoxicity studies with GW678248 indicate that the 50% cytotoxicity concentration is greater than the level of compound solubility and provides a selectivity index of >2,500-fold for WT, Y181C, or K103N HIV-1. This compound exhibits excellent preclinical antiviral properties and, as a prodrug designated GW695634, is being developed as a new generation of NNRTI for the treatment of HIV-1 in combination with other antiretroviral agents.

  16. Measurement of urinary biomarkers of parabens, benzophenone-3, and phthalates in a Belgian population.

    Science.gov (United States)

    Dewalque, Lucas; Pirard, Catherine; Charlier, Corinne

    2014-01-01

    Parabens, benzophenone-3 (BP3), and phthalates are commonly used as antimicrobial conservator, UV-filter, and plasticizer, respectively, and are thought to exhibit endocrine disrupting properties. These endocrine disrupting activities have been recently assumed to lead to cutaneous malignant melanoma. Humans are exposed to these chemicals through different sources such as food, personal care products, or cosmetics. In this study, we measured urinary levels of 4 parabens, BP3, and 7 metabolites of phthalates in samples collected from 261 participants living in and around Liege (Belgium). The analyses were carried out by liquid chromatography tandem mass spectrometry (LC-MS/MS) using isotopic dilution. To the best of our knowledge, this is the first time that the urinary levels of these 3 classes of chemicals are reported for the same general population in Belgium. Most of the parabens, the BP3, and all the phthalate metabolites were detected in 82.8 to 100.0% of the samples. For most of these chemicals, the exposure patterns significantly differ not only between children and adults, but also between males and females, especially with higher concentrations of parabens and phthalate metabolites in female and children subjects, respectively.

  17. Measurement of Urinary Biomarkers of Parabens, Benzophenone-3, and Phthalates in a Belgian Population

    Directory of Open Access Journals (Sweden)

    Lucas Dewalque

    2014-01-01

    Full Text Available Parabens, benzophenone-3 (BP3, and phthalates are commonly used as antimicrobial conservator, UV-filter, and plasticizer, respectively, and are thought to exhibit endocrine disrupting properties. These endocrine disrupting activities have been recently assumed to lead to cutaneous malignant melanoma. Humans are exposed to these chemicals through different sources such as food, personal care products, or cosmetics. In this study, we measured urinary levels of 4 parabens, BP3, and 7 metabolites of phthalates in samples collected from 261 participants living in and around Liege (Belgium. The analyses were carried out by liquid chromatography tandem mass spectrometry (LC-MS/MS using isotopic dilution. To the best of our knowledge, this is the first time that the urinary levels of these 3 classes of chemicals are reported for the same general population in Belgium. Most of the parabens, the BP3, and all the phthalate metabolites were detected in 82.8 to 100.0% of the samples. For most of these chemicals, the exposure patterns significantly differ not only between children and adults, but also between males and females, especially with higher concentrations of parabens and phthalate metabolites in female and children subjects, respectively.

  18. Effects of the UV filter benzophenone-2 on reproduction in fish

    International Nuclear Information System (INIS)

    Weisbrod, Christin J.; Kunz, Petra Y.; Zenker, Armin K.; Fent, Karl

    2007-01-01

    The UV filter benzophenone-2 (BP-2) is largely used in personal care products such as cosmetics and in numerous other materials for UV protection. Like other UV filters, BP-2 has been found to be estrogenic in vitro and in vivo, but potential effects on reproduction of fish are unknown. In this study, we evaluate whether BP-2 affects important reproductive parameters such as fecundity, gametogenesis and secondary sex characteristics. After a pre-exposure period of 19 days, reproductively mature fathead minnows (Pimephales promelas) were exposed to 0.002, 0.1, 1.2, 5.0 and 9.7 mg/L BP-2 for 15 days. BP-2 was accumulated in fish up to 3.1 μg/g body weight. In males, a dose-dependent vitellogenin induction and decrease in the number of nuptial tubercles occurred. Moreover, significant dose-related effects on gonads of male and female fish were observed. At concentrations of 1.2 mg/L and higher, spermatocyte and oocyte development was significantly inhibited in male and female fish, respectively. Testes of exposed males had much fewer spermatocytes and ovaries of exposed females had much fewer mature and more atretic follicles. Reproduction was negatively affected in a dose-dependent manner with a decrease in egg production at 5.0 mg/L and a complete cessation of spawning activity at 9.7 mg/L BP-2. Our findings show significant estrogenic effects of the common UV filter BP-2 on vitellogenin induction, secondary sex characteristics, gonadal development, and reproduction in fish

  19. Profiling of benzophenone derivatives using fish and human estrogen receptor-specific in vitro bioassays

    International Nuclear Information System (INIS)

    Molina-Molina, Jose-Manuel; Escande, Aurelie; Pillon, Arnaud; Gomez, Elena; Pakdel, Farzad; Cavailles, Vincent; Olea, Nicolas; Ait-Aissa, Selim; Balaguer, Patrick

    2008-01-01

    Benzophenone (BP) derivatives, BP1 (2,4-dihydroxybenzophenone), BP2 (2,2',4,4'-tetrahydroxybenzophenone), BP3 (2-hydroxy-4-methoxybenzophenone), and THB (2,4,4'-trihydroxybenzophenone) are UV-absorbing chemicals widely used in pharmaceutical, cosmetics, and industrial applications, such as topical sunscreens in lotions and hair sprays to protect skin and hair from UV irradiation. Studies on their endocrine disrupting properties have mostly focused on their interaction with human estrogen receptor alpha (hERα), and there has been no comprehensive analysis of their potency in a system allowing comparison between hERα and hERβ activities. The objective of this study was to provide a comprehensive ER activation profile of BP derivatives using ER from human and fish origin in a battery of in vitro tests, i.e., competitive binding, reporter gene based assays, vitellogenin (Vtg) induction in isolated rainbow trout hepatocytes, and proliferation based assays. The ability to induce human androgen receptor (hAR)-mediated reporter gene expression was also examined. All BP derivatives tested except BP3 were full hERα and hERβ agonists (BP2 > THB > BP1) and displayed a stronger activation of hERβ compared with hERα, the opposite effect to that of estradiol (E 2 ). Unlike E 2 , BPs were more active in rainbow trout ERα (rtERα) than in hERα assay. All four BP derivatives showed anti-androgenic activity (THB > BP2 > BP1 > BP3). Overall, the observed anti-androgenic potencies of BP derivatives, together with their proposed greater effect on ERβ versus ERα activation, support further investigation of their role as endocrine disrupters in humans and wildlife

  20. Kinetics of Chlorination of Benzophenone-3 in the Presence of Bromide and Ammonia.

    Science.gov (United States)

    Abdallah, Pamela; Deborde, Marie; Dossier Berne, Florence; Karpel Vel Leitner, Nathalie

    2015-12-15

    The aim of this study was to assess the impact of chlorination on the degradation of one of the most commonly used UV filters (benzophenone-3 (BP-3)) and the effects of bromide and ammonia on the kinetics of BP-3 elimination. Bromide and ammonia are rapidly converted to bromine and chloramines during chlorination. At first, the rate constants of chlorine, bromine and monochloramine with BP-3 were determined at various pH levels. BP-3 was found to react rapidly with chlorine and bromine, with values of apparent second order rate constants equal to 1.25(±0.14) × 10(3) M(-1)·s(-1) and 4.04(±0.54) × 10(6) M(-1)·s(-1) at pH 8.5 for kChlorine/BP-3 and kBromine/BP-3, respectively, whereas low monochloramine reactivity was observed (kNH2Cl/BP-3 = 0.112 M(-1)·s(-1)). To assess the impact of the inorganic content of water on BP-3 degradation, chlorination experiments with different added concentrations of bromide and/or ammonia were conducted. Under these conditions, BP-3 degradation was found to be enhanced in the presence of bromide due to the formation of bromine, whereas it was inhibited in the presence of ammonia. However, the results obtained were pH dependent. Finally, a kinetic model considering 18 reactions was developed using Copasi to estimate BP-3 degradation during chlorination in the presence of bromide and ammonia.

  1. Toxicokinetics and metabolisms of benzophenone-type UV filters in rats

    International Nuclear Information System (INIS)

    Jeon, Hee-Kyung; Sarma, Sailendra Nath; Kim, Youn-Jung; Ryu, Jae-Chun

    2008-01-01

    Sunscreens containing UV filters are recommended to reduce damage caused by solar UV radiation. Recently, benzophenone (BP)-type UV filters have become widely used as UV stabilizers in skin-moisturizing products and sunscreen lotions; however, very little information is available regarding the potential harmful effects of prolonged exposure to these compounds. Therefore, we investigated the toxicokinetics and metabolism of BP-type UV filters in rats using gas chromatography-mass spectrometry (GC-MS). To examine the metabolism of BP-type UV filters, we analyzed the parent compounds BP and 2-hydroxy-4-methoxybenzophenone (HMB). In rats, BP was mainly converted to benzhydrol (BH) and 4-hydroxybenzophenone (HBP) (i.e., type A UV filters). In contrast, HMB was converted into at least three intermediates, including 2,4-dihydroxybenzophenone (DHB), which was formed via o-demethylation and subsequently converted into 2,3,4-trihydroxybenzophenone (THB), and 2,2'-dihydroxy-4-methoxybenzophenone (DHMB), which formed via the aromatic hydroxylation of HMB (i.e., type B UV filters). Next, the toxicokinetic curve for BP showed a peak concentration (C max ) of 2.06 ± 0.46 μg/ml at approximately 4 h after BP administration. After a single oral dose of HMB, the C max of HMB reached 21.21 ± 11.61 μg/ml within 3 h (T max ), and then declined rapidly compared to the kinetic curve of BP. The concentration of these metabolites in rat blood decreased much more slowly over time compared to the parent compounds. Thus, our results indicate that such metabolites might have more significant adverse effects than the parent compounds over the long term

  2. Synthesis and characterization of new polyimide/organo clay nano composites containing benzophenone moieties in the main chain

    Energy Technology Data Exchange (ETDEWEB)

    Faghihi, K.; Ashouri, M.; Feyzi, A., E-mail: k-faghihi@araku.ac.ir [Arak University, Faculty of Science, Organic Polymer Chemistry Research Laboratory, 38158-879 Arak (Iran, Islamic Republic of)

    2013-08-01

    A series of nano composites consist of organic polyimide and organo-modified clay content varying from 0 to 5 wt %, were successfully prepared by in situ polymerization. Polyimide used as a matrix of nano composite was prepared through the reaction of 1,4-bis [4-aminophenoxy] butane and 3,3,4,4-benzophenone tetra carboxylic dianhydride in N,N-dimethylacetamide (Dmac). The resulting nano composite films were characterized by Ft-IR spectroscopy, X-ray diffraction, scanning electron microscopy and thermogravimetric analysis. (Author)

  3. Synthesis and characterization of new polyimide/organo clay nano composites containing benzophenone moieties in the main chain

    International Nuclear Information System (INIS)

    Faghihi, K.; Ashouri, M.; Feyzi, A.

    2013-01-01

    A series of nano composites consist of organic polyimide and organo-modified clay content varying from 0 to 5 wt %, were successfully prepared by in situ polymerization. Polyimide used as a matrix of nano composite was prepared through the reaction of 1,4-bis [4-aminophenoxy] butane and 3,3,4,4-benzophenone tetra carboxylic dianhydride in N,N-dimethylacetamide (Dmac). The resulting nano composite films were characterized by Ft-IR spectroscopy, X-ray diffraction, scanning electron microscopy and thermogravimetric analysis. (Author)

  4. Ultrasound promoted Barbier reactions and Csp3-Csp2 Stille coupling for the synthesis of diarylmethanes and substituted benzophenones.

    Science.gov (United States)

    Ocampo, Romina A; Koll, Liliana C; Mandolesi, Sandra D

    2013-01-01

    Here we present the preparation of a variety of diarylmethanes obtained via ultrasound Stille coupling under palladium catalysis between some substituted aryl compounds and benzyltributyltin compounds generated through sonicated Barbier reaction in a very short time reaction and excellent yield. The study reported below compares different methods to optimize the synthesis of usually unstable benzyltin derivatives and is another contribution to the investigation of Csp(3)-Csp(2) coupling process involving benzyl-aryl reagents. Substituted carboxylated benzophenones were easily prepared in a very good yield by oxidation of some diarylmethanes. Copyright © 2012 Elsevier B.V. All rights reserved.

  5. Synthesis, characterization and x-ray crystal structure of a dimethyltin (IV) dichloride complex of 2-acetylpyridine benzophenone azine

    International Nuclear Information System (INIS)

    Mustaffa Shamsuddin; Md Abu Affan; Ramli Atan

    1998-01-01

    Dimethyltin dichloride react with 2-ac ethylpyridine benzophenone azine (apba) in refluxing dry hexane to give (SnMe 2 Cl 2 (apba)) where the azine ligand acts as a bidentate N-N chelating ligand. The complex has been characterized by IR spectroscopy, 1 H and 13 C NMR spectroscopic data and elemental analyses. The crystal structure of the dimethyltin(IV) derivative has also been determined. Crystals are monoclinic with space group P2(1)/n with cell dimensions: a = 10.1819(3) Armstrong, b = 18.3113(5) Armstrong, c = 12.6451(4) Armstrong

  6. Characterization of electrogenerated polypyrrole-benzophenone films coated on poly(pyrrole-methyl metacrylate) optic-conductive fibers.

    Science.gov (United States)

    Abu-Rabeah, Khalil; Atias, Danit; Herrmann, Sebastien; Frenkel, Julia; Tavor, Dorith; Cosnier, Serge; Marks, Robert S

    2009-09-01

    A conductive surface was created for the development of a biosensing platform via chemical polymerization of pyrrole onto the surface of poly(methyl methacrylate) (PMMA) fibers, with a subsequent electrogeneration of a photoactive linker pyrrole-benzophenone (PyBz) monomer on the fiber surface. Irradiation of the benzophenone groups embedded in the polypyrrole (Ppy) films by UV (350 nm) formed active radicals, allowing covalent attachment of the desired biomaterials. Characterization and optimization of this platform were carried out, with the platform showing conductive, stable, thin, controllable, and light-transmissible film features. Various parameters such as time deposition, process temperature, and activator plus pyrrole monomer concentrations were examined in the study. The morphology and permeability of the optic-fiber PMMA fibers were investigated to examine mass transfer ability. Cyclic voltammetry and amperometry techniques were applied to characterize the electrical features of the surface and charge transfer. The platform potential was then demonstrated by the construction of both amperometric and optical biosensors.

  7. Thermal Degradation Kinetics Modeling of Benzophenones and Xanthones during High-Temperature Oxidation of Cyclopia genistoides (L.) Vent. Plant Material.

    Science.gov (United States)

    Beelders, Theresa; de Beer, Dalene; Joubert, Elizabeth

    2015-06-10

    Degradation of the major benzophenones, iriflophenone-3-C-glucoside-4-O-glucoside and iriflophenone-3-C-glucoside, and the major xanthones, mangiferin and isomangiferin, of Cyclopia genistoides followed first-order reaction kinetics during high-temperature oxidation of the plant material at 80 and 90 °C. Iriflophenone-3-C-glucoside-4-O-glucoside was shown to be the most thermally stable compound. Isomangiferin was the second most stable compound at 80 °C, while its degradation rate constant was influenced the most by increased temperature. Mangiferin and iriflophenone-3-C-glucoside had comparable degradation rate constants at 80 °C. The thermal degradation kinetic model was subsequently evaluated by subjecting different batches of plant material to oxidative conditions (90 °C/16 h). The model accurately predicted the individual contents of three of the compounds in aqueous extracts prepared from oxidized plant material. The impact of benzophenone and xanthone degradation was reflected in the decreased total antioxidant capacity of the aqueous extracts, as determined using the oxygen radical absorbance capacity and DPPH(•) scavenging assays.

  8. Benzophenone-type UV filters in surface waters: An assessment of profiles and ecological risks in Shanghai, China.

    Science.gov (United States)

    Wu, Ming-Hong; Xie, Deng-Guo; Xu, Gang; Sun, Rui; Xia, Xiao-Yu; Liu, Wen-Long; Tang, Liang

    2017-07-01

    Benzophenone-type UV filters (BP-UV filters) are frequently introduced into aquatic environment from several sources. The occurrence and fate of select BP-UV filters and their metabolites were investigated in this study. All target compounds were detected in water samples, except for 2, 3, 4-trihydroxybenzophenone (2, 3, 4-OH-BP). The concentration reached up 131ngL -1 for 5-benzoyl-4-hydroxy-2-ethoxybenzenesulfonic acid (BP-4), 30.0ngL -1 for 2-hydroxy-4-methoxybenzophenone (BP-3), and mean value of 158ngL -1 for benzophenone (BP). Concentrations of BP-UV filters were not related to recreational waters but with high population frequencies. In addition, five BP-UV filters, namely 2,2',4,4'-tetrahydroxybenzophenone (BP-2), 2,3,4-OH-BP, 2,4-dihydroxybenzophenone (BP-1), 4-hydroxybenzophenone (4-OH-BP) and BP were investigated for probable sources, and found that they originate from BP-3 metabolism. There is a similar source for BP-3, BP-4, BP-1, 4-OH-BP and BP. Environmental risk assessment (ERA) showed that risk quotients (RQs) of BP-4, BP-3 and BP were 2.7, 0.8 and 0.5, respectively. Copyright © 2017 Elsevier Inc. All rights reserved.

  9. Catalytic Oxidation of Benzophenone Hydrazone with Alumina-supported KMnO{sub 4} under Oxygen Atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Kang Hyeok; Ko, Kwang Youn [Ajou University, Suwon (Korea, Republic of)

    2006-02-15

    KMnO{sub 4}/alumina reagent, which is cheap and environmentally safe, can serve as a catalytic oxidant under O{sub 2} atmosphere for the oxidation of benzophenone hydrazone. To the best of our knowledge, the present works are the first example where KMnO{sub 4}/alumina reagent acts as a catalytic oxidant under O{sub 2} atmosphere. Diphenyldiazomethane (Ph{sub 2}CN{sub 2}) is widely used for the protection of carboxylic acids by conversion to their diphenylmethyl (dpm) esters since dpm group can be easily deprotected by mild acidic condition or hydrogenolysis, especially in the field of b-lactams and peptides. Diphenyldiazomethane has been prepared by the oxidation of benzophenone hydrazone with reagents such as active manganese dioxide, mercuric oxide, peracetic acid, iodosobenzene diacetate or OXONE. However, some methods suffer from a disadvantage such as toxic nature of reagent, strong oxidative conditions or incompatibility with certain functional groups. For example, OXONE may not be employed for the in situ protection of carboxylic acid containing sulfide group due to the possibility of the concomitant oxidation of sulfide group.

  10. Urinary concentrations of benzophenone-type ultra violet light filters and reproductive parameters in young men.

    Science.gov (United States)

    Adoamnei, Evdochia; Mendiola, Jaime; Moñino-García, Miriam; Vela-Soria, Fernando; Iribarne-Durán, Luz M; Fernández, Mariana F; Olea, Nicolás; Jørgensen, Niels; Swan, Shanna H; Torres-Cantero, Alberto M

    2018-02-09

    Benzophenone (BP)-type ultraviolet (UV) light filters are chemicals frequently added to personal care products, insect repellents, sunscreens, and beverage and food packaging to diminish the harmful effects of UV sunlight on human skin or foodstuffs. BP-type UV filters have shown negative effects on male reproduction function in in vitro and animal models, but human epidemiologic studies are limited. The goal of this study was to examine associations between urinary concentrations of BP-type UV filters and semen quality and reproductive hormone levels. This is a cross-sectional study with 215 young university students (18-23 years old) recruited between 2010 and 2011 in Southern Spain (Murcia Region). All men provided a urine, blood and semen sample on a single day. Urinary concentrations of 2,4-dihydroxybenzophenone (BP-1); 2,2',4,4'-tetrahydroxybenzophenone (BP-2); 2-hydroxy-4-methoxybenzophenone (BP-3); 2,2'-dihydroxy-4-methoxybenzophenone (BP-8) and 4-hydroxybenzophenone (4OH-BP) were measured by dispersive liquid-liquid microextraction and ultra-high performance liquid chromatography with tandem mass spectrometry detection. Semen quality was evaluated by measuring volume, sperm counts, motility and morphology. Serum samples were analyzed for reproductive hormones, including follicle-stimulating hormone (FSH), luteinizing hormone (LH), testosterone (T), inhibin B and estradiol (E2). Associations between urinary concentrations of BP-type UV filters and semen quality parameters and reproductive hormone levels were examined using linear regression, adjusting for potential confounders. Ninety-seven percent of the men had detectable urinary concentrations of at least one of the five BP-type UV filters quantified. After adjustment for important covariates (body mass index, smoking status and time of blood sample collection), there was a significant positive association between urinary BP-1 and BP-3 concentrations and serum FSH levels (β = 0.08, 95%CI: 0.009; 0

  11. Reaction of benzophenone UV filters in the presence of aqueous chlorine: kinetics and chloroform formation.

    Science.gov (United States)

    Duirk, Stephen E; Bridenstine, David R; Leslie, Daniel C

    2013-02-01

    The transformation of two benzophenone UV filters (Oxybenzone and Dioxybenzone) was examined over the pH range 6-11 in the presence of excess aqueous chlorine. Under these conditions, both UV filters were rapidly transformed by aqueous chlorine just above circumneutral pH while transformation rates were significantly lower near the extremes of the pH range investigated. Observed first-order rate coefficients (k(obs)) were obtained at each pH for aqueous chlorine concentrations ranging from 10 to 75 μM. The k(obs) were used to determine the apparent second-order rate coefficient (k(app)) at each pH investigated as well as determine the reaction order of aqueous chlorine with each UV filter. The reaction of aqueous chlorine with either UV filter was found to be an overall second-order reaction, first-order with respect to each reactant. Assuming elemental stoichiometry described the reaction between aqueous chlorine and each UV filter, models were developed to determine intrinsic rate coefficients (k(int)) from the k(app) as a function of pH for both UV filters. The rate coefficients for the reaction of HOCl with 3-methoxyphenol moieties of oxybenzone (OXY) and dioxybenzone (DiOXY) were k(1,OxY) = 306 ± 81 M⁻¹s⁻¹ and k(1,DiOxY) = 154 ± 76 M⁻¹s⁻¹, respectively. The k(int) for the reaction of aqueous chlorine with the 3-methoxyphenolate forms were orders of magnitude greater than the un-ionized species, k(2,OxY) = 1.03(±0.52) × 10⁶ M⁻¹s⁻¹ and k(2_1,DiOxY) = 4.14(±0.68) × 10⁵ M⁻¹s⁻¹. Also, k(int) for the reaction of aqueous chlorine with the DiOXY ortho-substituted phenolate moiety was k(2_2,DiOxY) = 2.17(±0.30) × 10³ M⁻¹s⁻¹. Finally, chloroform formation potential for OXY and DiOXY was assessed over the pH range 6-10. While chloroform formation decreased as pH increased for OXY, chloroform formation increased as pH increased from 6 to 10 for DiOXY. Ultimate molar yields of chloroform per mole of UV filter were pH dependent

  12. Synthesis and antiproliferative activity of benzophenone tagged pyridine analogues towards activation of caspase activated DNase mediated nuclear fragmentation in Dalton's lymphoma.

    Science.gov (United States)

    Al-Ghorbani, Mohammed; Thirusangu, Prabhu; Gurupadaswamy, H D; Girish, V; Shamanth Neralagundi, H G; Prabhakar, B T; Khanum, Shaukath Ara

    2016-04-01

    A series of benzophenones possessing pyridine nucleus 8a-l were synthesized by multistep reaction sequence and evaluated for antiproliferative activity against DLA cells by in vitro and in vivo studies. The results suggested that, compounds 8b with fluoro group and 8e with chloro substituent at the benzoyl ring of benzophenone scaffold as well as pyridine ring with hydroxy group exhibited significant activity. Further investigation in mouse model suggests that compounds 8b and 8e have the potency to activate caspase activated DNase (endonuclease) which is responsible for DNA fragmentation, a primary hallmark of apoptosis and thereby inhibits the Dalton's lymphoma ascites tumour growth. Copyright © 2016 Elsevier Inc. All rights reserved.

  13. Isolation, structural elucidation, MS profiling, and evaluation of triglyceride accumulation inhibitory effects of benzophenone C-glucosides from leaves of Mangifera indica L.

    Science.gov (United States)

    Zhang, Yi; Han, Lifeng; Ge, Dandan; Liu, Xuefeng; Liu, Erwei; Wu, Chunhua; Gao, Xiumei; Wang, Tao

    2013-02-27

    Seventy percent ethanol-water extract from the leaves of Mangifera indica L. (Anacardiaceae) was found to show an inhibitory effect on triglyceride (TG) accumulation in 3T3-L1 cells. From the active fraction, six new benzophenone C-glucosides, foliamangiferosides A(3) (1), A(4) (2), C(4) (3), C(5) (4), C(6) (5), and C(7) (6) together with 11 known benzophenone C-glucosides (7-17) were obtained. In this paper, isolation, structure elucidation (1-6), and MS fragment cleavage pathways of all 17 isolates were studied. 1-6 showed inhibitory effects on TG and free fatty acid accumulation in 3T3-L1 cells at 10 μM.

  14. Simultaneous determination of some phthalate metabolites, parabens and benzophenone-3 in urine by ultra high pressure liquid chromatography tandem mass spectrometry.

    Science.gov (United States)

    Dewalque, Lucas; Pirard, Catherine; Dubois, Nathalie; Charlier, Corinne

    2014-02-15

    Phthalates, parabens and 2-hydroxy-4-methoxybenzophenone or benzophone-3 are thought to act as endocrine disrupting chemicals, being able to disrupt the endocrine balance and therefore able to lead to some hormonal diseases. Numerous large-scale biomonitoring studies have detected the biomarkers of these compounds in more than 75% of the general population. To assess the exposure to these chemicals, we developed an analytical method based on a Solid Phase Extraction (SPE) prior to ultra high pressure liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) for the simultaneous measurement of seven phthalate metabolites (monobenzyl phthalate, mono-n-butyl phthalate, mono-iso-butyl phthalate, mono-2-ethylhexyl phthalate, mono-2-ethyl-5-hydroxyhexyl phthalate, mono-2-ethyl-5-oxohexyl phthalate, monoethyl phthalate), four parabens (methyl paraben, ethyl paraben, n-propyl paraben, n-butyl parabens) and benzophenone-3 in human urine. The distinction between unconjugated, glucuro- and sulfoconjugated forms was achieved using different enzymatic hydrolyses. The whole procedure was validated according to the total error approach, and was demonstrated to be linear (regression coefficient ranging from 0.987 to 0.998) and accurate (inter and intra assay precision parabens and benzophenone-3 were positively detected in almost all urine samples, with detection rates ranging from 40 to 100%. Levels measured ranged from parabens and benzophenone-3 were detected as glucuro- and sulfoconjugated species in variable proportions according to the target compound. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Preparation and characteristics of a flexible neutron and γ-ray shielding and radiation-resistant material reinforced by benzophenone

    Directory of Open Access Journals (Sweden)

    Pin Gong

    2018-04-01

    Full Text Available With a highly functional methyl vinyl silicone rubber (VMQ matrix and filler materials of B4C, PbO, and benzophenone (BP and through powder surface modification, silicone rubber mixing, and vulcanized molding, a flexible radiation shielding and resistant composite was prepared in the study. The dispersion property of the powder in the matrix filler was improved by powder surface modification. BP was added into the matrix to enhance the radiation resistance performance of the composites. After irradiation, the tensile strength, elongation, and tear strength of the composites decreased, while the Shore hardness of the composites and the crosslinking density of the VMQ matrix increased. Moreover, the composites with BP showed better mechanical properties and smaller crosslinking density than those without BP after irradiation. The initial degradation temperatures of the composites containing BP before and after irradiation were 323.6°C and 335.3°C, respectively. The transmission of neutrons for a 2-mm thick sample was only 0.12 for an Am–Be neutron source. The transmission of γ-rays with energies of 0.662, 1.173, and 1.332 MeV for 2-cm thick samples were 0.7, 0.782, and 0.795, respectively. Keywords: Flexible Composite, Neutron Shielding, Radiation Resistance, γ-ray Shielding

  16. Field-Amplified Sample Injection-Micellar Electrokinetic Chromatography for the Determination of Benzophenones in Food Simulants

    Directory of Open Access Journals (Sweden)

    Cristina Félez

    2015-07-01

    Full Text Available A field-amplified sample injection-micellar electrokinetic chromatography (FASI-MEKC method for the determination of 14 benzophenones (BPs in a food simulant used in migration studies of food packaging materials was developed, allowing almost baseline separation in less than 21 min. The use of a 10 mM sodium dodecyl sulfate (SDS solution as sample matrix was mandatory to achieve FASI enhancement of the analyzed BPs. A 21- to 784-fold sensitivity enhancement was achieved with FASI-MEKC, obtaining limits of detection down to 5.1–68.4 µg/L, with acceptable run-to-run precisions (RSD values lower than 22.3% and accuracy (relative errors lower than 21.0%. Method performance was evaluated by quantifying BPs in the food simulant spiked at 500 µg/L (bellow the established specific migration limit for BP (600 µg/L by EU legislation. For a 95% confidence level, no statistical differences were observed between found and spiked concentrations (probability at the confidence level, p value, of 0.55, showing that the proposed FASI-MEKC method is suitable for the analysis of BPs in food packaging migration studies at the levels established by EU legislation.

  17. C12-Ag wire as solid-phase microextraction fiber for determination of benzophenone ultraviolet filters in river water.

    Science.gov (United States)

    Li, Jian; Ma, Liyun; Tang, Minqiong; Xu, Li

    2013-07-12

    In the present study, a novel approach for fabrication of solid-phase microextraction (SPME) fiber based on silver wire was proposed. 3-(Mercaptopropyl) trimethoxysilane (MPTS) was self-assembled on the silver wire by the special interaction between Ag and S, producing MPTS-Ag wire. The MPTS-Ag wire was then functionalized with dodecyltrimethoxysilane via sol-gel approach, giving C12-Ag wire. The preparation conditions were systematically optimized. The prepared fiber was then used as the SPME fiber to extract three benzophenone UV filters from the river water. The developed method showed good linearity between 0.005 and 0.200 μg mL(-1) with regression determination coefficients in the range of 0.9929-0.9988 and detection limits ranging from 0.58 to 1.86 ng mL(-1). The C12-Ag fiber exhibited good stability and long lifetime, and could be an alternative to the traditional fused silica fiber. Copyright © 2013 Elsevier B.V. All rights reserved.

  18. Novel benzophenone-3 derivatives with promising potential as UV filters: Relationship between structure, photoprotective potential and phototoxicity.

    Science.gov (United States)

    González, María Teresa Páez; Fumagalli, Fernando; Benevenuto, Carolina Gomes; da Silva Emery, Flavio; Gaspar, Lorena Rigo

    2017-04-01

    Benzophenone-3 (BP-3) is a UV filter with absorption at the UVB and UVA wavelengths which has not been extensively studied in experiments involving its absorbing effects and toxicity. We synthetized four BP-3 derivatives and characterized their photoprotective potential by UV absorption and photodegradation, their phototoxicity potential by 3T3 Neutral Red Uptake (3T3 NRU PT) and their photoreactivity by the reactive oxygen species (ROS) assay. The UV absorption, photodegradation, phototoxicity and photoreactivity of the four BP-3 derivatives (BP-3 carbonate, BP-3 carbazole, BP-3 phenylamine and BP-3 methoxy-phenylamine) were evaluated and compared to those of BP-3. Results showed that all derivatives were photostable, except BP-3 carbonate, which did not absorb in the UVA range. BP-3 phenylamine and BP-3 methoxy-phenylamine were considered non-phototoxic and weakly photoreactive in the ROS assay, while the carbazole derivative was considered phototoxic and non-photoreactive due to its rigid structure. The UV spectra of BP-3 carbonate, BP-3 phenylamine and BP-3 methoxy-phenylamine showed the influence of hydrogen bonding on their UV absorption. Based on these results, we concluded that BP-3 phenylamine and BP-3 methoxy-phenylamine could be promising UVA filters. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Benzophenone 1 induced photogenotoxicity and apoptosis via release of cytochrome c and Smac/DIABLO at environmental UV radiation.

    Science.gov (United States)

    Amar, Saroj Kumar; Goyal, Shruti; Dubey, Divya; Srivastav, Ajeet K; Chopra, Deepti; Singh, Jyoti; Shankar, Jai; Chaturvedi, Rajnish K; Ray, Ratan Singh

    2015-12-15

    Solar UV radiation is main factor of photocarcinogenesis, photoageing, and phototoxicity; thus, protection from UV radiation is major concern. Sunscreens containing UV filters are suggested as sun safe practices, but safety of UV filters remains in controversies. Benzophenone-1 (BP1) is commonly used in sunscreens as UV blocker. We assessed the photogenotoxicity and apoptotic parameters in human keratinocytes (HaCaT cells) by western blot, immunocytochemistry, flowcytometry, comet assay and TEM imaging. Our results exposed that BP1 photosensitized and generated intracellular ROS (2.02 folds) under sunlight/UVR. Decrease in cell viability was recorded as 80.06%, 60.98% and 56.24% under sunlight, UVA and UVB, respectively. Genotoxic potential of BP1 was confirmed through photomicronuclei and CPDs formation. BP1 enhanced lipid peroxidation and leakage of LDH enzyme (61.7%). Apoptotic cells were detected by AnnexinV/PI staining and sub G1 population of cell cycle. BP1 induced up regulation of apoptotic proteins Bax/Bcl2 ratio, Apaf-1, cytochrome c, Smac/DIABLO and cleaved caspase 3 was noticed. Down regulation of pro caspase 3 was inhibited by Z-VAD-fmk (inhibitor of caspase). Thus, study established the involvement of BP1 in photogenotoxicity and apoptosis via release of cytochrome c and Smac/DIABLO. These findings suggest sunscreen user to avoid BP1 in cosmetics preparation for its topical application. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  20. Competition between "Meta Effect" Photochemical Reactions of Selected Benzophenone Compounds Having Two Different Substituents at Meta Positions.

    Science.gov (United States)

    Ma, Jiani; Li, Huai; Zhang, Xiting; Tang, Wen-Jian; Li, Mingde; Phillips, David Lee

    2016-10-21

    Recent studies conducted on some "meta effect" photochemical reactions focused on aromatic carbonyls having a substitution on one meta position of the benzophenone (BP) and anthraquinone parent compound. In this paper, two different substitutions were introduced with one at each meta position of the BP parent compound to investigate possible competition between different types of meta effect photochemistry observed in acidic solutions containing water. The photochemical pathways of 3-hydroxymethyl-3'-fluorobenzophenone (1) and 3-fluoro-3'-methylbenzophenone (2) were explored in several solvents, including acidic water-containing solutions, using time-resolved spectroscopic experiments and density functional theory computations. It is observed that 1 can undergo a photoredox reaction and 2 can undergo a meta-methyl deprotonation reaction in acidic water-containing solutions. Comparison of these results to those previously reported for the analogous BP derivatives that contain only one substituent at a meta position indicates the introduction of electron-donating (such as hydroxyl) and electron-withdrawing groups (such as F) on the meta positions of BP can influence the meta effect photochemical reactions. It was found that involvement of an electron-donating moiety facilitates the meta effect photochemical reactions by stabilizing the crucial reactive biradical intermediate associated with the meta effect photochemical reactions.

  1. A fast and simple air-assisted liquid-liquid microextraction procedure for the simultaneous determination of bisphenols, parabens, benzophenones, triclosan, and triclocarban in human urine by liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Rocha, Bruno Alves; de Oliveira, Anderson Rodrigo Moraes; Barbosa, Fernando

    2018-06-01

    The increasing awareness and public concern with hazard exposure to endocrine-disrupting chemicals calls for methods capable to handle numerous samples in short analysis time. In this present study, a novel method combining air-assisted liquid-liquid microextraction and liquid chromatography coupled to mass spectrometry was developed and validated for the extraction, preconcentration, and determination of 7 bisphenols (bisphenol A, bisphenol S, bisphenol AP, bisphenol P, bisphenol F, bisphenol AF, bisphenol Z), 7 parabens (methyl-, ethyl-, propyl-, butyl-, benzyl-paraben, methyl-protocatechuic acid, and ethyl-protocatechuic acid), 5 benzophenones (benzophenone-1, benzophenone-2, benzophenone-3, benzophenone-8, and 4-hydroxybenzophenone), and two antimicrobials (triclosan and triclocarban) in human urine samples. Type and volume of solvent, extraction time (cycles), pH sample, ionic strength, agitation, and needle dimensions were evaluated. The matrix-matched calibration curves of all analytes were linear with correlation coefficients higher than 0.99 in the range level of 1.0-20.0 ng mL -1 . The relative standard deviation, precision, at three concentrations (1.0, 10.0 and 20.0 ng mL -1 ) was lower than 15% with accuracy ranging from 90% to 114%. The biomonitoring capability of the new proposed method was confirmed with the analysis of 50 human urine samples randomly collected from Brazilian children. High urinary concentrations of several EDCs associated with usage of personal care products were found. Copyright © 2018 Elsevier B.V. All rights reserved.

  2. A benzophenone-bearing acid oligodimethacrylate and its application to the preparation of silver/gold nanoparticles/polymer nanocomposites

    International Nuclear Information System (INIS)

    Buruiana, Emil C.; Chibac, Andreea Laura; Buruiana, Tinca; Melinte, Violeta; Balan, Lavinia

    2013-01-01

    The synthesis of photosensitive urethane dimethacrylate that contains poly(ethylene oxide) sequence (PEG, M w : 400), carboxylic and benzophenone moieties, and its characterization by specific methods ( 1 H and 13 C NMR, FTIR, UV and electrospray ionization-mass spectroscopy) are reported. UV curing parameters of this macromer (BP-UDMA) alone and in monomer combinations was evaluated through FTIR spectroscopy and photo-differential scanning calorimetry using 1 wt% 4-(dimethylamino)phenylacetic acid as co-initiator or Irgacure 819 (Irg819). The results show that the photopolymerization rates of the BP-UDMA are higher in the case of Irg819 (R max P : 0.108 s −1 ) due to its synergic action, whereas the degree of conversion of C=C double bond (DC, after 120 s of UV irradiation) is over 77 %. When other co-monomers (non-acid urethane dimethacrylate and silyl urea methacrylate) are incorporated into the formulation, the photopolymerization rate (0.095–0.132 s −1 ) and DC (84.59–79.69 %) varied in reasonable limits. Depending of the photoinitiator type, as well as the monomer composition, the addition of 0.5, 1 and 3 wt% noble metal precursors (AgNO 3 and AuBr 3 ) led to the formation of hybrid composites with in situ-synthesized nanoparticles (NPs), where the variations in the intensity of the surface plasmon absorption bands appeared in the range 400–456 nm (Silver) or 500–553 nm (Gold), better results being obtained in the first initiating system. Homogeneous dispersion of nanoparticles into the polymer matrix was evidenced by EDX and TEM analysis, the last proving the existence of nanoparticles with sizes around 10 nm and variable morphologies. X-ray diffraction analysis complemented these results.

  3. Ultraviolet filters and heat shock proteins: effects in Chironomus riparius by benzophenone-3 and 4-methylbenzylidene camphor.

    Science.gov (United States)

    Martín-Folgar, Raquel; Aquilino, Mónica; Ozáez, Irene; Martínez-Guitarte, José-Luis

    2018-01-01

    Benzophenone-3 (BP3) and 4-methylbenzylidene camphor (4MBC) are common ultraviolet filters (UV filters), compounds considered as emergent contaminants, used in different products like plastics and personal care products. The levels of these compounds are rising in the wild, but the effects they have on invertebrates are poorly understood. Chironomus riparius is a benthic insect widely used in toxicology, and several studies have been previously performed in our laboratory to determine the effects these compounds have on this organism at the molecular level. We have shown that UV filters can alter the mRNA levels of heat shock protein 70 (Hsp70), one of the most studied heat shock proteins. Although these proteins are crucial for the survival of organisms, little data is available on the effects these emergent contaminants have on them, especially in invertebrates. Here, we analyzed the transcriptional activity of 12 genes covering the different groups of heat shock protein [Hsp10, Hsp17, Hsp21, Hsp22, Hsp23, Hsp24, Hsp27, Hsp34, Hsp40, Hsp60, Hsc70 (3), and Hsc70 (4)] in response to 0.1 and 1 mg/L concentrations of BP3 and 4MBC at 8 and 24 h. The results showed that some small Hsp (sHsp) genes were altered by these compounds, while the genes of proteins present in mitochondria, Hsp10 and Hsp60, did not change. sHsps are also involved in developmental processes, so the observed variations could be due to the endocrine disruption activity described for these compounds rather than to a stress response.

  4. Estrogenic potency of benzophenone UV filters in breast cancer cells: proliferative and transcriptional activity substantiated by docking analysis.

    Directory of Open Access Journals (Sweden)

    Gwenneg Kerdivel

    Full Text Available The results from recent studies show that some benzophenones (BPs and their hydroxylated metabolites can function as weak estrogens (E2 in the environment. However, little is known about the structure-activity relationship of these molecules. We have examined the effects of exposure to ten different BPs on the proliferation of estrogen receptor (ER-positive breast cancer cells and on the transcriptional activity of E2-target genes. We analyzed two genes that are tightly linked with estrogen-mediated proliferation, the CXCL12 and amphiregulin genes and two classical estrogen-responsive genes, the pS2 and progesterone receptor. Significant differences in the BPs efficiency to induce cell proliferation and endogenous E2-target gene expressions were observed. Using ERE-, Sp1-, AP1- and C3-reporter genes that contain different ER-binding sites in their promoter, we also showed significant differences in the BPs efficiency in activation of the ER transactivation. Together, our analyzes showed that the most active molecule is 4-hydroxy-BP. Docking analysis of the interaction of BPs in the ligand-binding pocket of ERα suggests that the minimum structural requirement for the estrogenic activity of BPs is a hydroxyl (OH group in the phenyl A-ring that allows interaction with Glu-353, Arg-394 or Phe-404, which enhances the stability between BPs and ERα. Our modeling also indicates a loss of interaction between the OH groups of the phenyl B-ring and His-524. In addition, the presence of some OH groups in the phenyl B-ring can create repulsion forces, which may constrain helix 12 in an unfavorable position, explaining the differential estrogenic effects of BPs. These results, together with our analysis of BPs for their potency in activation of cell proliferation and ER-mediated transcription, report an improved understanding of the mechanism and structure-activity relationship of BPs.

  5. Ecological risk assessment associated to the removal of endocrine-disrupting parabens and benzophenone-4 in wastewater treatment.

    Science.gov (United States)

    Molins-Delgado, Daniel; Díaz-Cruz, M Silvia; Barceló, Damià

    2016-06-05

    The occurrence of four widely used and endocrine disrupting parabens (PBs) (methylparaben, propylparaben, butylparaben and benzylparaben) and a polar UV filter (benzophenone-4) were determined in influent and effluent wastewater from the 19 major wastewater treatment plants (WWTPs) of Catalonia, Spain. For their analysis an on-line solid-phase extraction-liquid chromatography-tandem mass spectrometry (SPE-HPLC-MS/MS) method was developed and validated. Laboratory analysis revealed high levels for both PBs and BP4, with maximum concentrations of 5700ngL(-1) and 1806ngL(-1), respectively, in influent samples, and 137ngL(-1) and 1080ngL(-1), respectively in effluent wastewaters. Removal rates (RE%) for the target compounds in each WWTPs were calculated. RE% for parabens were almost 100%, whereas for BP4 values where in the range 5-91%. The half-life time (t1/2), hydraulic retention time (HRT), and annual mass load (ML) for each facility was estimated. Results indicated that there was no clear influence of HRT on the RE% of BP4. MLs for BP4 were in the range 0.9-110.1kgy(-1), with the highest values in the most populated areas. Finally, a risk assessment, estimated in terms of hazard quotients (HQs), was carried out for aquatic biota. HQs for the target compounds in effluent wastewaters indicated a negligible effect, whereas for some influent wastewaters' HQs pointed out that some species are at risk. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Effect of relative humidity on the migration of benzophenone from paperboard into the food simulant Tenax® and modelling hereof.

    Science.gov (United States)

    Barnkob, L L; Petersen, J H

    2013-01-01

    The aim of this study was to investigate the effect of relative humidity on the migration of benzophenone from paperboard into the food simulant Tenax®. Kinetic migration investigations were carried out with three relative humidities in the interval between 39% and >73%. All investigations were carried out at a constant temperature of 34°C. It was found that the migration of benzophenone after more than 30 days was 4.8 times higher at a relative humidity of 64%-71%, and 7.3 times higher at a relative humidity of >73%, compared with that at a relative humidity of 39%-49%. Diffusion and partition coefficients were derived from the results by using a software for modelling migration in multilayer materials. Both the diffusion coefficient and the partition coefficient, between paperboard and Tenax®, decrease with increasing relative humidity. The experimental results were correctly modelled only when the paperboard was regarded as a one-layer system as compared with a two-layer system: where the main part of the paperboard (B1) has a high diffusion rate and a thin part of the paperboard (B2) in contact with the foodstuff has a lower diffusion rate.

  7. Air-assisted dispersive liquid-liquid microextraction based on a new hydrophobic deep eutectic solvent for the preconcentration of benzophenone-type UV filters from aqueous samples.

    Science.gov (United States)

    Ge, Dandan; Zhang, Yi; Dai, Yixiu; Yang, Shumin

    2017-12-28

    Deep eutectic solvents are considered as new and green solvents that can be widely used in analytical chemistry such as microextraction. In the present work, a new dl-menthol-based hydrophobic deep eutectic solvent was synthesized and used as extraction solvents in an air-assisted dispersive liquid-liquid microextraction method for preconcentration and extraction of benzophenone-type UV filters from aqueous samples followed by high-performance liquid chromatography with diode array detection. In an experiment, the deep eutectic solvent formed by dl-menthol and decanoic acid was added to an aqueous solution containing the UV filters, and then the mixture was sucked up and injected five times by using a glass syringe, and a cloudy state was achieved. After extraction, the solution was centrifuged and the upper phase was subjected to high-performance liquid chromatography for analysis. Various parameters such as the type and volume of the deep eutectic solvent, number of pulling, and pushing cycles, solution pH and salt concentration were investigated and optimized. Under the optimum conditions, the developed method exhibited low limits of detection and limits of quantitation, good linearity, and precision. Finally, the proposed method was successfully applied to determine the benzophenone-type filters in environmental water samples with relative recoveries of 88.8-105.9%. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Quantification of Sunscreen Benzophenone-4 in Hair Shampoos by Hydrophilic Interactions Thin-Layer Chromatography/Densitometry or Derivative UV Spectrophotometry

    Directory of Open Access Journals (Sweden)

    Anna W. Sobańska

    2015-01-01

    Full Text Available Benzophenone-4 (BZ4 was separated from surfactants, dyes, preservatives, and other components of hair shampoos by thin-layer chromatography on silica gel 60 stationary phase, with ethyl acetate-ethanol-water-pH 6 phosphate buffer (15 : 7 : 5 : 1 v/v/v/v as mobile phase. Densitometry scanning of chromatograms was performed at 285 nm. The densitometric calibration curve for BZ4 was nonlinear (second-degree polynomial, with R>0.999. The limits of detection and quantification were ca. 0.03 and ca. 0.1 μg spot−1, respectively. The results obtained by HPTLC-densitometry were compared to those obtained by zero and 2nd derivative UV spectrophotometry. In the case of spectrophotometric methods, calibration curves were linear with R>0.9998. The chromatographic method was fully validated.

  9. Reactions of ligands from BT(B)P family with solvated electrons and benzophenone ketyl radicals in 1-octanol solutions. Pulse radiolysis study

    International Nuclear Information System (INIS)

    Sulich, A.; Grodkowski, J.; Mirkowski, J.; Kocia, R.

    2014-01-01

    Pulse radiolysis involving reactions of solvated electrons and benzophenone ketyl radicals in 1-octanol with selected compounds from bis-triazinyl pyridines and bis-triazinyl bipyridines, BT(B)P family, developed for extraction of trivalent actinides have been studied. The designated ligands were: 2,6-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-benzo-[1,2,4]triazin-3-yl) pyridine, 6,6'-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-benzo-[1,2,4-]triazin-3-yl) -[2,2']bipyridine, 6,6'-bis(5,6-diethyl-[1,2,4]triazin-3-yl)-[2,2']bipyridine and 6,6'-bis(5,6-dipentyl-[1,2,4]triazin-3-yl)-[2,2']bipyridine. Reactions of the ligands with solvated electrons in 1-octanol are fast. The rate constants were determined as equal to: k CyMe4BTP. = (2.4 ± 0.2) × 10 9 dm 3 mol -1 s -1 , k CyMe4BTBP = (1.7 ± 0.3) × 10 9 dm 3 mol -1 s -1 , k C2BTBP = (1.3 ± 0.3) × 10 9 dm 3 mol -1 s -1 and k C5BTBP = (1.7 ± 0.3) × 10 9 dm 3 mol -1 s -1 . Reactions of the ligands with benzophenone ketyl radicals are much slower and the measured rate constants were as follows: k CyMe4BTP = 6.7 × 10 7 dm 3 mol -1 s -1 and k CyMe4BTBP = 3.2 × 10 7 dm 3 mol -1 s -1 . (author)

  10. The UV-filter benzophenone-1 inhibits 17beta-hydroxysteroid dehydrogenase type 3: Virtual screening as a strategy to identify potential endocrine disrupting chemicals.

    Science.gov (United States)

    Nashev, Lyubomir G; Schuster, Daniela; Laggner, Christian; Sodha, Seloni; Langer, Thierry; Wolber, Gerhard; Odermatt, Alex

    2010-04-15

    The prevalence of male reproductive disorders and testicular cancer is steadily increasing. Because the exposure to chemicals disrupting natural hormone action has been associated with these diseases, it is important to identify endocrine disrupting chemicals (EDCs) and their targets of action. Here, a 3D-structural database that can be applied for virtual screening approaches to facilitate the identification of EDCs was constructed. The database was screened using pharmacophores of 17beta-hydroxysteroid dehydrogenase type 3 (17beta-HSD3), which catalyzes the last step of testosterone synthesis in testicular Leydig cells and plays an essential role during male sexual development. Among other chemicals, benzophenone (BP) UV-filters were predicted as potential 17beta-HSD3 inhibitors. Biological analyses revealed (2,4-dihydroxyphenyl)-phenylmethanone (also known as benzophenone-1, BP-1) as an inhibitor of human 17beta-HSD3 (IC(50) 1.05microM). BP-1 also efficiently blocked conversion of androstenedione to testosterone by mouse and rat 17beta-HSD3 in whole-organ enzyme assays. Moreover, BP-1 antagonized the testosterone-dependent activation of androgen receptors (IC(50) 5.7microM), suggesting synergistic anti-androgenic effects of BP-1 by preventing testosterone formation and blocking receptor activation. In addition, analyses of several commonly used UV-filters on estrogen- and androgen-metabolizing 17beta-HSD enzymes revealed 3-benzylidene camphor (3-BC) and 4-methylbenzylidene camphor (4-MBC) as low micromolar 17beta-HSD2 inhibitors. In conclusion, screening of virtual chemical structure libraries can facilitate the identification of compounds interfering with hormone action. The potential disruption of 17beta-HSD enzyme function by the UV-filters BP-1, 3-BC and 4-MBC requires further investigation and should be considered for safety assessment of these chemicals. 2009 Elsevier Inc. All rights reserved.

  11. Self-reported sunscreen use and urinary benzophenone-3 concentrations in the United States: NHANES 2003–2006 and 2009–2012

    International Nuclear Information System (INIS)

    Zamoiski, Rachel D.; Cahoon, Elizabeth K.; Michal Freedman, D.; Linet, Martha S.

    2015-01-01

    Background: Sunscreens protect against skin cancer and other harmful effects of solar ultraviolet radiation (UVR). Epidemiologic and public health surveys often rely on self-reported sunscreen use to estimate sun exposure and avoidance, but questions remain about the validity of self-reports. Benzophenone-3 (BP-3), a common sunscreen ingredient, can be detected in the urine. Prior studies suggest that BP-3 concentrations increase after application of sunscreen. Objectives: The goal of this study was to assess the validity of self-reported frequency of sunscreen use in relation to urinary BP-3 concentrations in a representative sample of the general US population, including in sub-groups defined by age, sex and race/ethnicity. Methods: To assess the relationship between categorical self-reported sunscreen use and creatinine-corrected urinary BP-3 concentrations, we conducted a linear regression adjusted for age, sex, race/ethnicity, six-month time period, body mass index, education, and sun avoidance behaviors. We tested for effect modification by age, sex, ethnicity and time period of measurement using multiplicative interaction terms and a F test. Results: BP-3 was positively associated with self-reported frequency of sunscreen use across all ages, sexes, race/ethnicities, and time periods. Crude and multivariate adjusted models were all statistically significant. R-square was relatively low for all models, ranging from 0.15 to 0.43. Conclusions: Urinary BP-3 is positively associated with self-reported frequency of sunscreen use in the general US population, even in groups with overall low sunscreen use. These results suggest that self-report is a valid, although weak, way of assessing relative frequencies of sunscreen usage in a population-based study. - Highlights: • Urinary benzophenone-3 (BP-3) is a metabolite of a common sunscreen ingredient. • We modeled urinary BP-3 against self-reported sunscreen usage. • We observed a positive association between

  12. Effects of benzophenone-3 exposure on endocrine disruption and reproduction of Japanese medaka (Oryzias latipes)—A two generation exposure study

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Sujin; Jung, Dawoon [School of Public Health, Seoul National University, Seoul 151-742 (Korea, Republic of); Kho, Younglim [Department of Health, Environment and Safety, Eulji University, Seongnam 461-713 (Korea, Republic of); Choi, Kyungho, E-mail: kyungho@snu.ac.kr [School of Public Health, Seoul National University, Seoul 151-742 (Korea, Republic of)

    2014-10-15

    Highlights: • Exposure to BP-3 led to adverse reproduction effects on Japanese medaka at 26 μg/L. • Changes in sex hormones and steroidogenic gene transcription were observed. • Parental exposure to BP-3 influenced on the growth of second generation fish. - Abstract: Benzophenone-3 (BP-3) has been widely used in sunscreens and cosmetics to protect human skin from the harmful effects of UV irradiation. While BP-3 has been frequently detected in surface waters, sediments and biota, only limited information is available on its in vivo toxicity, particularly in fish. In the present study the endocrine disrupting capacity of BP-3 and its underlying mechanisms were investigated using Japanese medaka (Oryzias latipes). Adult Japanese medaka pairs (F0) were exposed to 0, 4.7, 8.4, 26, or 90 μg/L (or 0, 15, 50, 150, or 500 μg/L of BP-3 based on nominal concentration) for 14 d and its effects on sex steroid hormones, and transcription of various associated genes were determined. Following additional 14 d of exposure, the F1 eggs reproduced were counted and were further exposed to 0, 5.4, 12, or 30 μg/L of BP-3 (or 0, 15, 50, or 150 μg/L based on nominal concentrations) until 30 d after hatching. Chemical analysis of the exposed media confirmed transformation of BP-3 to benzophenone-1 (BP-1), a more potent estrogen agonist. After 14 d of the adult fish exposure, plasma concentrations of testosterone (T) significantly increased in male fish. The 17β-estradiol (E2) to T (E2/T) ratio showed significant decreases in both male and female fish. Overall down-regulation of gonadal steroidogenic genes such as star, cyp11a, cyp17, hsd3b, hsd17b3, and cyp19a was also observed. After 28 d of exposure, the daily average egg reproduction per female was significantly reduced at 26 μg/L of BP-3. However, hatchability of F1 eggs was not affected by continuous exposure. After continued exposure until 30 dph, juvenile fish showed concentration-dependent decrease of condition factor

  13. Determination of benzophenones in lipophilic extract of Brazilian red propolis, nanotechnology-based product and porcine skin and mucosa: Analytical and bioanalytical assays.

    Science.gov (United States)

    Fasolo, Daniel; Bergold, Ana Maria; von Poser, Gilsane; Teixeira, Helder Ferreira

    2016-05-30

    Lipophilic compounds of Brazilian Red Propolis (BRP) have received increasing attention due to some interesting findings regarding their biological activities. This study was first aimed at evaluating the chemical composition of BRP n-hexane extract (HEXred) by UPLC-MS-PDA. Chemical investigation mainly resulted in the identification of polyprenylated benzophenones (PPBs) in this extract, named oblongifolin A, guttiferone E, and/or xanthochymol. After that, an isocratic HPLC-UV method was validated for the determination of total content of PPBs (at 260 nm) expressed as garcinol, a commercially available guttiferone E diastereoisomer. The method showed to be specific, precise, accurate, and linear (0.1-10 μg/mL) for the determination of PPBs in HEXred, BRP-loaded nanoemulsions, as well as, in porcine skin and mucosa samples after permeation/retention studies. The matrix effect was determined for all complex matrices, demonstrating low effect during the analysis. The stability-indicating method was verified by submitting HEXred to acidic, alkaline, oxidative, and thermal stress conditions. No interference of degradation products was detected during analysis. Therefore, the proposed analytical and bioanalytical methods proved to be simple and reliable for the determination of PPBs in the presence of different matrices. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Miniaturized hollow fiber assisted liquid-phase microextraction and gas chromatography-mass spectrometry for determination of benzophenone and derivates in human urine sample.

    Science.gov (United States)

    Kawaguchi, Migaku; Ito, Rie; Honda, Hidehiro; Koganei, Youji; Okanouchi, Noriya; Saito, Koichi; Seto, Yasuo; Nakazawa, Hiroyuki

    2009-01-15

    The determination of benzophenones (BPs) in human urine sample by miniaturized hollow fiber assisted liquid-phase microextraction (HF-LPME) and gas chromatography-mass spectrometry (GC-MS) is described. As analytes, BP, its metabolites benzhydrol (BP-OH) and 2-hydroxybenzophenone (2OH-BP), and its derivatives 2-hydroxy-4-methoxybenzophenone (BP-3) and 2-hydroxy-4-methoxy-4'-methylbenzophenone (BP-10) were selected. The detection limit and the quantification limit of BPs in human urine sample are 5-10 and 20-50 pg mL(-1), respectively. The calibration curve for BPs is linear with correlation coefficient higher than 0.99 in the range of 0.02-10 or 0.05-10 ng mL(-1). The average recoveries of BPs in human urine samples spiked with 0.5 and 5 ng mL(-1) BPs are 89.8-100.2% (RSD: 2.5-9.3%) and 89.3-99.9% (RSD: 2.9-3.7%), respectively. Ten human urine samples were analyzed using the present method. BP-OH and BP-3 were detected in all the samples within the range of 0.24-5.91 and 0.43-5.17 ng mL(-1), respectively. This simple, sensitive, and selective analytical method was successfully applied to the determination of trace amounts of BPs in human urine samples.

  15. Simultaneous determination of multiclass preservatives including isothiazolinones and benzophenone-type UV filters in household and personal care products by micellar electrokinetic chromatography.

    Science.gov (United States)

    Lopez-Gazpio, Josu; Garcia-Arrona, Rosa; Millán, Esmeralda

    2015-04-01

    In this work, a simple and reliable micellar electrokinetic chromatography method for the separation and quantification of 14 preservatives, including isothiazolinones, and two benzophenone-type UV filters in household, cosmetic and personal care products was developed. The selected priority compounds are widely used as ingredients in many personal care products, and are included in the European Regulation concerning cosmetic products. The electrophoretic separation parameters were optimized by means of a modified chromatographic response function in combination with an experimental design, namely a central composite design. After optimization of experimental conditions, the BGE selected for the separation of the targets consisted of 60 mM SDS, 18 mM sodium tetraborate, pH 9.4 and 10% v/v methanol. The MEKC method was checked in terms of linearity, LODs and quantification, repeatability, intermediate precision, and accuracy, providing appropriate values (i.e. R(2) ≥ 0.992, repeatability RSD values ˂9%, and accuracy 90-115%). Applicability of the validated method was successfully assessed by quantifying preservatives and UV filters in commercial consumer products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Determination of four paraben-type preservatives and three benzophenone-type ultraviolet light filters in seafoods by LC-QqLIT-MS/MS.

    Science.gov (United States)

    Han, Chao; Xia, Biqi; Chen, Xiangzhun; Shen, Jincan; Miao, Qian; Shen, Yan

    2016-03-01

    For the first time, an efficient and sensitive analytical method based on liquid chromatography-quadrupole linear ion trap-tandem mass spectrometry (LC-QqLIT-MS/MS) was developed for the simultaneous determination of four paraben-type preservatives and three benzophenone-type ultraviolet light filters in both plant (Sargassum fusiforme, porphyra, kelp) and animal (hairtail, yellow croaker, shrimp) seafood. The samples were extracted in methanol by pressurized liquid extraction (PLE), and the extracts were then cleaned up by mixed-mode cationic exchange (MCX) solid-phase extraction cartridges. Both isotope-labeled internal standards and matrix-matched calibration standards were used to alleviate and correct for the matrix effects, and the limits of quantification (LOQs) were 10.0μg kg(-1) for all target compounds. The average recoveries were in the range of 80.6-107.8% at three spiked concentration levels (10, 50 and 100μgkg(-1)) with relative standard deviations (RSDs) below 8.5%. The results suggest that very limited contamination of these seven emerging contaminants, mainly associated with PCPs, occurred in these common seafoods. Copyright © 2015 Elsevier Ltd. All rights reserved.

  17. Optimization of matrix solid-phase dispersion for the rapid determination of salicylate and benzophenone-type UV absorbing substances in marketed fish.

    Science.gov (United States)

    Tsai, Dung-Ying; Chen, Chien-Liang; Ding, Wang-Hsien

    2014-07-01

    A simple and effective method for the rapid determination of five salicylate and benzophenone-type UV absorbing substances in marketed fish is described. The method involves the use of matrix solid-phase dispersion (MSPD) prior to their determination by on-line silylation gas chromatography tandem mass spectrometry (GC-MS/MS). The parameters that affect the extraction efficiency were optimized using a Box-Behnken design method. The optimal extraction conditions involved dispersing 0.5g of freeze-dried powdered fish with 1.0g of Florisil using a mortar and pestle. This blend was then transferred to a solid-phase extraction (SPE) cartridge containing 1.0g of octadecyl bonded silica (C18), as the clean-up co-sorbent. The target analytes were then eluted with 7mL of acetonitrile. The extract was derivatized on-line in the GC injection-port by reaction with a trimethylsilylating (TMS) reagent. The TMS-derivatives were then identified and quantitated by GC-MS/MS. The limits of quantitation (LOQs) were less than 0.1ng/g. Copyright © 2014 Elsevier Ltd. All rights reserved.

  18. Oxidation of purine nucleotides by Triplet 3,3',4,4'-benzophenone tetracarboxylic acid in aqueous solution: pH-dependence.

    Science.gov (United States)

    Saprygina, Natalya N; Morozova, Olga B; Abramova, Tatyana V; Grampp, Günter; Yurkovskaya, Alexandra V

    2014-07-10

    The photo-oxidation of purine nucleotides adenosine-5'-monophosphate (AMP) and guanosine-5'-monophosphate (GMP) by 3,3',4,4'-benzophenone tetracarboxylic acid (TCBP) has been investigated in aqueous solutions using nanosecond laser flash photolysis (LFP) and time-resolved chemically induced dynamic nuclear polarization (CIDNP). The pH dependences of quenching rate constants and of geminate polarization are measured within a wide range of pH values. As a result, the chemical reactivity of reacting species in different protonation states is determined. In acidic solution (pH basic solutions it is significantly lower: kq = 2.6 × 10(8) M(-1) s(-1) (GMP, 4.9 9.4), kq = 1.0 × 10(8) M(-1) s(-1) (AMP, pH > 6.5). Surprisingly, the strong influence of the protonation state of the phosphoric group on the oxidation of adenosine-5'-monophosphate is revealed: the deprotonation of the AMP phosphoric group (6.5) decreases the quenching rate constant from 5.0 × 10(8) M(-1) s(-1) (4.9 6.5).

  19. Cell-specific biotransformation of benzophenone-2 and bisphenol-s in zebrafish and human in vitro models used for toxicity and estrogenicity screening.

    Science.gov (United States)

    Le Fol, Vincent; Aït-Aïssa, Selim; Cabaton, Nicolas; Dolo, Laurence; Grimaldi, Marina; Balaguer, Patrick; Perdu, Elisabeth; Debrauwer, Laurent; Brion, François; Zalko, Daniel

    2015-03-17

    Several human and fish bioassays have been designed to characterize the toxicity and the estrogenic activity of chemicals. However, their biotransformation capability (bioactivation/detoxification processes) is rarely reported, although this can influence the estrogenic potency of test compounds. The fate of two estrogenic chemicals, the UV filter benzophenone-2 (BP2) and the bisphenol A substitute bisphenol S (BPS) was deciphered in eight human and zebrafish in vitro cell models, encompassing hepatic and mammary cellular contexts. BP2 and BPS were metabolized into a variety of gluco- and sulfo-conjugated metabolites. Similar patterns of BP2 and BPS biotransformation were observed among zebrafish models (primary hepatocytes, ZFL and ZELH-zfER cell lines). Interestingly, metabolic patterns in zebrafish models and in the human hepatic cell line HepaRG shared many similarities, while biotransformation rates in cell lines widely used for estrogenicity testing (MELN and T47D-KBLuc) were quantitatively low and qualitatively different. This study provides new data on the comparative metabolism of BP2 and BPS in human and fish cellular models that will help characterize their metabolic capabilities, and underlines the relevance of using in vitro zebrafish-based bioassays when screening for endocrine disrupting chemicals.

  20. A novel approach to bar adsorptive microextraction: Cork as extractor phase for determination of benzophenone, triclocarban and parabens in aqueous samples.

    Science.gov (United States)

    Dias, Adriana Neves; da Silva, Ana Cristine; Simão, Vanessa; Merib, Josias; Carasek, Eduardo

    2015-08-12

    This study describes the use of cork as a new coating for bar adsorptive microextraction (BAμE) and its application in determining benzophenone, triclocarban and parabens in aqueous samples by HPLC-DAD. In this study bars with 7.5 and 15 mm of length were used. The extraction and liquid desorption steps for BAμE were optimized employing multivariate and univariate procedures. The desorption time and solvent used for liquid desorption were optimized by univariate and multivariate studies, respectively. For the extraction step the sample pH was optimized by univariate experiments while the parameters extraction time and ionic strength were evaluated using the Doehlert design. The optimum extraction conditions were sample pH 5.5, NaCl concentration 25% and extraction time 90 min. Liquid desorption was carried out for 30 min with 250 μL (bar length of 15 mm) or 100 μL (bar length of 7.5 mm) of ACN:MeOH (50:50, v/v). The quantification limits varied between 1.6 and 20 μg L(-1) (bar length of 15 mm) and 0.64 and 8 μg L(-1) (bar length of 7.5 mm). The linear correlation coefficients were higher than 0.98 for both bars. The method with 7.5 mm bar length showed recovery values between 65 and 123%. The bar-to-bar reproducibility and the repeatability were lower than 13% (n = 2) and 14% (n = 3), respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. The UV-absorber benzophenone-4 alters transcripts of genes involved in hormonal pathways in zebrafish (Danio rerio) eleuthero-embryos and adult males

    International Nuclear Information System (INIS)

    Zucchi, Sara; Bluethgen, Nancy; Ieronimo, Andrea; Fent, Karl

    2011-01-01

    Benzophenone-4 (BP-4) is frequently used as UV-absorber in cosmetics and materials protection. Despite its frequent detection in the aquatic environment potential effects on aquatic life are unknown. In this study, we evaluate the effects of BP-4 in eleuthero-embryos and in the liver, testis and brain of adult male fish on the transcriptional level by focusing on target genes involved in hormonal pathways to provide a more complete toxicological profile of this important UV-absorber. Eleuthero-embryos and males of zebrafish were exposed up to 3 days after hatching and for 14 days, respectively, to BP-4 concentrations between 30 and 3000 μg/L. In eleuthero-embryos transcripts of vtg1, vtg3, esr1, esr2b, hsd17ss3, cyp19b cyp19a, hhex and pax8 were induced at 3000 μg/L BP-4, which points to a low estrogenic activity and interference with early thyroid development, respectively. In adult males BP-4 displayed multiple effects on gene expression in different tissues. In the liver vtg1, vtg3, esr1 and esr2b were down-regulated, while in the brain, vtg1, vtg3 and cyp19b transcripts were up-regulated. In conclusion, the transcription profile revealed that BP-4 interferes with the expression of genes involved in hormonal pathways and steroidogenesis. The effects of BP-4 differ in life stages and adult tissues and point to an estrogenic activity in eleuthero-embryos and adult brain, and an antiestrogenic activity in the liver. The results indicate that BP-4 interferes with the sex hormone system of fish, which is important for the risk assessment of this UV-absorber.

  2. Widespread occurrence of benzophenone-type UV light filters in personal care products from China and the United States: an assessment of human exposure.

    Science.gov (United States)

    Liao, Chunyang; Kannan, Kurunthachalam

    2014-04-01

    Benzophenone-3 (BP-3) is a sunscreen agent used in a variety of personal care products (PCPs) for the protection of human skin and hair from damage by ultraviolet (UV) radiation. Concerns have been raised over exposure of humans to BP-3, owing to the estrogenic potential of this compound. Nevertheless, the levels and profiles of BP-3 in PCPs and sources of exposure of humans to this estrogenic compound are not well-known. In this study, concentrations of BP-3 were determined in seven categories of 231 PCPs collected from several cities in China (n = 117) and the United States (U.S.) (n = 114), using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). BP-3 was found in the majority (81%) of the samples analyzed, at concentrations as high as 0.148%. The highest BP-3 concentrations (geometric mean [GM]: 548; median: 530 ng/g) were found in skin lotions (including sunscreen lotions), followed by makeup products (284; 221 ng/g). PCPs collected from the U.S. contained higher concentrations of BP-3 than those collected from China. On the basis of the concentrations measured and daily usage rates of PCPs, we estimated the daily intake of BP-3 through dermal absorption from the use of PCPs. The GM and 95th percentile exposure doses to BP-3 were 0.978 and 25.5 μg/day, respectively, for adult women in China, which were 2 orders of magnitude lower than those found for adult women in the U.S. (24.4 and 5160 μg/day). Skin lotions and face creams contributed to the preponderance of daily BP-3 exposures (>80%).

  3. Pollution patterns and underlying relationships of benzophenone-type UV-filters in wastewater treatment plants and their receiving surface water.

    Science.gov (United States)

    Wu, Ming-Hong; Li, Jian; Xu, Gang; Ma, Luo-Dan; Li, Jia-Jun; Li, Jin-Song; Tang, Liang

    2018-05-15

    The environmental behaviors of emerging pollutants, benzophenone-type UV filters (BP-UV filters) and their derivatives were investigated in four wastewater treatment plants (WWTPs), and their receiving surface waters in Shanghai. The concentration level of selected BP-UV filters in the WWTPs was detected from ngL -1 to μgL -1 . BP (621-951ngL -1 ) and BP-3 (841-1.32 × 10 3 ngL -1 ) were the most abundant and highest detection frequency individuals among the target BP-UV filters in influents, whereas BP (198-400ngL -1 ), BP-4 (93.3-288ngL -1 ) and BP-3 (146-258ngL -1 ) were predominant in effluents. BP-UV filters cannot be completely removed and the total removal efficiency varied widely (-456% to 100%) during the treatment process. It can be inferred that the usage of BP and BP-3 are higher than other BP-UV filters in the study area. The lowest and highest levels were BP-2 (ND-7.66ngL -1 ) and BP-3 (68.5-5.01 × 10 3 ng L -1 ) in the receiving surface water, respectively. Interestingly, the seasonal variation of BP-3 is larger than those of other BP-UV filters in surface water from Shanghai. There is no obvious pollution pattern of BP-UV filters in the surface water from the cosmetic factory area. The correlation analysis of BP-UV filters between WWTPs effluents and nearby downstream water samples suggested that BP-UV filters emitted from some WWTPs might be the main source of receiving surface water. Preliminary risk assessment indicated that the levels of BP-UV filters detected by the effluent posed medium to high risk to fish as well as other aquatic organisms. Copyright © 2018 Elsevier Inc. All rights reserved.

  4. Widespread occurrence of bisphenol A diglycidyl ethers, p-hydroxybenzoic acid esters (parabens), benzophenone type-UV filters, triclosan, and triclocarban in human urine from Athens, Greece.

    Science.gov (United States)

    Asimakopoulos, Alexandros G; Thomaidis, Nikolaos S; Kannan, Kurunthachalam

    2014-02-01

    Biomonitoring of human exposure to bisphenol A diglycidyl ethers (BADGEs; resin coating for food cans), p-hydroxybenzoic acid esters (parabens; preservatives), benzophenone-type UV filters (BP-UV filters; sunscreen agents), triclosan (TCS; antimicrobials), and triclocarban (TCC; antimicrobials) has been investigated in western European countries and North America. Nevertheless, little is known about the exposure of Greek populations to these environmental chemicals. In this study, 100 urine samples collected from Athens, Greece, were analyzed by liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) for the determination of total concentrations of five derivatives of BADGEs, six parabens and their metabolite (ethyl-protocatechuate), five derivatives of BP-UV filters, TCS, and TCC. Urinary concentrations of BADGEs, parabens, ethyl-protocatechuate, BP-UV filters, TCS and TCC (on a volume basis) ranged 0.3-20.9 (geometric mean: 0.9), 1.6-1010 (24.2), <2-71.0 (2.1), 0.5-1120 (4.4), <0.5-2580 (8.0) and <0.5-1.9 (0.6) ng/mL, respectively. All 19 target chemicals were found in urine, and the highest detection rates were observed for methyl paraben (100%), bisphenol A bis (2,3-dihydroxypropyl) ether (90%), ethyl paraben (87%), 2,4-dihydroxybenzophenone (78%), propyl paraben (72%), and TCS (71%). Estimated daily intakes (EDIurine), calculated on the basis of the measured urinary concentrations, ranged from 0.023 μg/kg bw/day for Σ5BADGEs to 31.4 μg/kg bw/day for Σ6Parabens. © 2013.

  5. Metabolism of UV-filter benzophenone-3 by rat and human liver microsomes and its effect on endocrine-disrupting activity

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Yoko, E-mail: y-watanabe@nichiyaku.ac.jp [Graduate School of Biomedical and Health Sciences, Hiroshima University, Kasumi 1-2-3, Minami-ku, Hiroshima 734-8553 (Japan); Nihon Pharmaceutical University, Komuro 10281, Ina-machi, Saitama 362-0806 (Japan); Kojima, Hiroyuki; Takeuchi, Shinji [Hokkaido Institute of Public Health, Kita-19, Nishi-12, Kita-ku, Sapporo 060-0819 (Japan); Uramaru, Naoto [Nihon Pharmaceutical University, Komuro 10281, Ina-machi, Saitama 362-0806 (Japan); Sanoh, Seigo [Graduate School of Biomedical and Health Sciences, Hiroshima University, Kasumi 1-2-3, Minami-ku, Hiroshima 734-8553 (Japan); Sugihara, Kazumi [Faculty of Pharmaceutical Science, Hiroshima International University, Koshingai 5-1-1, Kure, Hiroshima 737-0112 (Japan); Kitamura, Shigeyuki [Nihon Pharmaceutical University, Komuro 10281, Ina-machi, Saitama 362-0806 (Japan); Ohta, Shigeru [Graduate School of Biomedical and Health Sciences, Hiroshima University, Kasumi 1-2-3, Minami-ku, Hiroshima 734-8553 (Japan)

    2015-01-15

    Benzophenone-3 (2-hydroxy-4-methoxybenzophenone; BP-3) is widely used as sunscreen for protection of human skin and hair from damage by ultraviolet (UV) radiation. In this study, we examined the metabolism of BP-3 by rat and human liver microsomes, and the estrogenic and anti-androgenic activities of the metabolites. When BP-3 was incubated with rat liver microsomes in the presence of NADPH, 2,4,5-trihydroxybenzophenone (2,4,5-triOH BP) and 3-hydroxylated BP-3 (3-OH BP-3) were newly identified as metabolites, together with previously detected metabolites 5-hydroxylated BP-3 (5-OH BP-3), a 4-desmethylated metabolite (2,4-diOH BP) and 2,3,4-trihydroxybenzophenone (2,3,4-triOH BP). In studies with recombinant rat cytochrome P450, 3-OH BP-3 and 2,4,5-triOH BP were mainly formed by CYP1A1. BP-3 was also metabolized by human liver microsomes and CYP isoforms. In estrogen reporter (ER) assays using estrogen-responsive CHO cells, 2,4-diOH BP exhibited stronger estrogenic activity, 2,3,4-triOH BP exhibited similar activity, and 5-OH BP-3, 2,4,5-triOH BP and 3-OH BP-3 showed lower activity as compared to BP-3. Structural requirements for activity were investigated in a series of 14 BP-3 derivatives. When BP-3 was incubated with liver microsomes from untreated rats or phenobarbital-, 3-methylcholanthrene-, or acetone-treated rats in the presence of NADPH, estrogenic activity was increased. However, liver microsomes from dexamethasone-treated rats showed decreased estrogenic activity due to formation of inactive 5-OH BP-3 and reduced formation of active 2,4-diOH BP. Anti-androgenic activity of BP-3 was decreased after incubation with liver microsomes. - Highlights: • Metabolic modification of the endocrine-disrupting activity of BP-3 was examined. • 2,4,5-TriOH BP and 3-OH BP-3 were identified as new BP-3 metabolites. • 2,4-DiOH BP and 2,3,4-triOH BP exhibited high or similar estrogenic activities. • Estrogenic activity of BP-3 was enhanced by incubation with rat liver

  6. Increased photocatalytic activity of Zn(II)/Cu(II) oxides and sulfides by coupling and supporting them onto clinoptilolite nanoparticles in the degradation of benzophenone aqueous solution.

    Science.gov (United States)

    Esmaili-Hafshejani, Javad; Nezamzadeh-Ejhieh, Alireza

    2016-10-05

    Photocatalytic activity of the coupled ZnO-CuO and ZnS-CuS semiconductors supported onto clinoptilolite nanoparticles (CNP) and micronized one (CMP) was studied in photodegradation of benzophenone (BP) aqueous solution. The ZnO-CuO/CNP (or MCP) and ZnS-CuS/CNP (or MCP) catalysts were prepared via calcination and sulfiding of their Zn(II)-Cu(II) ion-exchanged samples, respectively. XRD patterns confirmed loading of the mentioned semiconductors onto the zeolite, and nano dimension of the catalysts was confirmed by XRD and TEM results. Typical Tauc plots obtained from UV-vis DRS spectra showed red shifts for the band gap energies of the supported coupled semiconductors with respect to the supported monocomponent ones especially for ZnO/NCP and ZnS/NCP catalysts. Also, in both indirect and direct transitions, these red shifts were more considerable in the oxidic systems with respect to the sulfidic systems. Accordingly, the supported oxidic systems showed better photocatalytic activity than the sulfidic one. In the oxidic systems changing the dose of CuO played important role while in the sulfidic systems ZnS played considerable role in the degradation of BP. In the used systems, CuO and ZnS played the main e/h generators in the oxidic and sulfidic systems, respectively, while ZnO and CuS played the preventer e/h recombination. Based on the results, production of e/h is the rate limiting step in the used systems. The maximum degradation activity of the catalysts was obtained at: 0.12gL(-1) of ZnO0.80-CuO3.18/NCP and 0.10gL(-1) of ZnS1.39-CuS2.88/NCP catalysts, initial BP concentration of 30mgL(-1) at pH 7.5. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. Photochemical processes involving the UV absorber benzophenone-4 (2-hydroxy-4-methoxybenzophenone-5-sulphonic acid) in aqueous solution: reaction pathways and implications for surface waters.

    Science.gov (United States)

    De Laurentiis, Elisa; Minella, Marco; Sarakha, Mohamed; Marrese, Alessandro; Minero, Claudio; Mailhot, Gilles; Brigante, Marcello; Vione, Davide

    2013-10-01

    The sunlight filter benzophenone-4 (BP-4) is present in surface waters as two prevailing forms, the singly deprotonated (HA-) and the doubly deprotonated one (A(2-)), with pKa2 = 7.30 ± 0.14 (μ ± σ, by dissociation of the phenolic group). In freshwater environments, BP-4 would mainly undergo degradation by reaction with ·OH and direct photolysis. The form HA(-) has a second-order reaction rate constant with ·OH (k(·OH)) of (1.87 ± 0.31)·10(10) M(-1) s(-1) and direct photolysis quantum yield Φ equal to (3.2 ± 0.6)·10(-5). The form A(2-) has (8.46 ± 0.24)·10(9) M(-1) s(-1) as the reaction rate constant with ·OH and (7.0 ± 1.3)·10(-5) as the photolysis quantum yield. The direct photolysis of HA(-) likely proceeds via homolytic breaking of the O-H bond of the phenolic group to give the corresponding phenoxy radical, as suggested by laser flash photolysis experiments. Photochemical modelling shows that because of more efficient direct photolysis (due to both higher sunlight absorption and higher photolysis quantum yield), the A(2-) form can be degraded up to 3 times faster than HA(-) in surface waters. An exception is represented by low-DOC (dissolved organic carbon) conditions, where the ·OH reaction dominates degradation and the transformation kinetics of HA(-) is faster compared to A(2-). The half-life time of BP-4 in mid-latitude summertime would be in the range of days to weeks, depending on the environmental conditions. BP-4 also reacts with Br2(·-), and a rate constant k(Br2(·-),BP-4) = (8.05 ± 1.33)·10(8) M(-1) s(-1) was measured at pH 7.5. Model results show that reaction with Br2(·-) could be a potentially important transformation pathway of BP-4 in bromide-rich (e.g. seawater) and DOM-rich environments. Copyright © 2013 Elsevier Ltd. All rights reserved.

  8. Systemic absorption of the sunscreens benzophenone-3, octyl-methoxycinnamate, and 3-(4-methyl-benzylidene) camphor after whole-body topical application and reproductive hormone levels in humans

    DEFF Research Database (Denmark)

    Janjua, Nadeem Rezaq; Mogensen, Brian; Andersson, Anna-Maria

    2004-01-01

    Recent in vitro and animal studies have reported estrogen-like activity of chemicals used in sunscreen preparations. We investigated whether the three sunscreens benzophenone-3 (BP-3), octyl-methoxycinnamate (OMC), and 3-(4-methylbenzylidene) camphor (4-MBC) were absorbed and influenced endogenou...... unchanged but minor differences in testosterone levels were observed between the 2 wk. A minor difference in serum estradiol and inhibin B levels were observed in men only. These differences in hormone levels were not related to sunscreen exposure....... reproductive hormone levels in humans after topical application. In this 2-wk single-blinded study 32 healthy volunteers, 15 young males and 17 postmenopausal females, were assigned to daily whole-body topical application of 2 mg per cm(2) of basic cream formulation without (week 1) and with (week 2) the three...

  9. Synthesis and characterization of the 1.1 adducts of copper(1) halides with bidentatate N,N-bis(benzophenone)-1,2-diiminoethane Schiff bases: Crystal structures of [Cu(bz2en)2][CuX2](X=Br,l) complexes

    NARCIS (Netherlands)

    Kia, Reza; Mirkhani, Valiollah; Harkema, Sybolt; van Hummel, G.J.

    2007-01-01

    1:1 adducts of N,N′-bis(benzophenone)-1,2-diiminoethane (bz2en) with copper(I) chloride, bromide and iodide, [Cu(bz2en)2][CuX2] (X = Cl, Br, and I), have been synthesized and the structures of the solid bromide and iodide adducts were determined by X-ray crystallography from single-crystal data. The

  10. Benzophenone-type UV filters in urine and blood from children, adults, and pregnant women in China: Partitioning between blood and urine as well as maternal and fetal cord blood

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Tao; Sun, Hongwen; Qin, Xiaolei [College of Environmental Sciences and Engineering, Ministry of Education Key Laboratory of Pollution Processes and Environmental Criteria, Tianjin Key Laboratory of Environmental Remediation and Pollution Control, Nankai University, Tianjin 300071 (China); Wu, Qian [Wadsworth Center, New York State Department of Health, Albany, NY 12201 (United States); Department of Environmental Health Sciences, School of Public Health, State University of New York at Albany, Albany, NY 12201 (United States); Zhang, Yanfeng [College of Environmental Sciences and Engineering, Ministry of Education Key Laboratory of Pollution Processes and Environmental Criteria, Tianjin Key Laboratory of Environmental Remediation and Pollution Control, Nankai University, Tianjin 300071 (China); Ma, Jing [Applied Radiation Institute, School of Environmental and Chemical Engineering, Shanghai University, 99 Shangda Road, P.O. Box 144, Shanghai 200444 (China); Kannan, Kurunthachalam, E-mail: kkannan@wadsworth.org [Wadsworth Center, New York State Department of Health, Albany, NY 12201 (United States); Department of Environmental Health Sciences, School of Public Health, State University of New York at Albany, Albany, NY 12201 (United States); International Joint Research Center for Persistent Toxic Substances, State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090 (China)

    2013-09-01

    Limited information exists on the exposure of benzophenone (BP)-type UV filters (i.e., sunscreen compounds) in children, adults, and pregnant women in China. In this study, we determined the concentrations of five BP derivatives, BP-1, BP-2, BP-3, BP-8, and 4OH-BP in urine (n = 101) as well as paired specimens of blood and urine (n = 24 pairs) collected from adults; in matched maternal and fetal cord blood (n = 20 pairs) collected from pregnant women; and in blood collected from children (n = 10). 4OH-BP, BP-1, and BP-3 were found in 61%, 57%, and 25%, respectively, of the urine samples analyzed. 4OH-BP was found in all blood samples; BP-3 was found more frequently in the blood of adults (83%), followed, in decreasing order, by pregnant women (35%) and children (30%). Among all adults, urinary BP-3 concentrations were significantly (p < 0.001) positively correlated with urinary BP-1 concentrations. Nevertheless, no significant correlations were found between urinary concentrations of BP-3 (or BP-1) and 4OH-BP. Our results suggest that human exposure to BP-3 and BP-1 is related, whereas 4OH-BP originates from a discrete source. Females had higher urinary concentrations of BP-3, BP-1 and 4OH-BP than males. The distribution profiles of BP-1 and its parent compound (i.e., BP-3) in urine decreased with increasing age of donors (p < 0.05). The ratio of concentrations of BP-3 between blood and urine was 0.21 in adults, which was significantly lower than that for 4OH-BP (0.36). The concentration ratio of BPs between cord blood and maternal blood was higher for 4OH-BP (0.61) than that for BP-3 (0.48), which suggested greater trans-placental transfer potential of 4OH-BP. This is the first study to document the occurrence of BPs in paired urine and blood, and in matched maternal and fetal cord blood. Highlights: • Benzophenone (BP) concentrations are determined in paired blood and urine for the first time. • BP-3 and 4OH-BP partition preferentially into urine. • Cord to

  11. Benzophenone-type UV filters in urine and blood from children, adults, and pregnant women in China: Partitioning between blood and urine as well as maternal and fetal cord blood

    International Nuclear Information System (INIS)

    Zhang, Tao; Sun, Hongwen; Qin, Xiaolei; Wu, Qian; Zhang, Yanfeng; Ma, Jing; Kannan, Kurunthachalam

    2013-01-01

    Limited information exists on the exposure of benzophenone (BP)-type UV filters (i.e., sunscreen compounds) in children, adults, and pregnant women in China. In this study, we determined the concentrations of five BP derivatives, BP-1, BP-2, BP-3, BP-8, and 4OH-BP in urine (n = 101) as well as paired specimens of blood and urine (n = 24 pairs) collected from adults; in matched maternal and fetal cord blood (n = 20 pairs) collected from pregnant women; and in blood collected from children (n = 10). 4OH-BP, BP-1, and BP-3 were found in 61%, 57%, and 25%, respectively, of the urine samples analyzed. 4OH-BP was found in all blood samples; BP-3 was found more frequently in the blood of adults (83%), followed, in decreasing order, by pregnant women (35%) and children (30%). Among all adults, urinary BP-3 concentrations were significantly (p < 0.001) positively correlated with urinary BP-1 concentrations. Nevertheless, no significant correlations were found between urinary concentrations of BP-3 (or BP-1) and 4OH-BP. Our results suggest that human exposure to BP-3 and BP-1 is related, whereas 4OH-BP originates from a discrete source. Females had higher urinary concentrations of BP-3, BP-1 and 4OH-BP than males. The distribution profiles of BP-1 and its parent compound (i.e., BP-3) in urine decreased with increasing age of donors (p < 0.05). The ratio of concentrations of BP-3 between blood and urine was 0.21 in adults, which was significantly lower than that for 4OH-BP (0.36). The concentration ratio of BPs between cord blood and maternal blood was higher for 4OH-BP (0.61) than that for BP-3 (0.48), which suggested greater trans-placental transfer potential of 4OH-BP. This is the first study to document the occurrence of BPs in paired urine and blood, and in matched maternal and fetal cord blood. Highlights: • Benzophenone (BP) concentrations are determined in paired blood and urine for the first time. • BP-3 and 4OH-BP partition preferentially into urine. • Cord to

  12. Benzophenone-type UV filters in urine and blood from children, adults, and pregnant women in China: partitioning between blood and urine as well as maternal and fetal cord blood.

    Science.gov (United States)

    Zhang, Tao; Sun, Hongwen; Qin, Xiaolei; Wu, Qian; Zhang, Yanfeng; Ma, Jing; Kannan, Kurunthachalam

    2013-09-01

    Limited information exists on the exposure of benzophenone (BP)-type UV filters (i.e., sunscreen compounds) in children, adults, and pregnant women in China. In this study, we determined the concentrations of five BP derivatives, BP-1, BP-2, BP-3, BP-8, and 4OH-BP in urine (n=101) as well as paired specimens of blood and urine (n=24 pairs) collected from adults; in matched maternal and fetal cord blood (n=20 pairs) collected from pregnant women; and in blood collected from children (n=10). 4OH-BP, BP-1, and BP-3 were found in 61%, 57%, and 25%, respectively, of the urine samples analyzed. 4OH-BP was found in all blood samples; BP-3 was found more frequently in the blood of adults (83%), followed, in decreasing order, by pregnant women (35%) and children (30%). Among all adults, urinary BP-3 concentrations were significantly (pblood and urine was 0.21 in adults, which was significantly lower than that for 4OH-BP (0.36). The concentration ratio of BPs between cord blood and maternal blood was higher for 4OH-BP (0.61) than that for BP-3 (0.48), which suggested greater trans-placental transfer potential of 4OH-BP. This is the first study to document the occurrence of BPs in paired urine and blood, and in matched maternal and fetal cord blood. Copyright © 2013 Elsevier B.V. All rights reserved.

  13. Solid-Phase Extraction and Reverse-Phase HPLC: Application to Study the Urinary Excretion Pattern of Benzophenone-3 and its Metabolite 2,4-Dihydroxybenzophenone in Human Urine

    Directory of Open Access Journals (Sweden)

    Helena Gonzalez

    2008-01-01

    Full Text Available Background Benzophenone-3 (BZ-3 is a common ultraviolet (UV absorbing compound in sunscreens. It is the most bioavailable species of all UV-absorbing compounds after topical application and can be found in plasma and urine. Objectives The aim of this study was to develop a reverse-phase high performance liquid chromatography (HPLC method for determining the amounts BZ-3 and its metabolite 2,4-dihydroxybenzophenone (DHB in human urine. The method had to be suitable for handling a large number of samples. It also had to be rapid and simple, but still sensitive, accurate and reproducible. The assay was applied to study the urinary excretion pattern after repeated whole-body applications of a commercial sunscreen, containing 4% BZ-3, to 25 healthy volunteers. Methods Each sample was analyzed with regard to both conjugated/non-conjugated BZ-3 and conjugated/non-conjugated DHB, since both BZ-3 and DHB are extensively conjugated in the body. Solid-phase extraction (SPE with C8 columns was followed by reverse-phase HPLC. For separation a Genesis C18 column was used with an acethonitrile-water mobile phase and the UV-detector was set at 287 nm. Results The assay was linear r 2 > 0.99, with detection limits for BZ-3 and DHB of 0.01 µmol L -1 and 0.16 µmol L -1 respectively. Relative standard deviation (RSD was less than 10% for BZ-3 and less than 13% for DHB. The excretion pattern varied among the human volunteers; we discerned different patterns among the individuals. Conclusions The reverse-phase HPLC assay and extraction procedures developed are suitable for use when a large number of samples need to be analyzed and the method fulfilled our objectives. The differences in excretion pattern may be due to differences in enzyme activity but further studies, especially about genetic polymorphism, need to be performed to verify this finding.

  14. Benzophenone-1 stimulated the growth of BG-1 ovarian cancer cells by cell cycle regulation via an estrogen receptor alpha-mediated signaling pathway in cellular and xenograft mouse models

    International Nuclear Information System (INIS)

    Park, Min-Ah; Hwang, Kyung-A; Lee, Hye-Rim; Yi, Bo-Rim; Jeung, Eui-Bae; Choi, Kyung-Chul

    2013-01-01

    Highlights: ► BP-1 induced cell growth was reversed by an ER antagonist in BG-1 cells. ► BP-1 up-regulated the mRNA expression of cyclin D1. ► Up-regulation of cyclin D1 by BP-1 was reversed by an ER antagonist. ► BP-1 is a potential endocrine disruptor that exerts estrogenic effects. - Abstract: 2,4-Dihydroxybenzophenone (benzophenone-1; BP-1) is an UV stabilizer primarily used to prevent polymer degradation and deterioration in quality due to UV irradiation. Recently, BP-1 has been reported to bioaccumulate in human bodies by absorption through the skin and has the potential to induce health problems including endocrine disruption. In the present study, we examined the xenoestrogenic effect of BP-1 on BG-1 human ovarian cancer cells expressing estrogen receptors (ERs) and relevant xenografted animal models in comparison with 17-β estradiol (E2). In in vitro cell viability assay, BP-1 (10 −8 –10 −5 M) significantly increased BG-1 cell growth the way E2 did. The mechanism underlying the BG-1 cell proliferation was proved to be related with the up-regulation of cyclin D1, a cell cycle progressor, by E2 or BP-1. Both BP-1 and E2 induced cell growth and up-regulation of cyclin D1 were reversed by co-treatment with ICI 182,780, an ER antagonist, suggesting that BP-1 may mediate the cancer cell proliferation via an ER-dependent pathway like E2. On the other hand, the expression of p21, a regulator of cell cycle progression at G 1 phase, was not altered by BP-1 though it was down-regulated by E2. In xenograft mouse models transplanted with BG-1 cells, BP-1 or E2 treatment significantly increased the tumor mass formation compared to a vehicle (corn oil) within 8 weeks. In histopathological analysis, the tumor sections of E2 or BP-1 group displayed extensive cell formations with high density and disordered arrangement, which were supported by the increased number of BrdUrd positive nuclei and the over-expression of cyclin D1 protein. Taken together, these

  15. Palladium catalysed asymmetric alkylation of benzophenone Schiff ...

    Indian Academy of Sciences (India)

    Dongdaemun-Gu, Seoul 130-701, Republic of Korea. bDepartment of ..... Anionic effect of imidazolium based ionic liquids in catalytic asymmetric PT alkylationa promoted by palladium catalyst.b. Entry ... d: compared with the run involving catalyst only under similar PT conditions (entry 10, table 1) throw some light in this ...

  16. Dermal Uptake of Benzophenone-3 from Clothing

    DEFF Research Database (Denmark)

    Morrison, Glenn C.; Bekö, Gabriel; Weschler, Charles J.

    2017-01-01

    compartments, including clothing. Given its physical and chemical properties, we hypothesized that dermal uptake from clothing could contribute to the body burden of this compound. First, cotton shirts were exposed to air at an elevated concentration of BP-3 for 32 days; the final air concentration was 4.4 μg....../m3. Next, three participants wore the exposed shirts for 3 h. After 3 h of exposure, participants wore their usual clothing during the collection of urine samples for the next 48 h. Urine was analyzed for BP-3, a metabolite (BP-1), and six other UV filters. The rate of urinary excretion of the sum...... with predictions of steady-state models, suggest that dermal uptake of BP-3 from clothing could meaningfully contribute to overall body burden....

  17. Palladium catalysed asymmetric alkylation of benzophenone Schiff ...

    Indian Academy of Sciences (India)

    transfer catalysts for asym- metric alkylation of achiral Schiff base esters. Trans. Met. Chem. 35 249. (doi:10.1007/s11243-010-9416-4). 29. Wilkes J S 2002 A short history of ionic liquids from molten salts to neoteric solvents. Green Chem. 4 73. 30.

  18. Endocrine-disrupting effect of the ultraviolet filter benzophenone-3 in zebrafish, Danio rerio

    DEFF Research Database (Denmark)

    Kinnberg, Karin Lund; Petersen, Gitte I.; Albrektsen, Mette

    2015-01-01

    of BP-3 in zebrafish (Danio rerio) in the Fish Sexual Development Test (Organisation for Economic Co-operation and Development TG 234) and a 12 day adult male zebrafish study. In TG 234, exposure from 0 to 60 d posthatch caused a monotone dose-dependent skewing of the phenotypic sex ratio towards less...

  19. MAO-A inhibition profiles of some benzophenone glucosides from Gentiana verna subsp. pontica

    DEFF Research Database (Denmark)

    Kaya, Duygu; Jäger, Anna; Yalçin, Funda N

    2014-01-01

    Gentiana verna L. subsp. pontica (Soltok.) Hayek, G. pyrenaica L., and G. verna L. subsp. balcanica Pritchard from Turkey were tested for their MAO-A inhibitory effects. A photometric peroxidase linked MAO-A bioassay performed on the H20 extracts prepared from the methanolic extracts of the title...

  20. New Static Apparatus and Vapor Pressure of Reference Materials: Naphthalene, Benzoic Acid, Benzophenone, and Ferrocene

    Czech Academy of Sciences Publication Activity Database

    Monte, M.J.S.; Santos, L.M.N.F.; Fulem, Michal; Fonseca, J.M.S.; Sousa, C.A.D.

    2006-01-01

    Roč. 51, - (2006), s. 757-766 ISSN 0021-9568 Grant - others:FCT(PT) POCTI/QUI/43144/2001; FEDER(PT) SFRH/ BPD /18065/2004 Institutional research plan: CEZ:AV0Z10100521 Keywords : vapor pressure * reference substance * thermochemistry * construction Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.642, year: 2006

  1. Preparative Isolation and Purification of Five Flavonoid Glycosides and One Benzophenone Galloyl Glycoside from Psidium guajava by High-Speed Counter-Current Chromatography (HSCCC

    Directory of Open Access Journals (Sweden)

    Yindi Zhu

    2013-12-01

    Full Text Available Psidium guajava leaves have a diverse phytochemical composition including flavonoids, phenolics, meroterpenoids and triterpenes, responsible for the biological activities of the medicinal parts. In particular, flavonol glycosides show beneficial effects on type II diabetes mellitus. A simple and efficient HSCCC method has been developed for the preparative separation of five flavonoid glycosides and one diphenylmethane glycoside from P. guajava. A solvent system composed of n-hexane–ethyl acetate–methanol–water (0.7:4:0.8:4, v/v/v/v was optimized for the separation. The upper phase was used as the stationary phase, and the lower phase was used as the mobile phase. Under the optimized conditions, hyperoside (15.3 mg, isoquercitrin (21.1 mg, reynoutrin (65.2 mg, quercetin-3-O-β-D-arabinopyranoside (71.7 mg, quercetin-3-O-α-L-arabinofuranoside (105.6 mg and 2,4,6-trihydroxy-3,5-dimethylbenzophenone 4-O-(6''-O-galloyl-β-D-glucopyranoside (98.4 mg were separated from crude sample (19.8 g. The structures of all the isolates were identified by ESI-MS, 1H- and 13C-NMR analyses and their purities (>95% were determined using HPLC.

  2. Preparative isolation and purification of five flavonoid glycosides and one benzophenone galloyl glycoside from Psidium guajava by high-speed counter-current chromatography (HSCCC).

    Science.gov (United States)

    Zhu, Yindi; Liu, Yue; Zhan, Ying; Liu, Lin; Xu, Yajuan; Xu, Tunhai; Liu, Tonghua

    2013-12-16

    Psidium guajava leaves have a diverse phytochemical composition including flavonoids, phenolics, meroterpenoids and triterpenes, responsible for the biological activities of the medicinal parts. In particular, flavonol glycosides show beneficial effects on type II diabetes mellitus. A simple and efficient HSCCC method has been developed for the preparative separation of five flavonoid glycosides and one diphenylmethane glycoside from P. guajava. A solvent system composed of n-hexane-ethyl acetate-methanol-water (0.7:4:0.8:4, v/v/v/v) was optimized for the separation. The upper phase was used as the stationary phase, and the lower phase was used as the mobile phase. Under the optimized conditions, hyperoside (15.3 mg), isoquercitrin (21.1 mg), reynoutrin (65.2 mg), quercetin-3-O-β-D-arabinopyranoside (71.7 mg), quercetin-3-O-α-L-arabinofuranoside (105.6 mg) and 2,4,6-trihydroxy-3,5-dimethylbenzophenone 4-O-(6''-O-galloyl)-β-D-glucopyranoside (98.4 mg) were separated from crude sample (19.8 g). The structures of all the isolates were identified by ESI-MS, 1H- and 13C-NMR analyses and their purities (>95%) were determined using HPLC.

  3. Development of the larval amphibian growth and development assay: Effects of benzophenone-2 exposure in Xenopus laevis from embryo to juvenile

    Science.gov (United States)

    The Larval Amphibian Growth and Development Assay (LAGDA) is a globally harmonized chemical testing guideline developed by the U.S. Environmental Protection Agency in collaboration with Japan’s Ministry of Environment to support risk assessment. The assay is employed as a ...

  4. The UV-filter benzophenone-1 inhibits 17beta-hydroxysteroid dehydrogenase type 3: Virtual screening as a strategy to identify potential endocrine disrupting chemicals.

    OpenAIRE

    Nashev Lyubomir G; Schuster Daniela; Laggner Christian; Sodha Seloni; Langer Thierry; Wolber Gerhard; Odermatt Alex

    2010-01-01

    The prevalence of male reproductive disorders and testicular cancer is steadily increasing. Because the exposure to chemicals disrupting natural hormone action has been associated with these diseases it is important to identify endocrine disrupting chemicals (EDCs) and their targets of action. Here a 3D structural database that can be applied for virtual screening approaches to facilitate the identification of EDCs was constructed. The database was screened using pharmacophores of 17beta hydr...

  5. Evaluation of the endocrine activity of 2,4,6-tribromophenol, benzanthrone and benzophenone-2 based on Appendix 7.8-5 of REACH guidance document

    DEFF Research Database (Denmark)

    Duis, Karen; Holbech, Henrik; Velasco-Santamaría, Yohana M.

    Within a project funded by the German Federal Environment Agency, the practicability of Appendix 7.8-5 of REACH guidance document R.7b was evaluated using three case study substances. Shortcomings in the guidance were identified. An assessment of potential endocrine activity in aquatic vertebrates......, the main findings and the conclusions with regard to Appendix 7.8-5 are highlighted. (1) For benzanthrone, no binding to the estrogen receptor (ER) is predicted using QSAR methods, but potential metabolites with strong affinity to the ER were identified. At present, the endocrine activity...... of such metabolites is not considered in Appendix 7.8-5. Since many in vitro assays have limited metabolic capacity, this is a shortcoming for substances, for which no in vivo data are available. (2) Reporter gene assays indicate weak ER agonism of benzanthrone; in vitro results on androgen receptor mediated effects...

  6. Synthesis and stereochemical assignments of diastereomeric Ni(II) complexes of glycine Schiff base with (R)-2-(N-{2-[N-alkyl-N-(1-phenylethyl)amino]acetyl}amino)benzophenone; a case of configurationally stable stereogenic nitrogen.

    Science.gov (United States)

    Moriwaki, Hiroki; Resch, Daniel; Li, Hengguang; Ojima, Iwao; Takeda, Ryosuke; Aceña, José Luis; Soloshonok, Vadim A

    2014-01-01

    A family of chiral ligands derived from α-phenylethylamine and 2-aminobenzophenone were prepared by alkylation of the nitrogen atom. Upon reaction with glycine and a Ni(II) salt, these ligands were transformed into diastereomeric complexes, as a result of the configurational stability of the stereogenic nitrogen atom. Different diastereomeric ratios were observed depending on the substituent R introduced in the starting ligand, and stereochemical assignments were based on X-ray analysis, along with NMR studies and optical rotation measurements.

  7. Toxicopathological Effects of the Sunscreen UV Filter, Oxybenzone (Benzophenone-3), on Coral Planulae and Cultured Primary Cells and Its Environmental Contamination in Hawaii and the U.S. Virgin Islands.

    Science.gov (United States)

    Downs, C A; Kramarsky-Winter, Esti; Segal, Roee; Fauth, John; Knutson, Sean; Bronstein, Omri; Ciner, Frederic R; Jeger, Rina; Lichtenfeld, Yona; Woodley, Cheryl M; Pennington, Paul; Cadenas, Kelli; Kushmaro, Ariel; Loya, Yossi

    2016-02-01

    Toxicity persistence to the nontarget amphipod Hyalella curvispina in runoff events following chlorpyrifos applications to soy experimental plots was compared in conventional and no-till management. Two application scenarios were compared: an early-season application with the soil almost bare and a late-season application after the foliage had attained complete soil cover. H. curvispina was exposed to chlorpyrifos using two different test systems: a short-term (48 h) runoff water exposure and a long-term (10 days) soil exposure. Both commonly used crop management practices for soybean production resulted in runoff toxicity following pesticide applications and represent a toxicity risk for adjacent inland waters. Toxicity persistence was longer after the earlier than the late season application, likely because of higher volatilization and photodecomposition losses from the soy canopy than from the soil. For the early-season application, toxicity persisted longer in the no-till plots than in the conventional tillage plots. Suspended matter was higher in the conventional treatment. Chlorpyrifos sorption to suspended matter likely contributed to the shorter persistence. For the late-season application, toxicity persisted longer in the conventional treatment. The causes remain conjectural. The soil organic carbon content was higher in the no-till treatment. Sorption to organic matter might have contributed to the shorter chlorpyrifos toxicity persistence in no-till management. Late applications are more frequent and prevail longer throughout the soy growing season. Overall, the no-till management practice seems preferably because shorter toxicity persistence in runoff represents a lower environmental risk for the adjacent inland waters.

  8. Use of Competition Kinetics with Fast Reactions of Grignard Reagents

    DEFF Research Database (Denmark)

    Holm, Torkil

    2000-01-01

    or effects of polar substituents with isotopically or otherwise substituted benzophenones. A recently reported a-deuterium secondary KIE for the reaction of benzaldehyde with allylmagnesium bromide was observed at -78 °C , but was absent at room temperature. It is suggested that the reaction of benzophenone...

  9. Synthesis, spectroscopy and photochemistry of novel branched fluorescent nitro-stilbene derivatives with benzopheonone groups.

    Science.gov (United States)

    Gao, Fang; Liu, Jian; Peng, Huayong; Hu, Nvdan; Li, Hongru; Zhang, Shengtao

    2010-05-01

    In this article, we presented novel nitro-stilbene derivatives with one or two benzophenone groups as photoinitiators via multi-steps synthesis. The ultraviolet/visible spectroscopy and the emission spectroscopy of the compounds were determined in various solvents. The results showed that the ultraviolet/visible absorption spectroscopy of the derivatives with benzophenone moiety displayed overlap effects of nitro-stilbene and benzophenone parts. In non-polar solvents, the derivatives exhibited strong emission, while they displayed weak emission in modest and strong polar solvents. Dyes-linked benzopheonone groups displayed stronger fluorescence emission than simple chromophore parent molecules. Visible-light photoinitiating effects of the derivatives were investigated extensively. Methyl methacrylate could be photoinitiated efficiently by the derivatives with benzophenone moieties at very low concentration, even at 1 x 10(-5) mol/L. While the photopolymerization efficiency of styrene initiated by the derivatives was lower than that of methyl methacrylate. Our results showed that the dye-linked photoinitators had more efficient photoinitiating than the simple mixture of dye and photoinitator. Furthermore, the derivative with two benzophenone groups displayed more excellent photoiniatiating effects than the derivative with one benzophenone group. Thermodynamics driving for the occurrence of visible-light photoinduced intramolecular electron transfer from chromophore part to benzophenone part was evaluated. Benzopinacol moiety produced in photoreaction was confirmed by nuclear magnetic resonant spectroscopy. Thermal stability of the derivatives was analyzed.

  10. Percolation of triplet excitation in sol-gel matrix

    Science.gov (United States)

    Saha, D. C.; Misra, T. N.

    1996-11-01

    Triplet spectroscopy and energy migration among benzophenone chromophores have been studied in sol-gel matrix under steady state excitation. The energy migration process was observed by the rise of sensitised emission from triplet energy acceptors like, 1,4-dibromonaphthalene and 1-chloronaphthalene after excitation of benzophenone chromophore. The probability of donor excitation energy capture by the trap shows a critical concentration dependence on the benzophenone molecules. The percolation model has been applied to evaluate the critical exponents. The evaluated critical exponents are in very good agreement with three dimensional excitation transport.

  11. FAAS DETERMINATION OF THALLIUM AFTER ...

    African Journals Online (AJOL)

    -S) and tetradecyldimethylbenzylammonium chloride (TDBA) onto benzophenone in the pH range 10.0-11.5 from large volumes of aqueous solutions of various samples. After filtration, each solid mass consisting of thallium complex and ...

  12. Bisphenol A and other phenols in urine from Danish children and adolescents analyzed by isotope diluted TurboFlow-LC-MS/MS

    DEFF Research Database (Denmark)

    Frederiksen, Hanne; Aksglaede, Lise; Sorensen, Kaspar

    2013-01-01

    Bisphenol A (BPA), triclosan (TCS), benzophenone-3 (BP-3), dichoro- and phenyl phenols are industrial chemicals present in numerous consumer products such as polycarbonate plastics, preservatives in personal care products, sun screens, pesticides and fungicides, respectively, and they are all...

  13. Anisotropy of hardness and laser damage threshold of unidirectional organic NLO crystal in relation to the internal structure

    International Nuclear Information System (INIS)

    Natarajan, V.; Arivanandhan, M.; Sankaranarayanan, K.; Hayakawa, Y.

    2011-01-01

    Highlights: · Growth rate of the unidirectional organic crystals were measured and the variation in the growth rate was explained based on the attachment energy model. · Anisotropic behaviors of hardness and laser damage threshold of the unidirectional materials were analyzed. · The obtained results were explained based on the crystal structure of the material. - Abstract: Unidirectional benzophenone crystals were grown along , and directions by uniaxially solution crystallization method at ambient temperature. The growth rate of the grown crystals was varied with orientation. The optical absorption coefficients of benzophenone were measured as a function of wavelength. The optical absorption study reveals that the benzophenone crystal has very low absorption in the wavelength range of interest. Moreover, the laser damage threshold and micro hardness for , and oriented unidirectional benzophenone crystals were measured using a Q-switched Nd:YAG laser operating at 1064 nm radiation and Vicker's micro hardness tester, respectively. The laser damage threshold is larger for the and oriented crystals compared to oriented crystal at 1064 nm wavelength. The result is consistent with the hardness variation observed for the three different crystallographic directions of benzophenone crystal. The relation between the laser damage profile and mechanical hardness anisotropy is discussed based on the crystal structure of benzophenone.

  14. Synthetic ultraviolet light filtering chemical contamination of coastal waters of Virgin Islands National Park, St. John, U.S. Virgin Islands

    Science.gov (United States)

    Bargar, Timothy A.; Alvarez, David; Garrison, Virginia H.

    2015-01-01

    Contamination of surface waters by synthetic ultraviolet light (UV) filtering chemicals is a concern for the Virgin Islands National Park (VINP). Discrete water samples were collected from VINP bays to determine UV filter chemical presence in the coastal waters. Spatial distribution and the potential for partitioning between subsurface waters and the sea surface microlayer (SML) were also examined. The UV filter chemicals 4-methylbenzylidene camphor, benzophenone-3, octinoxate, homosalate, and octocrylene were detected at concentrations up to 6073 ng/L (benzophenone-3). Concentrations for benzophenone-3 and homosalate declined exponentially (r2 = 0.86 to 0.98) with distance from the beach. Limited data indicate that some UV filter chemicals may partition to the SML relative to the subsurface waters. Contamination of VINP coastal waters by UV filter chemicals may be a significant issue, but an improved understanding of the temporal and spatial variability of their concentrations would be necessary to better understand the risk they present.

  15. Influence of substituents of nickel(II) complexes of Schiff bases of substituted (S)-2-N-(benzylpropyl)aminobenzophenones and amino-acids on their asymmetric induction

    International Nuclear Information System (INIS)

    Nadvornik, M.; Lycka, A.; Gee, A.; Popkov, A.

    1999-01-01

    The aim of this work was to study of influence of substituents on benzophenone substituent on thermodynamic controlled induction of complexes as well as influence of substituents on benzyl group and on benzophenone on kinetically controlled asymmetric induction of complexes. [ 13 C]methyl iodide was used in the synthesis. Replace of benzyl group by 2,4,6-trimethylbenzyl group increase kinetically controlled asymmetric induction of synthesis of (S)-α-[ 13 C]methylalanine from 43% d.e. to 66% d.e

  16. Determination of three ultraviolet filters in sunscreen formulations and from skin penetration studies by high-performance liquid chromatography

    Directory of Open Access Journals (Sweden)

    Fernanda Maria Pinto Vilela

    2011-01-01

    Full Text Available An analytical procedure to quantify 3-benzophenone, octylmethoxycinnamate and octylsalicylate was validated and employed to assess these ultraviolet filters in sunscreen formulations and from skin penetration studies. The effect of the vehicle on the skin retention of these filters was investigated. HPLC and extraction procedure were found to be reliable when obtaining data for the sunscreen formulations and for evaluation skin penetration. The results demonstrated that a cream gel generated higher epidermal concentrations of these filters than a lotion or cream-based formulation. Additionally, when comparing the skin retentions of each filter using the same formulation, 3-benzophenone showed the highest skin retention.

  17. High-Performance Nano-Photoinitiators with Improved Safety for 3D Printing.

    Science.gov (United States)

    Han, Yanyang; Wang, Fei; Lim, Chin Yan; Chi, Hong; Chen, Dairong; Wang, FuKe; Jiao, Xiuling

    2017-09-27

    In this work, we report the first hybrid nanosized photoinitiators with low cytotoxicity and migration by coupling of polyhedral oligomeric silsesquioxanes (POSS) to benzophenone derivatives. This new series of photoinitiators were fully characterized and showed many favorable properties such as uniform sizes, extremely low tendency to migrate, less effect on resin viscosity, enhanced thermal stability and mechanical strength, increased photoactivity, and significantly lower cell toxicity compared to their corresponding benzophenone molecules. The utility of these hybrid nanosized photoinitiators in 3D printing was demonstrated in printing of various 3D structures with high resolution and accuracy.

  18. Percolation of triplet excitation in molecularly doped polymer, copolymer and rigid solution matrices

    Science.gov (United States)

    Saha, D. C.; Misra, T. N.; Talukdar, D.

    1999-12-01

    The triplet energy migration in benzophenone and 1,4 dibromonaphthalene doped polystyrene, methylmethacrylate-styrene copolymer and ethanol-methanol rigid glassy solution has been studied under steady state excitation. The probability of donor excitation energy capture by the traps shows a critical concentration dependence on benzophenone molecules. The percolation model has been successfully applied to evaluate the critical exponents. It is observed that in rigid glassy solution and in polystyrene matrices a three-dimensional triplet excitation migration topology is observed, whereas in copolymer matrix it is two-dimensional.

  19. I:\\AA-TYPESET\\CHEM\\2009\\Janse van Rensburg.vp

    African Journals Online (AJOL)

    NJD

    examine the actual influences and reason for this rotation. The bulk of research in this area has been .... was distilled over sodium metal/benzophenone under a nitrogen atmosphere prior to use, and stored over 3 Е .... liquid, which could not be recrystallized or purified due to its tackiness. 1H NMR (500 MHz, CDCl3) δ ...

  20. Fulltext PDF

    Indian Academy of Sciences (India)

    compound formed from μ1,1-azido clipping of two methoxido bridged [Cu2] complexes showing asymmetric coordination from benzophenone oxygen atoms and terminal azido groups. Keywords. Tetranuclear copper(II); azido; methoxido; phenoxido; X-ray structure; rhombiodal. 1. Introduction. In recent years, the utilization ...

  1. Synthesis and complexation characteristics of phenanthroline and bipyridine diols

    NARCIS (Netherlands)

    Koning, B.; Boer, J.W. de; Meetsma, A.; Kellogg, R.M.

    2004-01-01

    Neocuproine (2,9-dimethyl-1,10-phenanthroline) 1 was converted to achiral and chiral tetradentate phenanthroline diols 3a-c by addition to benzophenone, adamantanone and camphor, respectively. Analogously 6,6'-dimethyl-2,2'-bipyridine 2 was converted to diol 7a on base-induced addition to

  2. Intramolecular Charge Transfer of Conjugated Liquid Crystal Ferrocene Macromolecules - Synthesis and Characterization

    Science.gov (United States)

    2016-04-12

    properties are of interest because polarized light emitters or light absorption devices, such as OLEDS, solar cells or wave guides, filters and Faraday... distilled from KOH, THF (Aldrich) was also first distilled from KOH and then from sodium benzophenone until the typical blue complex was formed. All

  3. Vertical flow soil filter for the elimination of micro pollutants from storm and waste water

    DEFF Research Database (Denmark)

    Janzen, Niklas; Banzhaf, Stefan; Scheytt, Traugott

    2009-01-01

    ) to prevent clogging and was spiked with activated sludge to enhance microbial biomass and biodegradation potential. Compounds used as UV filters, antioxidants or plasticizers, namely 4-methylbenzylidene camphor (4-MBC), benzophenone-3 (BP-3), butylated hydroxytoluene (BHT), N-butylbenzenesulfonamide (NBBS...

  4. Structure and spectra of photochemically obtained nanosized silver particles in presence of modified porous silica

    OpenAIRE

    Galina Krylova; Anna Eremenko; Natalia Smirnova; Susie Eustis

    2005-01-01

    Mesoporous silica powders and films modified with organic sensitizer benzophenone were used as photocatalysts in the reaction of silver ion reduction by isopropyl alcohol under UV-irradiation with λ= 253.7 nm and 365 nm in presence of colloidal silica as stabilizer. Morphological changes of silver colloids during irradiation were studied using transmission electron microscopy, and correlated to the absorption spectra.

  5. Direct site-directed photocoupling of proteins onto surfaces coated with β-cyclodextrins

    DEFF Research Database (Denmark)

    Städe, Lars W; Wimmer, Reinhard; Stensballe, Allan

    2010-01-01

    . Insertion of pBpa was verified by matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectroscopy. A molecular dynamic simulation, with water as solvent, showed high solvent accessibility of the pBpa benzophenone group in N27pBpa-cutinase mutant. The formation of an inclusion...

  6. Bulletin of the Chemical Society of Ethiopia - Vol 19, No 1 (2005)

    African Journals Online (AJOL)

    FAAS DETERMINATION OF THALLIUM AFTER PRECONCENTRATION USING NITROSO-S AND TDBA ONTO BENZOPHENONE · EMAIL FREE FULL TEXT EMAIL FREE FULL TEXT · DOWNLOAD FULL TEXT DOWNLOAD FULL TEXT. Mohammad Ali Taher*, Sayed Ziae Mohammadi Mobarakeh, Fatameh Saber Mahani ...

  7. MIS-based sensors with hydrogen selectivity

    Science.gov (United States)

    Li,; Dongmei, [Boulder, CO; Medlin, J William [Boulder, CO; McDaniel, Anthony H [Livermore, CA; Bastasz, Robert J [Livermore, CA

    2008-03-11

    The invention provides hydrogen selective metal-insulator-semiconductor sensors which include a layer of hydrogen selective material. The hydrogen selective material can be polyimide layer having a thickness between 200 and 800 nm. Suitable polyimide materials include reaction products of benzophenone tetracarboxylic dianhydride 4,4-oxydianiline m-phenylene diamine and other structurally similar materials.

  8. New Metallic Oxide Electrodes for the Deposition of Functionalised Polymers

    Directory of Open Access Journals (Sweden)

    Grégoire Herzog

    2006-02-01

    Full Text Available This article explores the possibilities of using Sb doped SnO2 thin films as potential electrode substrates for biosensors. Two series of electrodes were modified with electrogenerated functionalised polymeric films. The polymers investigated were biotinylated poly(ruthenium pyrrole and poly(pyrrole benzophenone. AFM studies show polymer morphologies depending on the nature and roughness of the substrates.

  9. Synthesis of (R)-(-)-2-fluoronorapomorphine - A precursor for the synthesis of (R)-(-)-2-fluoro-N-[C]propylnorapomorphine for evaluation as a dopamine D agonist ligand for PET investigations

    DEFF Research Database (Denmark)

    Søndergaard, Kåre; Kristensen, Jesper Langgaard; Gillings, Nic

    2005-01-01

    of the triflate to the corresponding N-substituted benzophenone imine. After acidic hydrolysis the resulting aniline was transformed into the 2-fluoro compound via the Balz-Schiemann reaction. Hydrogenolysis of the N-benzyl group followed by deprotection of the catechol moiety using BBr provided 2...

  10. Bulletin of the Chemical Society of Ethiopia - Vol 20, No 2 (2006)

    African Journals Online (AJOL)

    Antioxidant benzophenones and xanthones from the root bark of Garcinia smeathmannii · EMAIL FREE FULL TEXT EMAIL FREE FULL TEXT DOWNLOAD FULL TEXT DOWNLOAD FULL TEXT. Alain Meli Lannang, Justin Komguem, Fernande Ngounou Ngninzeko, Jean Gustave Tangmouo, David Lontsi, Asma Ajaz, ...

  11. Nickel-Catalyzed Synthesis of Primary Aryl and Heteroaryl Amines via C–O Bond Cleavage

    KAUST Repository

    Yue, Huifeng

    2017-03-13

    A nickel-catalyzed protocol for the conversion of aryl and heteroaryl alcohol derivatives to primary and secondary aromatic amines via C(sp2)-O bond cleavage is described. The new amination protocol can be applied to a range of substrates bearing diverse functional groups and uses readily available benzophenone imines as an effective nitrogen source.

  12. Chemoselective C-benzoylation of phenols by using AlCl3 under ...

    African Journals Online (AJOL)

    Substituted phenols were chemo-selectively reacted with benzoylchloride in presence of aluminum chloride under solvent-free condition to afford the corresponding 2'-hydroxy aryl benzophenones in excellent yields (72-96%). Naphthol benzoylation resulted in lower yields as compared to phenols. Both reactions ...

  13. On the timing characteristics of low-yield fast scintillators

    International Nuclear Information System (INIS)

    Galligaris, F.; Ciuti, P.; Gabrielli, I.; Giacomich, R.

    1980-01-01

    The timing characteristics of Ne 111 scintillator quenched with 3% of benzophenone have been studied by the single photon counting technique. Its performances have been compared with the measured characteristics of unquenched Ne 111, PILOT U and NE 104 and with the data available in the literature. (orig.)

  14. Sunscreens in human plasma and urine after repeated whole-body topical application

    DEFF Research Database (Denmark)

    Janjua, N.R.; Kongshoj, B.; Andersson, A.M.

    2008-01-01

    Background The three chemical ultraviolet absorbers benzophenone-3 (BP-3), octyl-methoxycinnamate (OMC) and 3-(4-methylbenzylidene) camphor (4-MBC) are commercially used in sunscreens worldwide. Apart from sun protection, they may possess endocrine-disrupting effects in animals and in vitro...

  15. Sunscreens in human plasma and urine after repeated whole-body topical application

    DEFF Research Database (Denmark)

    Janjua, N R; Kongshoj, B; Andersson, A-M

    2008-01-01

    The three chemical ultraviolet absorbers benzophenone-3 (BP-3), octyl-methoxycinnamate (OMC) and 3-(4-methylbenzylidene) camphor (4-MBC) are commercially used in sunscreens worldwide. Apart from sun protection, they may possess endocrine-disrupting effects in animals and in vitro. For all three...

  16. Dae Hyun Kim

    Indian Academy of Sciences (India)

    Dae Hyun Kim. Articles written in Journal of Chemical Sciences. Volume 123 Issue 4 July 2011 pp 467-476. Palladium catalysed asymmetric alkylation of benzophenone Schiff base glycine esters in ionic liquids · Dae Hyun Kim Jin Kyu Im Dae Won Kim Minserk Cheong Hoon Sik Kim Deb Kumar Mukherjee · More Details ...

  17. GAS-LIQUID SOLUBILITIES OF THE METHANOL SYNTHESIS COMPONENTS IN VARIOUS SOLVENTS

    NARCIS (Netherlands)

    GRAAF, GH; SMIT, HJ; STAMHULS, EJ; BEENACKERS, AACM

    The solubilities of CO, CO2, H-2, CH3OH, and H2O were measured in hexadecane, octadecane, squalane, and benzophenone at 293-573 K and 1.013-90 bar using volume displacement and material balance techniques. The experimental results, consisting of 260 solubility data for 16 binary mixtures, were used

  18. Isolation and characterization of microsatellite markers in Garcinia ...

    Indian Academy of Sciences (India)

    K. V. RAVISHANKAR

    Abstract. Garcinia gummi-gutta (L.) Roxb. (Clusiaceae) is an endemic, semidomesticated, fruit-yielding tree species distributed in the. Western Ghats of India and Sri Lanka. Various bioactive phytochemicals, such as garcinol, benzophenones and xanthones are isolated from G. gummi-gutta and have shown antibacterial, ...

  19. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Asymmetric alkyl substitution of various benzophenone Schiff base substrates under biphasic conditions proceeded using optically active Palladium(II) complexes. The corresponding products were obtained in high yields but with moderate enantiomeric excess (ee). Addition of specific ionic liquids to the reaction medium ...

  20. Evaluation of the migration of 15 photo-initiators from cardboard packaging into Tenax(®) using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS).

    Science.gov (United States)

    Van Den Houwe, K; van de Velde, S; Evrard, C; Van Hoeck, E; Van Loco, J; Bolle, F

    2014-04-01

    Photo-initiators are widely used to cure ink on packaging materials used in food applications such as plastic films or cartonboards. In migration studies, food simulants are very often used to simulate food, like Tenax(®), which is the simulant for dry foodstuffs. In this paper a fast and reliable confirmation method for the determination of the following photo-initiators in Tenax(®) is described: benzophenone (BP), 4,4'-bis(diethylamino)benzophenone (DEAB), 2-chloro-9H-thioxanthen-9-one (CTX), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX), 2,4-diethyl-9H-thioxanthen-9-one (DETX), 2,2-dimethoxy-2-phenyl acetophenone (DMPA), 4-(dimethylamino)benzophenone (DMBP), 2-ethylanthraquinone (EA), ethyl-4-dimethylaminobenzoate (EDMAB), 1-hydroxylcyclohexyl phenyl ketone (HCPK), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone (HMMP), 2-isopropyl-9H-thioxanthen-9-one (ITX), 4-methylbenzophenone (MBP), Michler's ketone (MK), and 4-phenylbenzophenone (PBZ). After the migration study was completed, the simulant Tenax(®) was extracted using acetonitrile, followed by analysis on ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Quantification was carried out using benzophenone-d10 (BP-d10) as internal standard. The presented method is validated in terms of matrix effect, specificity, linearity, recovery, precision and sensitivity, showing the method can detect all photo-initiators at very low concentrations (LOD < 0.125 µg g(-1) for all substances). Finally, the procedure was applied to real samples, proving the capabilities of the presented method.

  1. Exposure to UV filters during summer and winter in Danish kindergarten children.

    Science.gov (United States)

    Krause, Marianna; Andersson, Anna-Maria; Skakkebaek, Niels E; Frederiksen, Hanne

    2017-02-01

    Ultra violet (UV) filters with known or suspected endocrine disrupting properties are widely used in sunscreens and other personal care products, clothing, food packaging and many other consumer products. Danish kindergarten children have sunscreens applied daily during summer to prevent skin burns. To estimate the assumed contribution of sunscreens to the total exposure to UV filters, we measured the urinary excretion of UV filters during summer and winter in kindergarten children. Spot- and first morning urines were collected during a summer and a winter day in 2013. A total of 266 urine samples were collected from 55 children and were analysed for content of benzophenone (BP), benzophenone-1 (BP-1), benzophenone-2 (BP-2), benzophenone-3 (BP-3), 5-chloro-2-hydroxybenzophenone (BP-7), 4-methyl-benzophenone (4-MBP), 4-hydroxybenzophenone (4-HBP), 3-(4-methylbenzylidene)-camphor (4-MBC), and 3-benzylidene camphor (3-BC) by LC-MS/MS. Of the analysed UV filters, the children excreted predominantly BP-1, BP-3 and 4-HBP. The urine levels were significantly higher in summer samples compared to winter samples, however exposure during winter was still evident. Furthermore, children with the highest concentrations of UV filters in summer urines also tended to be among those with the highest winter levels. Exposures to UV filters during summertime can partly be explained by the intended use of UV filters in sunscreens, which is considered to be beneficial for children during outdoor activities. However, exposure to UV filters all year round together with large inter-individual variation indicate that children's exposure to UV filters also comes from other consumer items, presumably highly influenced by the general lifestyle of an individual child: this is completely unintended, without benefit, and potentially harmful. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. Concentrations of Environmental Phenols and Parabens in Milk, Urine and Serum of Lactating North Carolina Women

    Science.gov (United States)

    Hines, Erin P.; Mendola, Pauline; vonEhrenstein, Ondine S.; Ye, Xiaoyun; Calafat, Antonia M.; Fenton, Suzanne E.

    2015-01-01

    Phenols and parabens show some evidence for endocrine disruption in laboratory animals. The goal of the Methods Advancement for Milk Analysis (MAMA) Study was to develop or adapt methods to measure parabens (methyl, ethyl, butyl, propyl) and phenols (bisphenol A (BPA), 2,4- and 2,5-dichlorophenol, benzophenone-3, triclosan) in urine, milk and serum twice during lactation, to compare concentrations across matrices and with endogenous biomarkers among 34 North Carolina women. These non-persistent chemicals were detected in most urine samples (53-100%) and less frequently in milk or serum; concentrations differed by matrix. Although urinary parabens, triclosan and dichlorophenols concentrations correlated significantly at two time points, those of BPA and benzophenone-3 did not, suggesting considerable variability in those exposures. These pilot data suggest that nursing mothers are exposed to phenols and parabens; urine is the best measurement matrix; and correlations between chemical and endogenous immune-related biomarkers merit further investigation. PMID:25463527

  3. [n-Butyl Alcohol-soluble Chemical Constituents of Psidium guajava Leaves].

    Science.gov (United States)

    Chen, Gang; Wan, Kai-hua; Fu, Hui-zheng; Yan, Qing-wei

    2015-03-01

    To study the chemical constituents of the leaves of Psidium guajava. The chemical constituents were isolated by column chromatography on silica gel, Sephadex LH-20 and MPLC. Their chemical structures were elucidated on the basis of special analysis. Seven compounds were isolated from n-butyl alcohol fraction, whose structures were elucidated as morin-3-O-α-L-arabopyranoside (1), morin-3-O-α-L-iyxopyranoside (2), 2,6-dihydroxy-4-O-β-D-glucopyranosyl-benzophenone (3), casuarictin (4),2,6-dihydroxy-3,5-dimethyl-4-O-(6"-O-galloyl-β-D-glucopyranosyl)-benzophenone(5), globulusin A(6), and kaempferol-3-O-β-D-(6"-galloyl) galactopyranoside (7). Compounds 3 and 5 ~ 7 are isolated from this plant for the first time.

  4. One new diphenylmethane glycoside from the leaves of Psidium guajava L.

    Science.gov (United States)

    Shu, Ji-Cheng; Chou, Gui-Xin; Wang, Zheng-Tao

    2012-11-01

    To investigate the chemical constituents of Psidium guajava L, the EtOH/H(2)O extract of the fresh leaves was subjected to various chromatography. One diphenylmethane, one benzophenone, and eight flavonoids were isolated and elucidated as 2,6-dihydroxy-3-formaldehyde-5-methyl-4-O-(6″-O-galloyl-β-D-glucopyranosyl)-diphenylmethane (1), 2,6-dihydroxy-3,5-dimethyl-4-O-(6″-O-galloyl-β-D-glucopyranosyl)-benzophenone (2), kaempferol (3), quercetin (4), quercitrin (5), isoquercitrin (6), guaijaverin (7), avicularin (8), hyperoside (9), reynoutrin (10) by spectroscopic methods, including 1D and 2D NMR and HR-ESI-MS spectrometry as well as by comparison with published data. Compounds 5 and 10 are obtained from P. guajava for the first time, and compound 1 is a new diphenylmethane compound.

  5. Determination of the UV filters worldwide authorised in sunscreens by high-performance liquid chromatography. Use of cyclodextrins as mobile phase modifier.

    Science.gov (United States)

    Chisvert, A; Pascual-Martí, M C; Salvador, A

    2001-07-06

    Simultaneous determination of organic UV filters worldwide authorised in sunscreen formulations was performed by HPLC with UV spectrophotometric detection. The filters determined were: benzophenone-4, benzophenone-3, butyl methoxydibenzoylmethane, octyl dimethyl PABA, octyl methoxycinnamate, homosalate and octyl salicylate. A C18 stationary phase and an isocratic mobile phase of ethanol-water-acetic acid (70:29.5:0.5) containing 65.4 mM of hydroxypropyl-beta-cyclodextrin, were used with a flow-rate of 0.6 ml/min. UV measurements were carried out at 313 nm. The time required for the analysis was 20 min and the limits of detection were between 1.5 and 2.3 mg/l. The procedure proposed provides a green analytical method with a basic instrumental configuration, it is fast and accurate and does not involve highly toxic organic solvents.

  6. Personal care products in surface, ground and wastewater of a complex aquifer system, a potential planning tool for contemporary urban settings.

    Science.gov (United States)

    Palmiotto, Marinella; Castiglioni, Sara; Zuccato, Ettore; Manenti, Angela; Riva, Francesco; Davoli, Enrico

    2018-05-15

    The use and discharge of personal care products (PCPs) result in their presence in the aquatic environment. This study investigates the occurrence and fate of some PCPs in wastewater, surface and groundwater in an urbanized area in the North of Italy. We investigated four UV filters: phenylbenzimidazole sulfonic acid (PBSA), benzophenone-3 (BP3), benzophenone-4 (BP4) and 4 methyl-benzilidine-camphor (4-MBC), and two antibacterial agents: triclosan (TCS) and triclocarban (TCC). BP3, BP4 and PBSA were detected in all WWTPs and concentrations ranged 27-822 ng/L (BP4 > PBSA > BP3). TCS was the only disinfectant detected in wastewater and ranged from urban trends and suggesting paths for the planning in urban regions and for appropriate investment and rehabilitation strategies of infrastructure. Copyright © 2018 Elsevier Ltd. All rights reserved.

  7. Complexity generation in fungal polyketide biosynthesis: a spirocycle-forming P450 in the concise pathway to the antifungal drug griseofulvin.

    Science.gov (United States)

    Cacho, Ralph A; Chooi, Yit-Heng; Zhou, Hui; Tang, Yi

    2013-10-18

    Griseofulvin (1) is a spirocyclic fungal natural product used in treatment of fungal dermatophytes. Formation of the spirocycle, or the grisan scaffold, from a benzophenone precursor is critical for the activity of 1. In this study, we have systematically characterized each of the biosynthetic enzymes related to the biogenesis of 1, including the characterization of a new polyketide synthase GsfA that synthesizes the benzophenone precursor and a cytochrome P450 GsfF that performs oxidative coupling between the orcinol and the phloroglucinol rings to yield the grisan structure. Notably, the finding of GsfF is in sharp contrast to the copper-dependent dihydrogeodin oxidase that performs a similar reaction in the geodin biosynthetic pathway. The biosynthetic knowledge enabled the in vitro total biosynthesis of 1 from malonyl-CoA using all purified enzyme components. This work therefore completely maps out the previously unresolved enzymology of the biosynthesis of a therapeutically relevant natural product.

  8. Sub-nanosecond plastic scintillator time response studies using laser produced x-ray pulsed excitation

    International Nuclear Information System (INIS)

    Tirsell, K.G.; Tripp, G.R.; Lent, E.M.; Lerche, R.A.; Cheng, J.C.; Hocker, L.; Lyons, P.B.

    1976-01-01

    The light emission time response of quenched NElll plastic scintillators has been measured using a streak camera (20 ps resolution) and 100 to 180 ps, 1.06 μm, laser-produced, pulsed, low energy x-ray excitation. Each light output pulse was obtained by deconvolution from the film data using the x-ray temporal response measured with an x-ray sensitive streak camera (10 ps resolution). Time response parameters are presented for benzophenone and acetophenone, quenching agents which most effectively reduce the decay time of the singlet component. Full width-half-maximums less than or equal to 260 ps were observed for NElll samples quenched with greater than or equal to 2 percent benzophenone. Results are given for unquenched samples consisting of different concentrations of butyl-PBD in PVT and for the phosphor ZnO doped with Ga

  9. Sub-nanosecond plastic scintillator time response studies using laser produced x-ray pulsed excitation

    International Nuclear Information System (INIS)

    Tirsell, K.G.; Tripp, G.R.; Lent, E.M.; Lerche, R.A.; Cheng, J.C.; Hocker, L.; Lyons, P.B.

    1977-01-01

    The light emission time response of quenched NE111 plastic scintillators has been measured using a streak camera (20 ps resolution) and 100 to 180 ps, 1.06 μm, laser-produced, pulsed, low energy x-ray excitation. Each light output pulse was obtained by deconvolution from the film data using the x-ray temporal response measured with an x-ray sensitive streak camera (10 ps resolution). Time response parameters are presented for benzophenone and acetophenone, quenching agents which most effectively reduce the decay time of the singlet component. Full width-half-maximums less than or equal to 260 ps were observed for NE111 samples quenched with greater than or equal to 2 percent benzophenone. Results are given for unquenched samples consisting of different concentrations of butyl-PBD in PVT and for the phosphor ZnO doped with Ga

  10. 4- {sup 18}F]fluoroarylalkylethers via an improved synthesis of n.c.a. 4- {sup 18}F]fluorophenol

    Energy Technology Data Exchange (ETDEWEB)

    Ludwig, Thomas; Ermert, Johannes E-mail: j.ermert@fz-juelich.de; Coenen, Heinz H

    2002-02-01

    This paper describes the improved synthesis of n.c.a. 4- {sup 18}F]fluorophenol for the preparation of {sup 18}F-labeled alkylarylethers. Nucleophilic fluorination of substituted benzophenone derivatives yielded n.c.a. 4- {sup 18}F]fluoro-4'-substituted benzophenones with 80- 90 % RCY, which were converted to benzoic acid phenylesters by treatment with peracetic acid. Strong electron-withdrawing substituents like nitro, cyano and trifluoromethyl favor a fluorophenyl-to-oxygen migration resulting in the formation of corresponding benzoic acid fluorophenylesters. N.c.a. {sup 18}F]fluorophenol is almost quantitatively formed after hydrolysis and can easily be converted with alkylhalides into n.c.a. {sup 18}F]fluoroarylalkylethers.

  11. Concentrations of environmental phenols and parabens in milk, urine and serum of lactating North Carolina women.

    Science.gov (United States)

    Hines, Erin P; Mendola, Pauline; von Ehrenstein, Ondine S; Ye, Xiaoyun; Calafat, Antonia M; Fenton, Suzanne E

    2015-07-01

    Phenols and parabens show some evidence for endocrine disruption in laboratory animals. The goal of the Methods Advancement for Milk Analysis (MAMA) Study was to develop or adapt methods to measure parabens (methyl, ethyl, butyl, propyl) and phenols (bisphenol A (BPA), 2,4- and 2,5-dichlorophenol, benzophenone-3, triclosan) in urine, milk and serum twice during lactation, to compare concentrations across matrices and with endogenous biomarkers among 34 North Carolina women. These non-persistent chemicals were detected in most urine samples (53-100%) and less frequently in milk or serum; concentrations differed by matrix. Although urinary parabens, triclosan and dichlorophenols concentrations correlated significantly at two time points, those of BPA and benzophenone-3 did not, suggesting considerable variability in those exposures. These pilot data suggest that nursing mothers are exposed to phenols and parabens; urine is the best measurement matrix; and correlations between chemical and endogenous immune-related biomarkers merit further investigation. Published by Elsevier Inc.

  12. Synthesis of nucleotide–amino acid conjugates designed for photo-CIDNP experiments by a phosphotriester approach

    Directory of Open Access Journals (Sweden)

    Tatyana V. Abramova

    2013-12-01

    Full Text Available Conjugates of 2’-deoxyguanosine, L-tryptophan and benzophenone designed to study pathways of fast radical reactions by the photo Chemically Induced Dynamic Nuclear Polarization (photo-CIDNP method were obtained by the phosphotriester block liquid phase synthesis. The phosphotriester approach to the oligonucleotide synthesis was shown to be a versatile and economic strategy for preparing the required amount of high quality samples of nucleotide–amino acid conjugates.

  13. Two New Chemical Constituents from the Stem Bark of Garcinia mangostana

    Directory of Open Access Journals (Sweden)

    Irene See

    2014-06-01

    Full Text Available A detailed chemical study on the ethyl acetate and methanol extracts of the stem bark of Garcinia mangostana resulted in the successful isolation of one new prenylated xanthone, mangaxanthone B (1, one new benzophenone, mangaphenone (2, and two known xanthones, mangostanin (3 and mangostenol (4. The structures of these compounds were elucidated through analysis of their spectroscopic data obtained using 1D and 2D NMR and MS techniques.

  14. Temporal variability in urinary excretion of bisphenol A and seven other phenols in spot, morning, and 24-h urine samples

    DEFF Research Database (Denmark)

    Lassen, Tina Harmer; Frederiksen, Hanne; Jensen, Tina Kold

    2013-01-01

    (ICCs). More than 70% of the urine samples had detectable levels of BPA, triclosan (TCS), benzophenone-3 (BP-3) and sum of 2,4-dichlorophenol and 2,5-dichlorophenol (σDCP). We found low to moderate ICCs for BPA (0.10-0.42) and σDCP (0.39-0.72), whereas the ICCs for BP-3 (0.69-0.80) and TCS (0...

  15. Excited State Evolution towards ligand loss and ligand chelation at group 6 metal carbonyl centres

    NARCIS (Netherlands)

    Manton, J.C.; Amirjalayer, S.; Coleman, A.C.; McMahon, S.; Harvey, E.C.; Greetham, G.M.; Clark, I.P.; Buma, W.J.; Woutersen, S.; Pryce, M.T.; Long, C.

    2014-01-01

    The photochem. and photophysics of three model "half-​sandwich" complexes (η6-​benzophenone)​Cr(CO)​3, (η6-​styrene)​Cr(CO)​3, and (η6-​allylbenzene)​Cr(CO)​3 were investigated using pico-​second time-​resolved IR spectroscopy and time-​dependent d. functional theory methods. The

  16. A Qualitative Assessment of Lontra longicaudis annectens Aquatic Habitats in Alvarado, Mexico

    OpenAIRE

    Gilberto Silva-López,; María Remedios Mendoza-López; Jesús Samuel Cruz-Sánchez; Oscar García-Barradas,; Gabriela López Suárez; Luis G. Abarca-Arenas; Francisco Gutiérrez-Mendieta; Armando Martínez Chacón

    2012-01-01

    A laboratory screening study following USEPA SW-846 test methods allowed the detection of organic compounds in the aquatic habitat of the Neotropical river otter (Lontra longicaudis annectens), in the Alvarado Lagoon System, Veracruz, Mexico. The compounds detected included 2-chlorocyclohexanol, phenylethylene glycol, benzophenone, ethanol-2-butoxyphosphate, styrene, p-xylene, ethylbenzene, trans-1,2- cyclohexanediol, di-2-ethylhexyl phthalate, benzeneacetaldehyde, hexadecane, tetracosane, do...

  17. Construction of Nontoxic Polymeric UV-Absorber with Great Resistance to UV-Photoaging

    OpenAIRE

    Huang, Zhong; Ding, Aishun; Guo, Hao; Lu, Guolin; Huang, Xiaoyu

    2016-01-01

    In this article, we developed a series of new nontoxic polymeric UV-absorbers through covalently attaching a benzophenone derivative onto the main chain of poly(vinyl chloride) (PVC) via mild and quantitative click chemistry. Azide groups were firstly introduced into the backbone of PVC via a nucleophilic reaction without affecting polymeric skeleton. Copper-catalyzed Husigen-Click cycloaddition reaction was performed between the pendant azide groups of PVC and alkynyl of (2-hydroxy-4-(prop-2...

  18. Design and application of natural product derived probes for activity based protein profiling

    OpenAIRE

    Battenberg, Oliver Alexander

    2015-01-01

    The identification of new antibacterial protein targets by activity based protein profiling (ABPP) is an important approach to face the increasing emergence of resistant bacteria. The scope of this work focuses on three new strategies for the labeling of antibacterial protein-targets with natural product derived ABPP-probes: A.) Evaluation of the intrinsic photo-reactivity of α-pyrones and pyrimidones for use as photo-crosslinkers. B.) Synthesis of a benzophenone-tag that combines photo-cross...

  19. Temperature induced reversible polymorphic phase transformations in a bis-hydrazone compound

    Science.gov (United States)

    Jayant, Vikrant; Das, Dinabandhu

    2018-03-01

    Two reversible polymorphic phase transformation of 2,3-butanedione, 2,3- bis[4,4‧-bis(diethylamino)benzophenone hydrazone] (DEBH) have been identified in DSC experiment. Topotactic phase transformation of three polymorphs has been observed in variable temperature Single Crystal X-ray Diffraction experiment. The reversible phase transformation of bulk material has been confirmed by Powder X-ray diffraction study.

  20. Electron transfer in reactions of ketones with organolithium reagents. A carbon-14 kinetic isotope effect probe

    International Nuclear Information System (INIS)

    Yamataka, H.; Fujimura, N.; Kawafuji, Y.; Hanafusa, T.

    1987-01-01

    Kinetic isotope effects have been determined for reactions of ketones labeled with carbon-14 at the carbonyl carbon with MeLi and Me 2 CuLi in diethyl ether at 0 0 C. Observed isotope effects were as follows: (C 6 H 5 ) 2 C double bonds O + MeLi, 12 k/ 14 k = 1.000 +/- 0.002; (C 6 H 5 ) 2 C double bonds O + Me 2 CuLi, 1.029 +/- 0.005; 2,4,6-Me 3 C 6 H 2 COC 6 H 5 + MeLi, 1.023 +/- 0.004. The relative reactivities of ortho-, meta-, and para-substituted benzophenones with these reagents were also determined by the competition experiments. These results are consistent with an electron-transfer step which is followed by a carbon-carbon bond-forming step that is or is not rate determining depending on the structure of ketones and reagents. The reaction of benzophenone with MeLi proceeds via rate-determining electron transfer; the change in nucleophile from MeLi to Me 2 CuLi shifts the rate-determining step from electron transfer to recombination; the change in ketone from benzophenone to 2,4,6-trimethylbenzophenone also shifts the rate-determining step from electron transfer to recombination because the latter step becomes slower for the more hindered ketone. The extent of the geometrical change of the substrate at the electron-transfer transition state of the reaction of benzophenone with MeLi was estimated to be small on the basis of the magnitude of the KIE and the rho value of the Hammett correlation

  1. Machine assisted reaction optimization: A self-optimizing reactor system for continuous-flow photochemical reactions

    KAUST Repository

    Poscharny, K.

    2018-04-07

    A methodology for the synthesis of oxetanes from benzophenone and furan derivatives is presented. UV-light irradiation in batch and flow systems allowed the [2 + 2] cycloaddition reaction to proceed and a broad range of oxetanes could be synthesized in manual and automated fashion. The identification of high-yielding reaction parameters was achieved through a new self-optimizing photoreactor system.

  2. Mechanistic Features of the Reactions of Organomagnesium Compounds

    DEFF Research Database (Denmark)

    Holm, Torkil; Crossland, Ingolf

    2000-01-01

    in Grignard reagents.2.3.1. The Schlenk equilibrium.2.3.2. Selfassociation in Grignard reagents.2.3.3. Association between RMgX and carbonyl compounds.3. Reactions of benzophenone(s) with Grignard reagents.3.1. Prediction of a radical mechanism and early evidence. 3.2. Reactivity series and linear free energy...... process.3.6. CIDNP observations.3.7 A new school in the study of the reaction of benzophenone with Grignard reagents.4. Polar concerted reaction mechanisms.4.1. Addition to aliphatic ketones.4.2. Addition to acid derivatives4.3. Concerted transfer of b-hydrogen. Reduction. 5. Reactions with a......1. Introduction. 2. Properties of Grignard reagents. 2.1. Thermochemistry of alkylmagnesium reagents.2.1.1. Heat of formation of Grignard reagents.2.1.2. C-Mg bond dissociation energies.2.1.3. The oxygen-magnesium bond.2.2. Oxidation potentials of Grignard reagents. 2.3. Association equilibria...

  3. Hydrogen-transfer and charge-transfer in photochemical and radiation induced reactions. Progress report, November 1, 1975--October 31, 1976

    International Nuclear Information System (INIS)

    Cohen, S.G.

    1976-10-01

    The relative importance of light absorption, quenching of triplet, and hydrogen transfer repair has been examined in retardation by mercaptans of photoreduction of aromatic ketones by alcohols. In the reduction of benzophenone by 2-propanol, retardation is efficient and, after correction for the first two effects, is due entirely to hydrogen-transfer repair, as indicated by deuterium labeling. In reduction of acetophenone by α-methylbenzyl alcohol, repair by hydrogen transfer is also operative. In reduction of benzophenone by benzhydrol, retardation is less efficient and is due to quenching, as the ketyl radical does not abstract hydrogen from mercaptan rapidly in competition with coupling. Deuterium isotope effects are discussed in terms of competitive reactions. Photoreduction of benzophenone by 2-butylamine and by triethylamine is retarded by aromatic mercaptans and disulfides. Of the retardation not due to light absorption and triplet quenching by the sulfur compounds, half is due to hydrogen-transfer repair, as indicated by racemization and deuterium labeling. The remainder is attributed to quenching by the sulfur compound of the charge-transfer-complex intermediate. Photoreduction by primary and secondary amines, but not by tertiary amines, is accelerated by aliphatic mercaptans. The acceleration is attributed to catalysis of hydrogen transfer by the mercaptan in the charge-transfer complex. The effect is large in hydrocarbon solvent, less in polar organic solvents and absent in water

  4. Mechanistic investigations of novel photoinitiators for radical polymerization

    International Nuclear Information System (INIS)

    Griesser, M.

    2012-01-01

    Nowadays, there is a wide variety of photoinitiators (PIs) available for radical polymerizations. A common example are two-component (Type II) systems such as benzophenone and tertiary amines. However these systems also suffer from problems due to bimolecularity. These include the possible back electron transfer (BET) leading to deactivation, as well as the solvent cage effect, occurring in highly viscous media. The aim of this thesis was to investigate the reaction mechanism of several photoinitiating systems, which show superior performance. Moreover, they exhibit additional benefits such as circumvention of oxygen inhibition by decarboxylation. Thereby this work helps to understand the molecular basis of the performance of different PI systems. In vestigated PIs included benzaldoxime esters, covalently linked benzophenone and N-phenylglycine as well as derivatives of both systems. Furthermore a PI based on benzophenone extended by ethynyl moeities is discussed. The main tool in this investigation was photo-CIDNP (chemically induced dynamic nuclear polarization), an NMR based technique for studying radical reactions. A complementary view was obtained with TR-EPR (time-resolved electron paramagnetic resonance), which provides direct information about the active radical species. The results were further compared with quantum mechanical calculations (DFT) of the magnetic properties of the radicals. The theoretical approach was further applied to other paramagnetic species such as donor-acceptor systems. (author) [de

  5. Comparative UPLC-QTOF-MS-based metabolomics and bioactivities analyses of Garcinia oblongifolia.

    Science.gov (United States)

    Li, Ping; AnandhiSenthilkumar, Harini; Wu, Shi-biao; Liu, Bo; Guo, Zhi-yong; Fata, Jimmie E; Kennelly, Edward J; Long, Chun-lin

    2016-02-01

    Garcinia oblongifolia Champ. ex Benth. (Clusiaceae) is a well-known medicinal plant from southern China, with edible fruits. However, the phytochemistry and bioactivity of the different plant parts of G. oblongifolia have not been studied extensively. Comparative metabolic profiling and bioactivities of the leaf, branch, and fruit of G. oblongifolia were investigated. A total of 40 compounds such as biflavonoids, xanthones, and benzophenones were identified using UPLC-QTOF-MS and MS(E), including 15 compounds reported for the first time from this species. Heatmap analyses found that benzophenones, xanthones, and biflavonoids were predominately found in branches, with benzophenones present in relatively high concentrations in all three plant parts. Xanthones were found to have limited distribution in fruit while biflavonoids were present at only low levels in leaves. In addition, the cytotoxic (MCF-7 breast cancer cell line) and antioxidant (ABTS and DPPH chemical tests) activities of the crude extracts of G. oblongifolia indicate that the branch extract exhibits greater bioactivity than either the leaf or the fruit extracts. Orthogonal partial least squares discriminate analysis was used to find 12 marker compounds, mainly xanthones, from the branches, including well-known antioxidants and cytotoxic agents. These G. oblongifolia results revealed that the variation in metabolite profiles can be correlated to the differences in bioactivity of the three plant parts investigated. This UPLC-QTOF-MS strategy can be useful to identify bioactive constituents expressed differentially in the various plant parts of a single species. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Hormonal activity, cytotoxicity and developmental toxicity of UV filters.

    Science.gov (United States)

    Balázs, Adrienn; Krifaton, Csilla; Orosz, Ivett; Szoboszlay, Sándor; Kovács, Róbert; Csenki, Zsolt; Urbányi, Béla; Kriszt, Balázs

    2016-09-01

    Ultraviolet (UV) filters are commonly used compounds in personal care products and polymer based materials, as they can absorb solar energy in the UVA and UVB spectrum. However, they are able to bind to hormone receptors and have several and different types of hormonal activities determined by in vitro assays. One of the aims of this work was to measure the hormonal and cytotoxic activities of four frequently used UV filters using bioluminescence based yeast test organisms. Using Saccharomyces cerevisiae BLYES and BLYAS strains allowed the rapid and reliable detection of agonist and antagonist hormonal activities, whereas BLYR strain served to measure cytotoxicity. Results confirmed that all tested UV filters show multiple hormonal activities. Cytotoxicity is detected only in the case of benzophenone-3. Research data on the toxic effects of benzophenone-3, especially on aquatic organisms are scarce, so further investigations were carried out regarding its cytotoxic and teratogenic effects on bacteria and zebrafish (Danio rerio) embryos, respectively. Results revealed the cytotoxicity of benzophenone-3 not only to yeasts but to bacteria, as well as its ability to influence zebrafish embryo hatching and development. Copyright © 2016 Elsevier Inc. All rights reserved.

  7. UV filters analyzed by isotope diluted TurboFlow-LC-MS/MS in urine from Danish children and adolescents.

    Science.gov (United States)

    Frederiksen, Hanne; Nielsen, Ole; Skakkebaek, Niels E; Juul, Anders; Andersson, Anna-Maria

    2017-03-01

    Experimental studies indicate that some chemicals with UV blocking properties (known as UV filters) can act as endocrine disruptors. UV filters are used in sunscreens and other cosmetic- and personal care products, as well as in other consumer products such as food packaging, clothing and furniture textiles to protect the products against UV radiation. Here we present the urinary excretion of suspected endocrine active UV filters in Danish children and adolescents recruited from the general population. The content of benzophenone (BP), benzophenone-1 (BP-1), benzophenone-2 (BP-2), benzophenone-3 (BP-3), 5-chloro-2- hydroxybenzophenone (BP-7), 4-hydroxybenzophenone (4-HBP), 4-methyl-benzophenone (4-MBP), 3-(4- methylbenzylidene)-camphor (4-MBC) and 3-benzylidene camphor (3-BC) were monitored in 24h urine and two consecutive first morning samples from 129 healthy Danish children and adolescents (6-21 yrs). All 387 samples were collected during the autumn (Nov. 2007) and were analyzed by a new on-line TurboFlow-LC-MS/MS method developed for simultaneous biomonitoring of these nine UV filters in urine. BP-3 and BP-1 were detected in more than 80% of the 24h samples and were significantly correlated (R 2 =0.815). BP, 4-HBP and BP-2 were found in 43, 15 and 5% of the samples, respectively. The median (range) concentrations of the UV-filters in 24-h urine were as follows: BP-3, 0.92 (LOD-115); BP-1, 0.54 (LOD-44.6); BP,UV filters; BP-7, 4-MBP, 4-MBC or 3-BC were detected in urine. A highly significant correlation between first morning and 24h urine levels of BP-3, BP-1 and 4-HBP from the same day was observed. Our project on UV filters analyzed by a new robust and sensitive LC-MS/MS method in Danish children and adolescents showed that almost all individuals were exposed to UV filters. Sun protection products have been claimed to be a major source of exposure to sunscreens. However since all children in the present study were exposed during autumn where sunscreens are not

  8. Preconception and prenatal urinary concentrations of phenols and birth size of singleton infants born to mothers and fathers from the Environment and Reproductive Health (EARTH) study.

    Science.gov (United States)

    Messerlian, Carmen; Mustieles, Vicente; Minguez-Alarcon, Lidia; Ford, Jennifer B; Calafat, Antonia M; Souter, Irene; Williams, Paige L; Hauser, Russ

    2018-02-22

    Although pregnancy concentrations of some phenols have been associated with infant size at birth, there is limited data on the effect of preconception exposure. We aimed to examine paternal and maternal preconception and maternal prenatal urinary phenol concentrations in relation to birth weight and head circumference. We evaluated 346 singletons born to 346 mothers and 184 fathers (184 couples) from a prospective preconception cohort of subfertile couples from the Environment and Reproductive Health (EARTH) Study in Boston, USA. We used multiple urine samples collected before the index pregnancy in both men and women to estimate mean preconception urinary benzophenone-3, triclosan, butylparaben, propylparaben, methylparaben, or ethylparaben concentrations. We also estimated mean maternal prenatal urinary phenol concentrations by averaging trimester-specific urine samples. Birth weight and head circumference were abstracted from delivery records. We estimated the association of natural log-phenol concentrations with birth outcomes using multivariable linear regression models, adjusting for known confounders. In adjusted models, each log-unit increase in paternal preconception benzophenone-3 concentration was associated with a 137 g increase in birth weight (95% CI: 60, 214). Additional adjustment for prenatal benzophenone-3 concentration strengthened this association. None of the maternal preconception phenol concentrations were associated with birth weight. However, maternal prenatal triclosan concentrations were associated with a 38 g decrease in birth weight (95% CI: -76, 0). Few associations were observed between phenols and head circumference except for a decrease of 0.27 cm (95% CI: -54, 0) in relation to maternal preconception methylparaben concentration. Although our findings should be interpreted in light of inherent study limitations, these results suggest potential evidence of associations between some paternal or maternal phenol concentrations and

  9. Maternal exposure to UV filters: associations with maternal thyroid hormones, IGF-I/IGFBP3 and birth outcomes.

    Science.gov (United States)

    Krause, M; Frederiksen, H; Sundberg, K; Jørgensen, F S; Jensen, L N; Nørgaard, P; Jørgensen, C; Ertberg, P; Petersen, J H; Feldt-Rasmussen, U; Juul, A; Drzewiecki, K T; Skakkebaek, N E; Andersson, A M

    2018-02-01

    Several chemical UV filters/absorbers ('UV filters' hereafter) have endocrine-disrupting properties in vitro and in vivo . Exposure to these chemicals, especially during prenatal development, is of concern. To examine maternal exposure to UV filters, associations with maternal thyroid hormone, with growth factor concentrations as well as to birth outcomes. Prospective study of 183 pregnant women with 2nd trimester serum and urine samples available. Maternal concentrations of the chemical UV filters benzophenone-1 (BP-1) and benzophenone-3 (BP-3) in urine and 4-hydroxy-benzophenone (4-HBP) in serum were measured by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The relationships between 2nd trimester maternal concentrations of the three chemical UV filters and maternal serum concentrations of thyroid hormones and growth factors, as well as birth outcomes (weight, height, and head and abdominal circumferences) were examined. Positive associations between maternal serum concentrations of 4-HBP and triiodothyronine (T 3 ), thyroxine (T 4 ), insulin-like growth factor I (IGF-I) and its binding protein IGFBP3 were observed in mothers carrying male fetuses. Male infants of mothers in the middle 4-HBP exposure group had statistically significantly lower weight and shorter head and abdominal circumferences at birth compared to the low exposure group. Widespread exposure of pregnant women to chemical UV filters and the possible impact on maternal thyroid hormones and growth factors, and on fetal growth, calls for further studies on possible long-term consequences of the exposure to UV filters on fetal development and children's health. © 2018 The authors.

  10. Problem Definition Studies on Potential Environmental Pollutants. V. Physical, Chemical, Toxicological, and Biological Properties of Seven Chemicals used in Pyrotechnic Compositions

    Science.gov (United States)

    1979-10-01

    Microorganisms: Induces cancerous growth in the marine alga Porphyra tenera. 1,4-Di-p-toluidino- No information was retrieved. anthvaquinone 1,4-D𔄀LuiLLU-2,3...IRONMiNTAI. CONSIDERATIONS Behavior in Soil and Water De . ..radation. No infnr wasrtri...d, UUL nis the imine of 4,4’bis(N,N-dimethylamino)benzophenone...Escherichia coli culture , a T2 bacteriophage, and auramine. Auramine at a concentration of 0.66 x 10-3 M produced no growth change in E. coli but produced

  11. Sub-nanosecond plastic scintillators

    International Nuclear Information System (INIS)

    Lyons, P.B.; Caldwell, S.E.; Hocker, L.P.; Crandall, D.G.; Zagarino, P.A.; Cheng, J.; Tirsell, G.; Hurlbut, C.R.

    1976-01-01

    Quenched plastic scintillators have been developed that yield much faster short decay components and greatly reduced long decay components compared to conventional plastic scintillators. The plastics are produced through the addition of selected quench agents to NE111 plastic scintillator that result in reduced total light output. Eight different agents have been studied. Benzophenone and piperidine are two of the most effective quench agents. Data are presented both for short and long decay components. The plastics are expected to make significant contributions in areas of plasma diagnostics

  12. Urinary concentrations of environmental phenols in pregnant women in a pilot study of the National Children's Study

    Energy Technology Data Exchange (ETDEWEB)

    Mortensen, Mary E., E-mail: MMortensen@cdc.gov [National Center for Environmental Health, Centers for Disease Control and Prevention, Atlanta, GA (United States); Calafat, Antonia M.; Ye, Xiaoyun; Wong, Lee-Yang [National Center for Environmental Health, Centers for Disease Control and Prevention, Atlanta, GA (United States); Wright, David J. [Westat, Inc. Rockville, MD (United States); Pirkle, James L. [National Center for Environmental Health, Centers for Disease Control and Prevention, Atlanta, GA (United States); Merrill, Lori S. [Westat, Inc. Rockville, MD (United States); Moye, John [NCS Program Office, Eunice Kennedy Shriver National Institute for Child Health and Human Development, National Institutes for Health, Bethesda, MD (United States)

    2014-02-01

    Environmental phenols are a group of chemicals with widespread uses in consumer and personal care products, food and beverage processing, and in pesticides. We assessed exposure to benzophenone-3, bisphenol A (BPA), triclosan, methyl- and propyl parabens, and 2,4- and 2,5-dichlorophenol or their precursors in 506 pregnant women enrolled in the National Children's Study (NCS) Vanguard Study. We measured the urinary concentrations of the target phenols by using online solid-phase extraction–isotope dilution high performance liquid chromatography–tandem mass spectrometry. NCS women results were compared to those of 524 similar-aged women in the National Health and Nutrition Examination Survey (NHANES) 2009–2010, and to 174 pregnant women in NHANES 2005–2010. In the NCS women, we found significant racial/ethnic differences (p<0.05) in regression adjusted mean concentrations of benzophenone-3, triclosan, 2,4- and 2,5-dichlorophenol, but not of BPA. Urinary 2,4- and 2,5-dichlorophenol concentrations were highly correlated (r=0.66, p<0.0001). Except for BPA and triclosan, adjusted mean concentrations were significantly different across the 7 study sites. Education was marginally significant for benzophenone-3, triclosan, propyl paraben, and 2,5-dichlorophenol. Urinary concentrations of target phenols in NCS pregnant women and U.S. women and pregnant women were similar. In NCS pregnant women, race/ethnicity and geographic location determined urinary concentrations of most phenols (except BPA), suggesting differential exposures. NCS Main Study protocols should collect urine biospecimens and information about exposures to environmental phenols. - Highlights: • Limited biomonitoring data are available in pregnant women. • Seven urinary phenols were measured in 506 third trimester women enrolled in the NCS. • Urine benzophenone-3, triclosan, 2,4- and 2,5-dichlorophenol differed by race/ethnicity. • Urinary concentrations of 2,4- and 2,5-dichlorophenol were

  13. Urinary concentrations of environmental phenols in pregnant women in a pilot study of the National Children's Study

    International Nuclear Information System (INIS)

    Mortensen, Mary E.; Calafat, Antonia M.; Ye, Xiaoyun; Wong, Lee-Yang; Wright, David J.; Pirkle, James L.; Merrill, Lori S.; Moye, John

    2014-01-01

    Environmental phenols are a group of chemicals with widespread uses in consumer and personal care products, food and beverage processing, and in pesticides. We assessed exposure to benzophenone-3, bisphenol A (BPA), triclosan, methyl- and propyl parabens, and 2,4- and 2,5-dichlorophenol or their precursors in 506 pregnant women enrolled in the National Children's Study (NCS) Vanguard Study. We measured the urinary concentrations of the target phenols by using online solid-phase extraction–isotope dilution high performance liquid chromatography–tandem mass spectrometry. NCS women results were compared to those of 524 similar-aged women in the National Health and Nutrition Examination Survey (NHANES) 2009–2010, and to 174 pregnant women in NHANES 2005–2010. In the NCS women, we found significant racial/ethnic differences (p<0.05) in regression adjusted mean concentrations of benzophenone-3, triclosan, 2,4- and 2,5-dichlorophenol, but not of BPA. Urinary 2,4- and 2,5-dichlorophenol concentrations were highly correlated (r=0.66, p<0.0001). Except for BPA and triclosan, adjusted mean concentrations were significantly different across the 7 study sites. Education was marginally significant for benzophenone-3, triclosan, propyl paraben, and 2,5-dichlorophenol. Urinary concentrations of target phenols in NCS pregnant women and U.S. women and pregnant women were similar. In NCS pregnant women, race/ethnicity and geographic location determined urinary concentrations of most phenols (except BPA), suggesting differential exposures. NCS Main Study protocols should collect urine biospecimens and information about exposures to environmental phenols. - Highlights: • Limited biomonitoring data are available in pregnant women. • Seven urinary phenols were measured in 506 third trimester women enrolled in the NCS. • Urine benzophenone-3, triclosan, 2,4- and 2,5-dichlorophenol differed by race/ethnicity. • Urinary concentrations of 2,4- and 2,5-dichlorophenol were

  14. Radical isomerization and hydrogen--deuterium exchange in reactions of silver p-tert-butylbenzoate

    International Nuclear Information System (INIS)

    Fields, E.K.; Meyerson, S.

    1978-01-01

    Silver p-tert-butylbenzoate decomposes at 300 0 C to products that retain the tert-butyl group intact. Among these products are five isomeric di-tert-butylbiphenyls, evidently resulting by isomerization of the first-formed p-tert-butylphenyl radical. With labeled benzophenone and benzene, the silver salt gives products in which much protium--deuterium exchange has occurred. The photolyzed silver salt arylates 1,2,4-trichlorobenzene; thermal decomposition in benzonitrile yields triphenyltriazine in addition to the radical arylation product. 9 tables

  15. Comparison Between Ionizing and Non-Ionizing Radiation Technologies for Wastewater Remediation

    International Nuclear Information System (INIS)

    Capobianco, Massimo L.; Esposito, Biagio; Navacchia, Maria Luisa; Pretali, Luca; Saracino, Michela; Zanelli, Alberto; Emmi, Salvatore S.

    2012-01-01

    A study on the decomposition of a surfactant (SDBS) and of four emerging pollutants (ofloxacin, carbamazepine, benzophenone-3, benzophenenone-4) in a multicomponent system is presented. These pollutants are decomposed in water by a few types of Advanced Oxidation Processes. The remediation methods included UV and γ-rays, all running in atmospheric conditions. It is shown that UV degradation methods can be improved by adding a photocatalyst (TiO 2 ), or a radical mediator (H 2 O 2 ). The processes were monitored step by step, by determining the concentration of pollutants by UV, HPLC and a specific surfactant selective kit, and measuring the total organic carbon content. (author)

  16. Pentanidium-catalyzed enantioselective phase-transfer conjugate addition reactions

    KAUST Repository

    Ma, Ting

    2011-03-09

    A new chiral entity, pentanidium, has been shown to be an excellent chiral phase-transfer catalyst. The enantioselective Michael addition reactions of tert-butyl glycinate-benzophenone Schiff base with various α,β- unsaturated acceptors provide adducts with high enantioselectivities. A successful gram-scale experiment at a low catalyst loading of 0.05 mol % indicates the potential for practical applications of this methodology. Phosphoglycine ester analogues can also be utilized as the Michael donor, affording enantioenriched α-aminophosphonic acid derivatives and phosphonic analogues of (S)-proline. © 2011 American Chemical Society.

  17. UV-induced reaction kinetics in dilinoleoylphosphatidylcholine monolayers with incorporated photosensitizers

    Directory of Open Access Journals (Sweden)

    DEJAN MARKOVIC

    2006-04-01

    Full Text Available Mixed insoluble monolayers (Langmuir films of 1,2-di-O-linoleoyl-3-sn-phosphatidylcholine (1,2-DLPC and incorporated benzophenone-type photosensitizers at an air-water interface were exposed to prolonged UV-irradiation. The irradiation was initiated at a particular fixed molecular packing value. Changes of the surface pressure during the UV-induced photolysis of the sensitizers were plotted against the irradiation time and the results were interpreted in terms of themolecular lipid / sensitizer ratios inside the monolayers.

  18. Advances in analytical methods and occurrence of organic UV-filters in the environment — A review

    Energy Technology Data Exchange (ETDEWEB)

    Ramos, Sara; Homem, Vera, E-mail: vhomem@fe.up.pt; Alves, Arminda; Santos, Lúcia

    2015-09-01

    UV-filters are a group of compounds designed mainly to protect skin against UVA and UVB radiation, but they are also included in plastics, furniture, etc., to protect products from light damage. Their massive use in sunscreens for skin protection has been increasing due to the awareness of the chronic and acute effects of UV radiation. Some organic UV-filters have raised significant concerns in the past few years for their continuous usage, persistent input and potential threat to ecological environment and human health. UV-filters end up in wastewater and because wastewater treatment plants are not efficient in removing them, lipophilic compounds tend to sorb onto sludge and hydrophilics end up in river water, contaminating the existing biota. To better understand the risk associated with UV-filters in the environment a thorough review regarding their physicochemical properties, toxicity and environmental degradation, analytical methods and their occurrence was conducted. Higher UV-filter concentrations were found in rivers, reaching 0.3 mg/L for the most studied family, the benzophenone derivatives. Concentrations in the ng to μg/L range were also detected for the p-aminobenzoic acid, cinnamate, crylene and benzoyl methane derivatives in lake and sea water. Although at lower levels (few ng/L), UV-filters were also found in tap and groundwater. Swimming pool water is also a sink for UV-filters and its chlorine by-products, at the μg/L range, highlighting the benzophenone and benzimidazole derivatives. Soils and sediments are not frequently studied, but concentrations in the μg/L range have already been found especially for the benzophenone and crylene derivatives. Aquatic biota is frequently studied and UV-filters are found in the ng/g-dw range with higher values for fish and mussels. It has been concluded that more information regarding UV-filter degradation studies both in water and sediments is necessary and environmental occurrences should be monitored more

  19. Sub-nanosecond plastic scintillators

    International Nuclear Information System (INIS)

    Lyons, P.B.; Caldwell, S.E.; Hocker, L.P.; Crandall, D.G.; Zagarino, P.A.; Cheng, J.; Tirsell, G.; Hurlbut, C.R.

    1977-01-01

    Quenched plastic scintillators have been developed that yield much faster short decay components and greatly reduced long decay components compared to conventional plastic scintillators. The plastics are produced through the addition of selected quench agents to NE111 plastic scintillator that result in reduced total light output. Eight different agents have been studied. Benzophenone and piperidine are two of the most effective quench agents. Data are presented both for short and long decay components. The plastics are expected to make significant contributions in areas of plasma diagnostics

  20. Suitable photo-resists for two-photon polymerization using femtosecond fiber lasers

    KAUST Repository

    Rajamanickam, V.P.

    2014-06-01

    We present suitable materials with good optical and mechanical properties, simple processing, efficient and optimized for two-photon polymerization (TPP) with femtosecond fiber lasers. We selected readily available acrylic monomer Bisphenol A ethoxylate diacrylate (BPA-EDA) with three different photo-initiators (PIs), isopropyl thioxanthone (ITX), 7-diethylamino-3-thenoylcoumarin (DETC), and 4,4′ bis(diethylamino) benzophenone (BDEB), since their absorption spectra match well with the laser wavelength at 780 nm. These PIs grant efficient radical generation, reactivity and high solubility in acrylic monomers. Finally, good optical and mechanical properties are demonstrated by the fabrication of different micro-structures.

  1. Functional barrier in two-layer recycled PP films for food packaging applications

    Science.gov (United States)

    Scarfato, P.; Di Maio, L.; Milana, M. R.; Feliciani, R.; Denaro, M.; Incarnato, L.

    2014-05-01

    A preliminary study on bi-layer virgin/contaminated polypropylene co-extruded films was performed in order to evaluate the possibility to realize an effective functional barrier in PP-based multi-layer systems. In particular, the specific migration in 10% v/v aqueous ethanol of two surrogate contaminants (phenyl-cyclohexane and benzophenone) contained in the contaminated layer across the PP functional barrier was measured at different times and the results were compared with those obtained from a contaminated mono-layer polypropylene film. Moreover, the thermal and mechanical performances of the produced films were investigated.

  2. The application of PS printing plate with Biimidazole photosensitive initiating systems

    International Nuclear Information System (INIS)

    Li Lidong; Xu Jinqi; Gao Fang; Yang Yongyuan

    1999-01-01

    The ultraviolet photosensitive initiating system is composed of 4,4'-bis(N,N'-dimethyl-amino)benzophenone(MK), 2-chlorohexaarylbiimidazole(o-C1-HABI) and a hydrogen donor co-initiator n-dodecyl mercaptan(SH). Under the irradiation by high pressure mercury lamp, the relationship between the photo-polymerization rate of MMA and the concentration of each component of the system, including MK, o-C1-HABI and SH, was studied. The excellent results have been obtained through studying the system's application on PS lithographic printing plate

  3. Percolation of triplet excitation in restricted geometries

    Science.gov (United States)

    Saha, D. C.; Misra, T. N.; Talukdar, D.

    1996-04-01

    Migration of benzophenone triplet excitations in polymethylmethacrylate and methylmethacrylate-styrene copolymer has been studied under steady state excitation by using 1-chloronapthalene as a trap. The excitation energy capture efficiency by a trap has been obtained as a function of the donor concentration at various trap concentrations. Percolation model has been successfully applied to evaluate the critical exponents. The evaluated critical exponents are in very good agreement with three dimensional triplet excitation migration topology in polymethylmethacrylate and two dimensional one in the copolymer.

  4. Synthesis and reactions of triphenylphosphine-O-benzophenonimine and derivatives

    International Nuclear Information System (INIS)

    Elamin, Manahil Babiker

    1999-08-01

    O-Amino benzophenone and its para and meta isomers were prepared using Friedl-Craft benzoylation. Their azides were also prepared via their diazonium salts. The azide of o-amino benzophenone in its reduced form (o-benzylaniline) and its cyclic ketal were synthesised. All azides thus formed were reacted separately with triphenylphosphine to give the corresponding phosphinimines, the Wittig reagents nitrogen analog. The reactivity of the phosphorous bond. (P=N) in the different phosphoranes were studied by two types of reactions: (1) the Wittig type of reaction using benzaldehyde and its into derivatives with each of the above prepared phosphinimines. While triphenylphosphine-m-benzophenonimine (ii) and the triphenylphosphine benzophenonimine ethylene acetal (v) and it's reduced form triphenylphosphine-o-benzophenonimine (iv) react giving the corresponding schiffis bases. However, the ortho (i) and the para (iii) isomers failed to react. This lack of reactivity is presumably due to their great stability which came about through the extensive resonance that reduced the nucleophilicity of the nitrogen nucleophiles. (2) The phophinimines each was irradiated using Hanovia medium pressure UV lamp. Also the ortho and para isomers were not affected while others reacted giving the corresponding azo-compound and triphenylphosphine. they were separated and detected by chromatography.(Author)

  5. Determination of Polar Compounds in Guava Leaves Infusions and Ultrasound Aqueous Extract by HPLC-ESI-MS

    Directory of Open Access Journals (Sweden)

    Elixabet Díaz-de-Cerio

    2015-01-01

    Full Text Available Literature lacks publications about polar compounds content in infusion or guava leaves tea. Because of that, a comparison between different times of infusion and a conventional ultrasound aqueous extract was carried out. Several polar compounds have been identified by HPLC-ESI-MS and their antioxidant activity was evaluated by FRAP and ABTS assays. Four different classes of phenolic compounds (gallic and ellagic acid derivatives, flavonols, flavanones, and flavan-3-ols and some benzophenones were determined. The quantification results reported that the order, in terms of concentration of the classes of polar compounds in all samples, was flavonols > flavan-3-ols > gallic and ellagic acid derivatives > benzophenones > flavanones. As expected, the aqueous extract obtained by sonication showed the highest content in the compounds studied. Significative differences were noticed about the different times of infusion and five minutes was the optimal time to obtain the highest content in polar compounds using this culinary method. All the identified compounds, except HHDP isomers and naringenin, were positively correlated with antioxidant activity.

  6. Efficient sample preparation method based on solvent-assisted dispersive solid-phase extraction for the trace detection of butachlor in urine and waste water samples.

    Science.gov (United States)

    Aladaghlo, Zolfaghar; Fakhari, Alireza; Behbahani, Mohammad

    2016-10-01

    In this work, an efficient sample preparation method termed solvent-assisted dispersive solid-phase extraction was applied. The used sample preparation method was based on the dispersion of the sorbent (benzophenone) into the aqueous sample to maximize the interaction surface. In this approach, the dispersion of the sorbent at a very low milligram level was achieved by inserting a solution of the sorbent and disperser solvent into the aqueous sample. The cloudy solution created from the dispersion of the sorbent in the bulk aqueous sample. After pre-concentration of the butachlor, the cloudy solution was centrifuged and butachlor in the sediment phase dissolved in ethanol and determined by gas chromatography with flame ionization detection. Under the optimized conditions (solution pH = 7.0, sorbent: benzophenone, 2%, disperser solvent: ethanol, 500 μL, centrifuged at 4000 rpm for 3 min), the method detection limit for butachlor was 2, 3 and 3 μg/L for distilled water, waste water, and urine sample, respectively. Furthermore, the preconcentration factor was 198.8, 175.0, and 174.2 in distilled water, waste water, and urine sample, respectively. Solvent-assisted dispersive solid-phase extraction was successfully used for the trace monitoring of butachlor in urine and waste water samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Superhydrophobic durable coating based on UV-photoreactive silica nanoparticles

    International Nuclear Information System (INIS)

    Nahum, T.; Dodiuk, H.; Dotan, A.; Kenig, S.; Lellouche, J. P.

    2015-01-01

    Superhydrophobic surfaces with contact angle (CA) >150 and sliding angle (SA) <10 have been aroused curiosity over the years due to their various applications. Superhydrophobicity can be obtained tailoring the chemistry and the roughness of the surface, mimicking the Lotus flower. Most superhydrophobic surfaces based on secondary bonding lose their roughness in harsh conditions and are unsuitable for practical applications. Photoreactive SiO 2 nanoparticles (NPs) based on benzophenone (BP) can be a very effective tool for formation of reactive species that function as a molecular bridge by covalent bonding between the NP and any polymer matrix with C-C and C-H bonds. The present work focused on thermoset radiation curing urethane acrylate. Upon UV irradiation reactive excited nπ* triplet benzophenone species are formed and react through hydrogen abstraction to form ketyl radicals which interact with a radicals from the UV irradiated polymer matrix to yield covalent bonding. Roughness was achieved by dipping the substrate in SiO 2 @BPs NPs dispersion followed by irradiation. Fluoroalkylsilane was used to obtain hydrophobic top layer. AFM nano manipulation was used to verify the immobilization of NPs. Evaluation of durability was made using air flow at 300 km/hr. Preliminary results indicate the formation of super hydrophobic surfaces (CA>150 and SA<10) with improved stability

  8. Superhydrophobic durable coating based on UV-photoreactive silica nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Nahum, T.; Dodiuk, H.; Dotan, A.; Kenig, S. [Department of Plastics Engineering, Shenkar College of Engineering and Design, 12 Anna Frank Street, Ramat Gan 52526 (Israel); Lellouche, J. P. [Department of Chemistry, Nanomaterials Research Center, Institute of Nanotechnology and Advanced Materials, Bar-Ilan University, Ramar-Gan, 52900 (Israel)

    2015-05-22

    Superhydrophobic surfaces with contact angle (CA) >150 and sliding angle (SA) <10 have been aroused curiosity over the years due to their various applications. Superhydrophobicity can be obtained tailoring the chemistry and the roughness of the surface, mimicking the Lotus flower. Most superhydrophobic surfaces based on secondary bonding lose their roughness in harsh conditions and are unsuitable for practical applications. Photoreactive SiO{sub 2} nanoparticles (NPs) based on benzophenone (BP) can be a very effective tool for formation of reactive species that function as a molecular bridge by covalent bonding between the NP and any polymer matrix with C-C and C-H bonds. The present work focused on thermoset radiation curing urethane acrylate. Upon UV irradiation reactive excited nπ* triplet benzophenone species are formed and react through hydrogen abstraction to form ketyl radicals which interact with a radicals from the UV irradiated polymer matrix to yield covalent bonding. Roughness was achieved by dipping the substrate in SiO{sub 2}@BPs NPs dispersion followed by irradiation. Fluoroalkylsilane was used to obtain hydrophobic top layer. AFM nano manipulation was used to verify the immobilization of NPs. Evaluation of durability was made using air flow at 300 km/hr. Preliminary results indicate the formation of super hydrophobic surfaces (CA>150 and SA<10) with improved stability.

  9. Effects of mercaptans and disulfides on photochemical and high energy radiation induced reactions. Progress report, November 1, 1974--October 31, 1975

    International Nuclear Information System (INIS)

    Cohen, S.G.

    1975-10-01

    A chain reaction may be formulated at alkaline pH in terms of e - /sub aq/ acting as a source of - OH as a reactant and H. regenerating e - /sub aq/. This may account for radiolytic conversion of CO to formate with high G. 60 Co γ-radiolysis of alkaline aqueous acetonitrile and acetamide gave no evidence of a chain; extensive hydrolysis of methyl acetate is now attributed to non-radiolytic, normal hydrolysis. Aromatic mercaptans are found to retard photoreduction of a benzophenone by aliphatic amines, largely by hydrogen atom-transfer repair reactions. Aliphatic mercaptans accelerate photoreduction, apparently by affecting the reduction to quenching ratio in the intermediate charge-transfer complex. In photoreduction of a benzophenone by 2,3-butylene glycol at pH 3, the glycol is converted, not to 3-hydroxy-2-butanone, but to 2-butanone, and about 4 molecules of this are formed per molecule of ketone reduced. A short chain appears to be established. Mercaptan appears to accelerate the reduction of the ketone and retard the formation of 2-butanone

  10. Determination of ultraviolet filter activity on coconut oil cosmetic cream

    Science.gov (United States)

    Widiyati, Eni

    2017-08-01

    A research on determination of ultraviolet (UV) filter activity of cosmetic cream with coconut oil as raw material has been done. The cream was made by mixing the oil phase (coconut oil, stearic acid, lanolin and cetyl alcohol) at 70°C and the water phase (glycerin, aquadest and triethanolamine) at 70°C, while stirring until reached a temperature of 35°C. It was made also a cream with inorganic sunscreen TiO2 and organic sunscreen benzophenone-3 as a comparison. To study the UV filter activity, each cream was determined the UV absorption using UV spectrophotometer. The results show that cosmetic cream with coconut oil as raw material absorbs UV rays in the region of UV-C, whereas the cream with TiO2 absorbs the UV rays from UV-C to UV-A and cream with benzophenone-3 absorbs the UV rays from UV-B to UV-A region. This means that, the cosmetic cream with coconut oil as raw material has an activity as UV-C filter. If this cream is expected to have an activity as a sunscreen, it must be added an inorganic or organic sunscreen or a mixture of both as an active materials.

  11. Associations of prenatal exposure to phenols with birth outcomes

    International Nuclear Information System (INIS)

    Tang, Rong; Chen, Min-jian; Ding, Guo-dong; Chen, Xiao-jiao; Han, Xiu-mei; Zhou, Kun; Chen, Li-mei; Xia, Yan-kai; Tian, Ying; Wang, Xin-ru

    2013-01-01

    Many phenols are known to mimic or antagonize hormonal activities and may adversely affect fetal growth. A study of 567 pregnant women was conducted to investigate the relationship between prenatal phenol exposure and birth outcomes, including birth weight, length, and gestational age. We measured the concentrations of bisphenol A, benzophenone-3, 4-n-octylphenol and 4-n-nonylphenol in maternal urine and examine their association with birth outcomes. Categories of urinary benzophenone-3 concentration were associated with decreased gestational age in all infants (p for trend = 0.03). Between middle and low exposure groups, we also found bisphenol A was negatively associated with gestational duration (β adjusted = −0.48 week; 95% confidence interval: −0.91, −0.05). After stratification by gender, we found the consistent results in infant boys with those in all infants, but we did not observe significant association for girls. In conclusion, we found prenatal phenol exposure was sex-specifically related to birth outcomes. -- Highlights: •We examined relationship of prenatal exposure to phenols with birth outcomes. •We determined urinary concentrations of various phenols. •BP-3 and BPA were negatively associated with gestational age. •There was sex-specific association between phenol exposure and birth outcomes. -- Prenatal phenol exposure was sex-specifically related to birth outcomes

  12. 3-D LTCC microfluidic device as a tool for studying nanoprecipitation

    Science.gov (United States)

    Schianti, J. N.; Cerize, N. P. N.; Oliveira, A. M.; Derenzo, S.; Góngora-Rubio, M. R.

    2013-03-01

    Nanoparticles have been used to improve the properties of many cosmetic products, mainly the sunscreens materials using nanoencapsulation or nanosuspensions, improving the contact with active molecules, enhancing the sun protection effect and facilitating formulations in industrial products. Microfluidic devices offer an important possibility in producing nanoparticles in a simple way, in one step bottom up technique, continuum process with low polidispersivity, low consumption of reagents and additives. In this work, we microfabricated a 3-D LTCC microfluidic device to study the nanoprecipitation of Benzophenone-3, used as a sunscreen in pharmaceutical products. It was observed that some parameters influence the particle size related to the total fluid flow on device, the ratio between phases, and the Benzophenone-3 initial concentration. The influence of applied voltages on particle sizes was tested also. For the processing, a high voltage was applied in a Kovar tube inserted in the 3D device. The use of microfluidic device resulted in particles with 100 up to 800 nm of size, with polispersivity index below 0.3 and offering an interesting way to obtain nanoparticles. These studies are still ongoing, but early results indicate the possibility of obtaining B-3 nanostructured material.

  13. Ketoprofen removal by O₃ and O₃/UV processes: kinetics, transformation products and ecotoxicity.

    Science.gov (United States)

    Illés, Erzsébet; Szabó, Emese; Takács, Erzsébet; Wojnárovits, László; Dombi, András; Gajda-Schrantz, Krisztina

    2014-02-15

    Ozonation (O3) and its combination with ultraviolet radiation (O3/UV) were used to decompose ketoprofen (KET). Depending on the initial KET concentration, fourteen to fifty time's faster KET degradation was achieved using combined O3/UV method compared to simple ozonation. Using both methods, formation of four major aromatic transformation products were observed: 3-(1-hydroxyethyl)benzophenone, 3-(1-hydroperoxyethyl) benzophenone, 1-(3-benzoylphenyl) ethanone and 3-ethylbenzophenone. In the combined treatment the degradation was mainly due to the direct effect of UV light, however, towards the end of the treatment, O3 highly contributed to the mineralization of small carboxylic acids. High (~90%) mineralization degree was achieved using the O3/UV method. Toxicity tests performed using representatives of three trophic levels of the aquatic ecosystems (producers, consumers and decomposers) Pseudokirchneriella subcapitata green algae, Daphnia magna zooplanktons and Vibrio fischeri bacteria showed that under the used experimental conditions the transformation products have significantly higher toxicity towards all the test organisms, than KET itself. The bacteria and the zooplanktons showed higher tolerance to the formed products than algae. The measured toxicity correlates well with the concentration of the aromatic transformation products, therefore longer treatments than needed for complete degradation of KET are strongly suggested, in order to avoid possible impact of aromatic transformation products on the aquatic ecosystem. Copyright © 2013 Elsevier B.V. All rights reserved.

  14. Degradation pathway of malachite green in a novel dual-tank photoelectrochemical catalytic reactor

    International Nuclear Information System (INIS)

    Diao, Zenghui; Li, Mingyu; Zeng, Fanyin; Song, Lin; Qiu, Rongliang

    2013-01-01

    Highlights: • A novel dual-tank photoelectrochemical catalytic reactor was designed. • Malachite green degraded in bipolar double-effect mode. • Salt bridge replaced by a cation exchange membrane in the reactor. • Degradation pathways of malachite green in the cathode and anode tanks were similar. -- Abstract: A novel dual-tank photoelectrochemical catalytic reactor was designed to investigate the degradation pathway of malachite green. A thermally formed TiO 2 /Ti thin film electrode was used as photoanode, graphite was used as cathode, and a saturated calomel electrode was employed as the reference electrode in the reactor. In the reactor, the anode and cathode tanks were connected by a cation exchange membrane. Results showed that the decolorization ratio of malachite green in the anode and cathode was 98.5 and 96.5% after 120 min, respectively. Malachite green in the two anode and cathode tanks was oxidized, achieving the bipolar double effect. Malachite green in both the anode and cathode tanks exhibited similar catalytic degradation pathways. The double bond of the malachite green molecule was attacked by strong oxidative hydroxyl radicals, after which the organic compound was degraded by the two pathways into 4,4-bis(dimethylamino) benzophenone, 4-(dimethylamino) benzophenone, 4-(dimethylamino) phenol, and other intermediate products. Eventually, malachite green was degraded into oxalic acid as a small molecular organic acid, which was degraded by processes such as demethylation, deamination, nitration, substitution, addition, and other reactions

  15. Degradation pathway of malachite green in a novel dual-tank photoelectrochemical catalytic reactor

    Energy Technology Data Exchange (ETDEWEB)

    Diao, Zenghui [Department of Environmental Engineering, Jinan University, Guangzhou 510630 (China); School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Li, Mingyu, E-mail: tlimy@jnu.edu.cn [Department of Environmental Engineering, Jinan University, Guangzhou 510630 (China); Zeng, Fanyin; Song, Lin [Department of Environmental Engineering, Jinan University, Guangzhou 510630 (China); Qiu, Rongliang [School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China)

    2013-09-15

    Highlights: • A novel dual-tank photoelectrochemical catalytic reactor was designed. • Malachite green degraded in bipolar double-effect mode. • Salt bridge replaced by a cation exchange membrane in the reactor. • Degradation pathways of malachite green in the cathode and anode tanks were similar. -- Abstract: A novel dual-tank photoelectrochemical catalytic reactor was designed to investigate the degradation pathway of malachite green. A thermally formed TiO{sub 2}/Ti thin film electrode was used as photoanode, graphite was used as cathode, and a saturated calomel electrode was employed as the reference electrode in the reactor. In the reactor, the anode and cathode tanks were connected by a cation exchange membrane. Results showed that the decolorization ratio of malachite green in the anode and cathode was 98.5 and 96.5% after 120 min, respectively. Malachite green in the two anode and cathode tanks was oxidized, achieving the bipolar double effect. Malachite green in both the anode and cathode tanks exhibited similar catalytic degradation pathways. The double bond of the malachite green molecule was attacked by strong oxidative hydroxyl radicals, after which the organic compound was degraded by the two pathways into 4,4-bis(dimethylamino) benzophenone, 4-(dimethylamino) benzophenone, 4-(dimethylamino) phenol, and other intermediate products. Eventually, malachite green was degraded into oxalic acid as a small molecular organic acid, which was degraded by processes such as demethylation, deamination, nitration, substitution, addition, and other reactions.

  16. Separation and preparation of xanthochymol and guttiferone E by high performance liquid chromatography and high speed counter-current chromatography combined with silver nitrate coordination reaction.

    Science.gov (United States)

    Li, Jun; Gao, Ruixi; Zhao, Dan; Huang, Xianju; Chen, Yu; Gan, Fei; Liu, Hui; Yang, Guangzhong

    2017-08-18

    Xanthochymol (XCM) and guttiferone E (GFE), a pair of π bond benzophenone isomers from Garcinia xanthochymus, were once reported to be difficult or impossible to separate. The present study reports the successful separation of these two isomers through high performance liquid chromatography (HPLC), as well as their effective isolation using high speed counter-current chromatography (HSCCC) based on the silver nitrate (AgNO 3 ) coordination reaction. First, an effective HPLC separation system was developed, achieving a successful baseline separation with resolution of 2.0. Based on the partition coefficient (K) resolved by HPLC, the two-phase solvent system was determined as n-hexane, methanol and water with the uncommon volume ratio of 4:6:1. A crude extract of Garcinia xanthochymus (0.2g) was purified by normal HSCCC and refined with AgNO 3 -HSCCC. Monomers of XCM and GFE were identified by HPLC, mass spectrometry (MS) and nuclear magnetic resonance (NMR). The results demonstrate the separation and isolation of π bond benzophenone isomers using ordinary octadecyl silane (C 18 ) columns and HSCCC. Copyright © 2017 Elsevier B.V. All rights reserved.

  17. How Does the C-Halogen Bond Break in the Photosubstitution Reaction of 3-Fluorobenzophenone in Acidic Aqueous Solutions?

    Science.gov (United States)

    Huang, Jinqing; Ma, Jiani; Li, Mingde; Liu, Mingyue; Zhang, Xiting; Phillips, David Lee

    2015-10-02

    The efficient photosubstitution reaction of m-fluorobenzophenone and the related photohydration reactions were systematically investigated in acidic aqueous solutions. The mechanisms and intermediates were directly characterized by femtosecond transient absorption spectroscopy and nanosecond time-resolved resonance Raman spectroscopy, which is supported by density functional theory calculations. This photosubstitution was found to be a two-step process, based on the observation of a meta-hydration intermediate. The protonation of the ketone was confirmed as a crucial precursor step for further photochemical reactions as indicated by the observation of the absorption spectrum of an excited triplet protonated species. More interestingly, the efficient photosubstitution reaction could selectively occur under specific conditions. Control experiments on a series of halogen-substituted benzophenones were conducted to study the influence of the solution acidity, substituent positions, and the kind of substituted halogens on the efficiency in forming the corresponding hydroxyl photosubstitution product. Some practical conditions in predicting the efficiency of the photosubstitution reaction of interest are summarized, and they were successfully used to predict when the photosubstitution reaction takes place for some other halogen-substituted benzophenone derivatives. The driving force of this photosubstitution reaction may provide insights into several possible applications which are also briefly discussed.

  18. Neurotoxic effect of active ingredients in sunscreen products, a contemporary review

    Directory of Open Access Journals (Sweden)

    Joanna A. Ruszkiewicz

    Full Text Available Sunscreen application is the main strategy used to prevent the maladies inflicted by ultraviolet (UV radiation. Despite the continuously increasing frequency of sunscreen use worldwide, the prevalence of certain sun exposure-related pathologies, mainly malignant melanoma, is also on the rise. In the past century, a variety of protective agents against UV exposure have been developed. Physical filters scatter and reflect UV rays and chemical filters absorb those rays. Alongside the evidence for increasing levels of these agents in the environment, which leads to indirect exposure of wildlife and humans, recent studies suggest a toxicological nature for some of these agents. Reviews on the role of these agents in developmental and endocrine impairments (both pathology and related mechanisms are based on both animal and human studies, yet information regarding the potential neurotoxicity of these agents is scant. In this review, data regarding the neurotoxicity of several organic filters: octyl methoxycinnamate, benzophenone-3 and −4, 4-methylbenzylidene camphor, 3-benzylidene camphor and octocrylene, and two allowed inorganic filters: zinc oxide and titanium dioxide, is presented and discussed. Taken together, this review advocates revisiting the current safety and regulation of specific sunscreens and investing in alternative UV protection technologies. Keywords: Neurotoxicity, Sunscreen, Zinc oxide, Titanium dioxide, Octyl methoxycinnamate, Benzophenone-3, 4-Methylbenzylidene camphor, Octocrylene

  19. UV filters, ingredients with a recognized anti-inflammatory effect.

    Directory of Open Access Journals (Sweden)

    Céline Couteau

    Full Text Available BACKGROUND: To explain observed differences during SPF determination using either an in vivo or in vitro method, we hypothesized on the presence of ingredients having anti-inflammatory properties. METHODOLOGY/PRINCIPAL FINDINGS: To research our hypothesis, we studied the 21 UV filters both available on the market and authorized by European regulations and subjected these filters to the phorbol-myristate-acetate test using mice. We then catalogued the 13 filters demonstrating a significant anti-inflammatory effect with edema inhibition percentages of more than 70%. The filters are: diethylhexyl butamido triazone (92%, benzophenone-5 and titanium dioxide (90%, benzophenone-3 (83%, octocrylène and isoamyl p-methoxycinnamate (82%, PEG-25 PABA and homosalate (80%, octyl triazone and phenylbenzimidazole sulfonic acid (78%, octyl dimethyl PABA (75%, bis-ethylhexyloxyphenol methoxyphenyl triazine and diethylamino hydroxybenzoyl hexylbenzoate (70%. These filters were tested at various concentrations, including their maximum authorized dose. We detected a dose-response relationship. CONCLUSIONS/SIGNIFICANCE: The anti-inflammatory effect of a sunscreen ingredient may affect the in vivo SPF value.

  20. Presence of UV filters in surface water and the effects of phenylbenzimidazole sulfonic acid on rainbow trout (Oncorhynchus mykiss) following a chronic toxicity test.

    Science.gov (United States)

    Grabicova, Katerina; Fedorova, Ganna; Burkina, Viktoriia; Steinbach, Christoph; Schmidt-Posthaus, Heike; Zlabek, Vladimir; Kocour Kroupova, Hana; Grabic, Roman; Randak, Tomas

    2013-10-01

    UV filters belong to a group of compounds that are used by humans and are present in municipal waste-waters, effluents from sewage treatment plants and surface waters. Current information regarding UV filters and their effects on fish is limited. In this study, the occurrence of three commonly used UV filters - 2-phenylbenzimidazole-5-sulfonic acid (PBSA), 2-hydroxy-4-methoxybenzophenone (benzophenone-3, BP-3) and 5-benzoyl-4-hydroxy-2-methoxy-benzenesulfonic acid (benzophenone-4, BP-4) - in South Bohemia (Czech Republic) surface waters is presented. PBSA concentrations (up to 13μgL(-1)) were significantly greater than BP-3 or BP-4 concentrations (up to 620 and 390ngL(-1), respectively). On the basis of these results, PBSA was selected for use in a toxicity test utilizing the common model organism rainbow trout (Oncorhynchus mykiss). Fish were exposed to three concentrations of PBSA (1, 10 and 1000µgL(-1)) for 21 and 42 days. The PBSA concentrations in the fish plasma, liver and kidneys were elevated after 21 and 42 days of exposure. PBSA increased activity of certain P450 cytochromes. Exposure to PBSA also changed various biochemical parameters and enzyme activities in the fish plasma. However, no pathological changes were obvious in the liver or gonads. Copyright © 2013 Elsevier Inc. All rights reserved.

  1. Combination of retinyl palmitate and UV-filters: phototoxic risk assessment based on photostability and in vitro and in vivo phototoxicity assays.

    Science.gov (United States)

    Benevenuto, Carolina Gomes; Guerra, Lucas Offenbecker; Gaspar, Lorena Rigo

    2015-02-20

    This study aimed to assess the phototoxic potential of combined UV-filters and retinyl palmitate (RP) in the presence or not of bemotrizinol (BMTZ), employing photostability and in vitro and in vivo phototoxicity assays. The formulations tested contained octocrylene (OCT), octyl methoxycinnamate (OMC), benzophenone-3 (BZP-3) and RP (photostable) or octocrylene (OCT), octyl methoxycinnamate (OMC), avobenzone (AVO) and RP (less photostable). Both formulations were supplemented with bemotrizinol. Photostability was evaluated by exposing, or not, formulations spread on a glass plate to UVA/UVB irradiation. The resulting products were quantified by HPLC analysis. In vitro phototoxicity of UV-filters and combinations were evaluated using 3T3 viable monolayer fibroblast cultures submitted, or not, to irradiation according to OECD TG 432. In vivo photoallergy and photoxicity were assessed by clinical studies (photopatch test). Photostability assays showed that UV-filter bemotrizinol was a better photostabilizer for RP/benzophenone-3 than for RP/avobenzone. The in vitro phototoxicity of the combination RP/avobenzone was reduced by bemotrizinol. Clinical studies did not indicate phototoxic or photoallergenic potentials in all formulations tested. It is concluded that the 3T3 NRU phototoxicity test may be considered a supplementary assay in formulation developments, since it can detect chemically unstable and potentially phototoxic combinations. However, extrapolation of in vitro positive results to human photopatch tests may be performed only to a limited extent. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Occurrence, distribution and ecological risk assessment of multiple classes of UV filters in surface waters from different countries.

    Science.gov (United States)

    Tsui, Mirabelle M P; Leung, H W; Wai, Tak-Cheung; Yamashita, Nobuyoshi; Taniyasu, Sachi; Liu, Wenhua; Lam, Paul K S; Murphy, Margaret B

    2014-12-15

    Organic UV filters are common ingredients of personal care products (PCPs), but little is known about their distribution in and potential impacts to the marine environment. This study reports the occurrence and risk assessment of twelve widely used organic UV filters in surface water collected in eight cities in four countries (China, the United States, Japan, and Thailand) and the North American Arctic. The number of compounds detected, Hong Kong (12), Tokyo (9), Bangkok (9), New York (8), Los Angeles (8), Arctic (6), Shantou (5) and Chaozhou (5), generally increased with population density. Median concentrations of all detectable UV filters were UV filter levels in Hong Kong. In general, spatial patterns varied with sampling month and all compounds showed higher concentrations in the wet season except benzophenone-4 (BP-4). Probabilistic risk assessment showed that 4-methylbenzylidene camphor (4-MBC) posed greater risk to algae, while benzophenone-3 (BP-3) and ethylhexyl methoxycinnamate (EHMC) were more likely to pose a risk to fishes and also posed high risk of bleaching in hard corals in aquatic recreational areas in Hong Kong. This study is the first to report the occurrence of organic UV filters in the Arctic and provides a wider assessment of their potential negative impacts in the marine environment. Copyright © 2014 Elsevier Ltd. All rights reserved.

  3. Environmental occurrence and ecological risk assessment of organic UV filters in marine organisms from Hong Kong coastal waters.

    Science.gov (United States)

    Sang, Ziye; Leung, Kelvin Sze-Yin

    2016-10-01

    Organic UV filters, now considered to be emerging contaminants in aquatic ecosystems, are being intensively tracked in environmental waters worldwide. However, their environmental fate and impact of these contaminants on marine organisms remains largely unknown, especially in Asia. This work elucidates the occurrence and the ecological risks of seven UV filters detected in farmed fish, wild mussels and some other wild organisms collected from local mariculture farms in Hong Kong. For all of the organisms, ethylhexyl methoxycinnamate (EHMC) and octyl dimethyl p-aminobenzoic acid (OD-PABA) were the predominant contaminants with the highest concentrations up to 51.3 and 24.1ng/g (dw), respectively; lower levels were found for benzophenone-8 (BP-8), octocrylene (OC) and benzophenone-3 (BP-3) from UV filters indicated a positive correlation between their measured concentrations and the anthropogenic activities responsible for their direct emission. The ecological risk assessment specific to the marine aquatic environment was carried out. The risk quotient (RQ) values of EHMC and BP-3 were calculated as 3.29 and 2.60, respectively, indicating these two UV filters may pose significant risks to the marine aquatic environment. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Ecotoxicological evaluation of four UV filters using marine organisms from different trophic levels Isochrysis galbana, Mytilus galloprovincialis, Paracentrotus lividus, and Siriella armata.

    Science.gov (United States)

    Paredes, E; Perez, S; Rodil, R; Quintana, J B; Beiras, R

    2014-06-01

    Due to the concern about the negative effects of exposure to sunlight, combinations of UV filters like 4-Methylbenzylidene-camphor (4-MBC), Benzophenone-3 (BP-3), Benzophenone-4 (BP-4) and 2-Ethylhexyl-4-methoxycinnamate (EHMC) are being introduced in all kind of cosmetic formulas. These chemicals are acquiring a concerning status due to their increasingly common use and the potential risk for the environment. The aim of this study is to assess the behaviour of these compounds in seawater, the toxicity to marine organisms from three trophic levels including autotrophs (Isochrysis galbana), herbivores (Mytilus galloprovincialis and Paracentrotus lividus) and carnivores (Siriella armata), and set a preliminary assessment of potential ecological risk of UV filters in coastal ecosystems. In general, EC50 results show that both EHMC and 4-MBC are the most toxic for our test species, followed by BP-3 and finally BP-4. The most affected species by the presence of these UV filters are the microalgae I. galbana, which showed toxicity thresholds in the range of μg L(-1) units, followed by S. armata>P. Lividus>M. galloprovincialis. The UV filter concentrations measured in the sampled beach water were in the range of tens or even hundreds of ng L(-1). The resulting risk quotients showed appreciable environmental risk in coastal environments for BP-3 and 4-MBC. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. Determination of Iron Species by Combination of Solvent Assisted-Dispersive Solid Phase Extraction and Spectrophotometry

    Directory of Open Access Journals (Sweden)

    Zahra Dehghani

    2015-06-01

    Full Text Available A simple, rapid and sensitive solvent assisted-dispersive solid phase extraction method was developed for the extraction of iron(II prior to its spectrophotometric determination. The Fe(II reacted with 2,4,6-tris(2-pyridyl-1,3,5-triazine, neutralized with sodium dodecyl sulfate and extracted onto the fine particles of benzophenone which were formed upon rapid injection of a mixture of benzophenone as the sorbent and ethanol as the disperser solvent into the aqueous solution. After phase separation, the sedimented phase containing the complex was dissolved in ethanol and the analyte concentration was determined by measuring its absorption at 594 nm. Total iron was determined after the reduction of Fe(III to Fe(II with hydroxylamine hydrochloride. Under the optimized conditions, an enhancement factor of 32, the detection limit of 0.16 µg l-1, and the relative standard deviation of 1.9% (n = 6 at 20 µg l-1 concentration level of Fe(II were achieved. The method was successfully applied to the determination of iron species in water samples and total iron in infant dry formula milk, apple, rice, spinach and parsley samples.

  6. Widespread occurrence of estrogenic UV-filters in aquatic ecosystems in Switzerland

    Energy Technology Data Exchange (ETDEWEB)

    Fent, Karl, E-mail: karl.fent@bluewin.c [University of Applied Sciences (FHNW), School of Life Sciences, Gruendenstrasse 40, CH-4132 Muttenz (Switzerland); Swiss Federal Institute of Technology (ETH Zurich), Department of Environmental Sciences, CH-8092 Zuerich (Switzerland); Zenker, Armin [University of Applied Sciences (FHNW), School of Life Sciences, Gruendenstrasse 40, CH-4132 Muttenz (Switzerland); Rapp, Maja [Swiss Federal Institute of Technology (ETH Zurich), Institute of Environmental Engineering, Wolfgang-Pauli-Strasse 15, CH-8093 Zuerich (Switzerland)

    2010-05-15

    We performed a trace analytical study covering nine hormonally active UV-filters by LC-MS/MS and GC-MS in river water and biota. Water was analysed at 10 sites above and below wastewater treatment plants in the river Glatt using polar organic chemical integrative samplers (POCIS). Four UV-filters occurred in the following order of decreasing concentrations; benzophenone-4 (BP-4) > benzophenone-3 (BP-3) > 3-(4-methyl)benzylidene-camphor (4-MBC) > 2-ethyl-hexyl-4-trimethoxycinnamate (EHMC). BP-4 ranged from 0.27 to 24.0 mug/POCIS, BP-3, 4-MBC and EHMC up to 0.1 mug/POCIS. Wastewater was the most important source. Levels decreased with higher river water flow. No significant in-stream removal occurred. BP-3, 4-MBC and EHMC were between 6 and 68 ng/L in river water. EHMC was accumulated in biota. In all 48 macroinvertebrate and fish samples from six rivers lipid-weighted EHMC occurred up to 337 ng/g, and up to 701 ng/g in 5 cormorants, suggesting food-chain accumulation. UV-filters are found to be ubiquitous in aquatic systems. - Several UV-filters from cosmetics and materials protection occur in rivers and EHMC accumulates in biota.

  7. Rapid Screening of Chemical Constituents inRhizoma Anemarrhenaeby UPLC-Q-TOF/MS Combined with Data Postprocessing Techniques.

    Science.gov (United States)

    Shan, Lanlan; Wu, Yuanyuan; Yuan, Lei; Zhang, Yani; Xu, Yanyan; Li, Yubo

    2017-01-01

    Rhizoma Anemarrhenae , a famous traditional Chinese medicine (TCM), is the dried rhizome of Anemarrhena asphodeloides Bge. ( Anemarrhena Bunge of Liliaceae). The medicine presents anti-inflammatory, antipyretic, sedative, and diuretic effects. The chemical constituents of Rhizoma Anemarrhenae are complex and diverse, mainly including steroidal saponins, flavonoids, phenylpropanoids, benzophenones, and alkaloids. In this study, UPLC-Q-TOF/MS was used in combination with data postprocessing techniques, including characteristic fragments filter and neutral loss filter, to rapidly classify and identify the five types of substances in Rhizoma Anemarrhenae . On the basis of numerous literature reviews and according to the corresponding characteristic fragments produced by different types of compounds in combination with neutral loss filtering, we summarized the fragmentation patterns of the main five types of compounds and successfully screened and identified 32 chemical constituents in Rhizoma Anemarrhenae . The components included 18 steroidal saponins, 6 flavonoids, 4 phenylpropanoids, 2 alkaloids, and 2 benzophenones. The method established in this study provided necessary data for the study on the pharmacological effects of Rhizoma Anemarrhenae and also provided the basis for the chemical analysis and quality control of TCMs to promote the development of a method for chemical research on TCMs.

  8. Advances in analytical methods and occurrence of organic UV-filters in the environment--A review.

    Science.gov (United States)

    Ramos, Sara; Homem, Vera; Alves, Arminda; Santos, Lúcia

    2015-09-01

    UV-filters are a group of compounds designed mainly to protect skin against UVA and UVB radiation, but they are also included in plastics, furniture, etc., to protect products from light damage. Their massive use in sunscreens for skin protection has been increasing due to the awareness of the chronic and acute effects of UV radiation. Some organic UV-filters have raised significant concerns in the past few years for their continuous usage, persistent input and potential threat to ecological environment and human health. UV-filters end up in wastewater and because wastewater treatment plants are not efficient in removing them, lipophilic compounds tend to sorb onto sludge and hydrophilics end up in river water, contaminating the existing biota. To better understand the risk associated with UV-filters in the environment a thorough review regarding their physicochemical properties, toxicity and environmental degradation, analytical methods and their occurrence was conducted. Higher UV-filter concentrations were found in rivers, reaching 0.3mg/L for the most studied family, the benzophenone derivatives. Concentrations in the ng to μg/L range were also detected for the p-aminobenzoic acid, cinnamate, crylene and benzoyl methane derivatives in lake and sea water. Although at lower levels (few ng/L), UV-filters were also found in tap and groundwater. Swimming pool water is also a sink for UV-filters and its chlorine by-products, at the μg/L range, highlighting the benzophenone and benzimidazole derivatives. Soils and sediments are not frequently studied, but concentrations in the μg/L range have already been found especially for the benzophenone and crylene derivatives. Aquatic biota is frequently studied and UV-filters are found in the ng/g-dw range with higher values for fish and mussels. It has been concluded that more information regarding UV-filter degradation studies both in water and sediments is necessary and environmental occurrences should be monitored more

  9. Effect of solvents on the bulk growth of 4-aminobenzophenone single crystals: A potential material for blue and green lasers

    Science.gov (United States)

    Natarajan, V.; Usharani, S.; Arivanandhan, M.; Anandan, P.; Hayakawa, Y.

    2015-06-01

    Although 4-aminobenzophenone (4-ABP) is the best derivative of benzophenone with 260 times higher second harmonic generation (SHG) efficiency than potassium dihydrogen phosphate (KDP), growth of high quality bulk crystal still remains a difficult task. In the present work, the effect of solvents on solubility and growth aspects of 4-ABP was investigated to grow inclusion free 4-ABP crystals. The growth processes were discussed based on solute-solvent interaction in two different growth media of ethyl acetate and ethanol. The growth rate and thereby solvent inclusions are relatively higher in ethyl acetate grown crystal than the crystal grown from ethanol. The structural, thermal and optical properties of 4-ABP crystals were studied. The enthalpy of 4-ABP melting process was estimated from differential thermal analysis. The optical transmission study shows that 4-ABP crystals grown from ethanol has high transparency compared to ethyl acetate grown sample due to solvent inclusion in the later crystal.

  10. Development of an in vitro thin-film solid-phase microextraction method to determine the bioavailability of xenoestrogens in soil.

    Science.gov (United States)

    Engler, Katherine Neafsey; Lemley, Ann T

    2013-09-01

    Biosolids applied to agricultural fields, parks, and other areas represent significant sources of estrogen-like endocrine disrupting compound (EEDC) inputs to soil. It is important to determine the bioavailability of EEDCs in soil to inform risk assessment concerning their environmental presence; Eisenia fetida (earthworms) are typically used in traditional in vivo bioavailability experiments. The development of an in vitro bioavailability method will decrease time, expense, and use of solvents in future analyses. A thin-film solid-phase microextraction (TF-SPME) method for determining the bioavailability of several EEDCs detected in biosolids was developed and optimized. It was found that the TF-SPME method could be used to calculate equilibrium porewater concentrations of diethylhexyl phthalate, bisphenol A, benzophenone, and triclosan at environmentally relevant concentrations in artificial soil within 88 min. The potential and limitations of using TF-SPME-generated porewater concentrations to predict E. fetida tissue concentrations are discussed. Copyright © 2013 SETAC.

  11. Kinetic Isotope Effects in the Reduction of Methyl Iodide

    DEFF Research Database (Denmark)

    Holm, Torkil

    1999-01-01

    a Grignard reagent to methyl iodide, and for reduction of methyl iodide with tributyltin hydride or with gaseous hydrogen iodide. Very small KIE's were found for electron transfer to methyl iodide from magnesium in ether or from sodium in ammonia. The reason may be that these reactions are transport......a-Deuterium kinetic isotope effects (KIE's) have been determined for the reaction of methyl iodide with a series of reducing agents. Reagents which transfer hydride ion in an SN2 reaction show small inverse or small normal KIE's. Reagents which transfer an electron to methyl iodide to produce...... methyl radical show large normal KIE's up to 20 % per a-D. Large KIE's were found for the reaction of methyl iodide with sodium, for Pd-catalyzed reaction of methyl iodide with hydrogen, for ET at a platinum cathode, for ET from benzophenone ketyl or from sodium naphthalenide, for iron catalyzed ET from...

  12. Biocontrol evaluation of extracts and a major component, clusianone, from Clusia fluminensis Planch. & Triana against Aedes aegypti

    Science.gov (United States)

    Anholeti, Maria C; Duprat, Rodrigo C; Figueiredo, Maria R; Kaplan, Maria AC; Santos, Marcelo Guerra; Gonzalez, Marcelo S; Ratcliffe, Norman A; Feder, Denise; Paiva, Selma R; Mello, Cicero B

    2015-01-01

    Studies evaluated the effects of hexanic extracts from the fruits and flowers ofClusia fluminensis and the main component of the flower extract, a purified benzophenone (clusianone), against Aedes aegypti. The treatment of larvae with the crude fruit or flower extracts from C. fluminensis did not affect the survival ofAe. aegypti (50 mg/L), however, the flower extracts significantly delayed development of Ae. aegypti. In contrast, the clusianone (50 mg/L) isolate from the flower extract, representing 54.85% of this sample composition, showed a highly significant inhibition of survival, killing 93.3% of the larvae and completely blocking development of Ae. aegypti. The results showed, for the first time, high activity of clusianone against Ae. aegypti that both killed and inhibited mosquito development. Therefore, clusianone has potential for development as a biopesticide for controlling insect vectors of tropical diseases. Future work will elucidate the mode of action of clusianone isolated from C. fluminensis. PMID:26200711

  13. THE INFLUENCE OF SELECTED ORGANIC MICROPOLLUTANTS ON WATER ECOSYSTEMS

    Directory of Open Access Journals (Sweden)

    Edyta Anna Kudlek

    2017-06-01

    Full Text Available The paper presents a literature review in terms of the impact of selected micropollutants from the group of pharmaceutical compounds, food preservatives, pesticides and organic UV filters on various plants and animals species, which inhabit the water ecosystems. During own studies the impact of concentrations of micropollutants in the water environment on selected indicator organisms was evaluated. The study was conducted using saltwater Aliivibrio fischer bacteria, freshwater Daphnia magna and saltwater Artemia fanciscana crustaceans, as well as vascular plants Lemna minor. It was shown that the test organisms are characterized by a different sensitivity for the presence of micropollutants. For all applied tests an increase in the response of indicator organisms with the increasing compound concentration was observed. It demonstrates the growing toxic impact of micropollutants. The solution of benzophenone-3 at a concentration of 5 mg/dm3 was characterized by the highest toxic effects against both bacteria, crustaceans and vascular plants.

  14. Characterization of phenolic and other polar compounds in peel and flesh of pink guava (Psidium guajava L. cv. 'Criolla') by ultra-high performance liquid chromatography with diode array and mass spectrometric detection.

    Science.gov (United States)

    Rojas-Garbanzo, Carolina; Zimmermann, Benno F; Schulze-Kaysers, Nadine; Schieber, Andreas

    2017-10-01

    Pink guava (Psidium guajava L.) is a highly consumed fruit in tropical countries. Despite of interesting research on health effects of this fruit, investigations into the profile of secondary plant metabolites are scarce. In this study, the phenolic compounds in the peel and flesh of pink guava were characterized by ultra-high performance liquid chromatography with diode array and mass spectrometric detection. Sixty phenolic compounds were characterized by MS 2 and classified as ellagitannins, flavones, flavonols, flavanols, proanthocyanidins, dihydrochalcones, and anthocyanidins, and non-flavonoids such as phenolic acid derivatives, stilbenes, acetophenones, and benzophenones. Forty-two polyphenols are reported for the first time in both peel and flesh, and twenty-four compounds were detected for the first time in P. guajava, e.g., phlorizin, nothofagin, astringin, chrysin-C-glucoside, valoneic acid bilactone, cinnamoyl-glucoside, and two dimethoxycinnamoyl-hexosides. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. Distribution of Non-Persistent Endocrine Disruptors in Two Different Regions of the Human Brain

    DEFF Research Database (Denmark)

    van der Meer, Thomas P; Artacho-Cordón, Francisco; Swaab, Dick F

    2017-01-01

    Non-persistent endocrine disrupting chemicals (npEDCs) can affect multiple organs and systems in the body. Whether npEDCs can accumulate in the human brain is largely unknown. The major aim of this pilot study was to examine the presence of environmental phenols and parabens in two distinct brain...... and BMI parabens were measured by isotope dilution TurboFlow-LC-MS/MS. In the hypothalamus, seven suspect npEDCs (bisphenol A, triclosan, triclocarban and methyl-, ethyl-, n-propyl-, and benzyl paraben) were detected, while five npEDCs (bisphenol A......, benzophenone-3, triclocarban, methyl-, and n-propyl paraben) were found in the white-matter brain tissue. We observed higher levels of methylparaben (MeP) in the hypothalamic tissue of obese subjects as compared to controls (p = 0.008). Our findings indicate that some suspected npEDCs are able to cross...

  16. Red propolis: Chemical composition and pharmacological activity

    Directory of Open Access Journals (Sweden)

    Luciane Corbellini Rufatto

    2017-07-01

    Full Text Available Propolis has been used worldwide for years in folk medicine and currently marketed by the pharmaceutical industry. In Brazil, propolis was classified into 13 groups based on their organoleptics and physicochemical characteristics. The 13th type named red propolis has been an important source of investigation since late 90s. Their property comes from the countless compounds, including terpenes, pterocarpans, prenylated benzophenones and especially the flavonoids. This last compound class has been indicated as the responsible for its potent pharmacological actions, highlighting the antimicrobial, anti-inflammatory, antioxidant, healing and antiproliferative activities. The red propolis can also be found in other countries, especially Cuba, which has similar features as the Brazilian. Therefore, with the compilation of 80 papers, this review aims to provide a key reference for researchers interested in natural products and discovery of new active compounds, such as from propolis.

  17. Response of ultrafast scintillators

    International Nuclear Information System (INIS)

    Cheng, J.C.; Lerche, R.A.; Tirsell, K.G.; Tripp, G.R.

    1976-01-01

    Measurements of the properties of subnanosecond, quenched NE111 plastic scintillators with various concentrations of acetophenone and benzophenone are presented. These quenching agents have been found to very significantly decrease the NE111 decay time. Measurements are made using UV and laser produced x-ray radiations. The scintillations are detected using a visible streak camera with 10 ps resolution. The paper will include measurements of: (1) 10-90 percent rise time, (2) FWHM, (3) decay time, (4) relative scintillator efficiencies, (5) amplitudes vs. time measurements of the long decay component. All temporal measurements are obtained from a gold cathode ultrafast x-ray streak camera, and the detailed x-ray energy spectrum above 1 keV is also measured using an array of x-ray PIN diodes equipped with the appropriate K-edge filters. Details of the experimental measurements are discussed and anticipated applications are included

  18. Response of ultrafast scintillators

    International Nuclear Information System (INIS)

    Cheng, J.C.; Lerche, R.A.; Tripp, G.R.; Coleman, L.W.

    1976-09-01

    Measurements of the properties of subnanosecond, quenched NE111 plastic scintillators with various concentrations of acetophenone and benzophenone are presented. These quenching agents have been found to very significantly decrease the NE111 decay time. Measurements are made using UV and laser produced x-ray radiations. The scintillations are detected using a visible streak camera with 10 ps resolution. Measurements of: (1) 10-90 percent rise time, (2) FWHM, (3) decay time, (4) relative scintillator efficiencies, and (5) amplitudes vs. time measurements of the long decay component are presented. All temporal measurements are obtained from a gold cathode ultrafast x-ray streak camera, and the detailed x-ray energy spectrum above 1 keV is also measured using an array of x-ray PIN diodes equipped with the appropriate K-edge filters. Details of the experimental measurements are discussed and anticipated applications are included

  19. A Neutron Streak Camera Designed for ICF Fuel Ion Temperature

    Science.gov (United States)

    Chen, Jiabin; Liao, Hua; Chen, Ming

    2007-11-01

    A neutron streak camera was designed for inertial confinement fusion (ICF) fuel ion temperature diagnostic. It is made of a 1 cm thick x8 cm diam piece of 3% benzophenone quenched plastic scintillator with about a 190 ps FWHM and a streak tube (55ps time resolution) with large-area photocathode (φ30 mm) showed no slit. The electron beam from the photocathode is focused into a little spot (φ1mm). Then the spot is scanned directly and multiplied by an internal microchannel plate. This greatly improves the sensitivity of the tube. The neutron streak camera combines the advangtages of scintillation detector (with high neutron detection efficiency) and of streak camera (with fast time response). The whole detection system time resolution is 300ps and can record neutron time of flight signals from ICF implosion target with yields of 10^7 DT neutron per shot.

  20. Crystallization and preliminary crystallographic analysis of an acridone-producing novel multifunctional type III polyketide synthase from Huperzia serrata

    Energy Technology Data Exchange (ETDEWEB)

    Morita, Hiroyuki [Mitsubishi Kagaku Institute of Life Sciences (MITILS), 11 Minamiooya, Machida, Tokyo 194-8511 (Japan); Kondo, Shin; Kato, Ryohei [Innovation Center Yokohama, Mitsubishi Chemical Corporation, 1000 Kamoshida, Aoba, Yokohama, Kanagawa 227-8502 (Japan); Wanibuchi, Kiyofumi; Noguchi, Hiroshi [School of Pharmaceutical Sciences, University of Shizuoka and the COE21 Program, Shizuoka 422-8526 (Japan); Sugio, Shigetoshi, E-mail: sugio.shigetoshi@mw.m-kagaku.co.jp [Innovation Center Yokohama, Mitsubishi Chemical Corporation, 1000 Kamoshida, Aoba, Yokohama, Kanagawa 227-8502 (Japan); Abe, Ikuro, E-mail: sugio.shigetoshi@mw.m-kagaku.co.jp [School of Pharmaceutical Sciences, University of Shizuoka and the COE21 Program, Shizuoka 422-8526 (Japan); PRESTO, Japan Science and Technology Agency, Kawaguchi, Saitama 332-0012 (Japan); Kohno, Toshiyuki, E-mail: sugio.shigetoshi@mw.m-kagaku.co.jp [Mitsubishi Kagaku Institute of Life Sciences (MITILS), 11 Minamiooya, Machida, Tokyo 194-8511 (Japan)

    2007-07-01

    An acridone-producing novel type III polyketide synthase from H. serrata has been overexpressed in E. coli, purified and crystallized. Diffraction data have been collected to 2.0 Å. Polyketide synthase 1 (PKS1) from Huperzia serrata is a plant-specific type III polyketide synthase that shows an unusually versatile catalytic potential, producing various aromatic tetraketides, including chalcones, benzophenones, phlorogulucinols and acridones. Recombinant H. serrata PKS1 expressed in Escherichia coli was crystallized using the hanging-drop vapour-diffusion method. The crystals belonged to space group I222 or I2{sub 1}2{sub 1}2{sub 1}, with unit-cell parameters a = 73.3, b = 85.0, c = 137.7 Å, α = β = γ = 90.0°. Diffraction data were collected to 2.0 Å resolution using synchrotron radiation at BL24XU of SPring-8.

  1. Study of maleic anhydride and styrene grafted onto polypropylene induced by UV irradiation

    International Nuclear Information System (INIS)

    Li Zhenzhong; He Wei; Guo Hongjun; Zhang Wenxiong; Ma Yalin

    2007-01-01

    Maleic anhydride (MAH) and styrene (St) grafted onto polypropylene (PP) were prepared by UV irradiation. Effects of the irradiation time, monomer and initiator content on the grafting rate and melt flow rate (MFR) were studied. The results show that the optimal duration of UV irradiation is 30s. The grafting rate increases with initiator content when initiator content less than 0.6 phr, the MFR value of grafted PP reaches the highest point when benzophenone (BP) content is 0.4 phr. The content of MAH and St have an effect on the grafting rate and MFR value of the grafted PP, and the optimal contents of monomer is 4 phr. The existence of St as a comonomer reduces apparently the MFR value of grafted PP greatly. Grafted PP present significant changes in crystallization and fusion peaks, indicating differences in crystal size and formation after grafting reaction. (authors)

  2. Effects of the novel poly(methyl methacrylate) (PMMA)-encapsulated organic ultraviolet (UV) filters on the UV absorbance and in vitro sun protection factor (SPF).

    Science.gov (United States)

    Wu, Pey-Shiuan; Huang, Lan-Ni; Guo, Yi-Cing; Lin, Chih-Chien

    2014-02-05

    Sunscreens are thought to protect skin from many of the harmful effects of ultraviolet (UV) light and the photostability of sunscreens is thus an important concern in their application. Therefore, to discover new UV filters or to modify well-known UV filters are presents an important way for development of sunscreens. In this study, we presented several novel poly(methyl methacrylate) (PMMA) encapsulated organic UV filters, including encapsulated benzophenone-3 (TB-MS), avobenzone (TA-MS), octyl methoxycinnamate (TO-MS) and diethylamino hydroxybenzoyl hexyl benzoate (TD-MS). Our results have demonstrated that PMMA-encapsulated UV filters have improved safety, photoprotective ability and photostability. We proposed therefore that these PMMA-encapsulated UV filters can be used as ingredients for sunscreen products in the future. Copyright © 2014 Elsevier B.V. All rights reserved.

  3. Recent Advances on Endocrine Disrupting Effects of UV Filters.

    Science.gov (United States)

    Wang, Jiaying; Pan, Liumeng; Wu, Shenggan; Lu, Liping; Xu, Yiwen; Zhu, Yanye; Guo, Ming; Zhuang, Shulin

    2016-08-03

    Ultraviolet (UV) filters are used widely in cosmetics, plastics, adhesives and other industrial products to protect human skin or products against direct exposure to deleterious UV radiation. With growing usage and mis-disposition of UV filters, they currently represent a new class of contaminants of emerging concern with increasingly reported adverse effects to humans and other organisms. Exposure to UV filters induce various endocrine disrupting effects, as revealed by increasing number of toxicological studies performed in recent years. It is necessary to compile a systematic review on the current research status on endocrine disrupting effects of UV filters toward different organisms. We therefore summarized the recent advances on the evaluation of the potential endocrine disruptors and the mechanism of toxicity for many kinds of UV filters such as benzophenones, camphor derivatives and cinnamate derivatives.

  4. A 2-(2’-pyridylquinoline ruthenium(II complex as an active catalyst for the transfer hydrogenation of ketones

    Directory of Open Access Journals (Sweden)

    Zacharopoulos Nikolaos

    2016-01-01

    Full Text Available The ruthenium(II complex cis-[RuCl2(PPh32(L1] (1 where L1 = 2-(2’-pyridylquinoline was obtained in high yield from the reaction of [RuCl2(PPh33] with L1. The new compound was characterized by different spectroscopic methods including FT-IR, UV-Vis, NMR (1H, 31P spectroscopy along with a mass spectrometric analysis (ESI-MS and conductivity measurements. 31P NMR spectroscopy provided evidence that the two PPh3 ligands are orientated trans to each other in an octahedral environment. Complex (1 was tested in the transfer hydrogenation of various ketones in 2-propanol at 82 oC. The catalytic activity of (1 displayed quantitative conversions for benzophenone and 4-chloroacetophenone.

  5. Easy access to nucleophilic boron through diborane to magnesium boryl metathesis

    Science.gov (United States)

    Pécharman, Anne-Frédérique; Colebatch, Annie L.; Hill, Michael S.; McMullin, Claire L.; Mahon, Mary F.; Weetman, Catherine

    2017-04-01

    Organoboranes are some of the most synthetically valuable and widely used intermediates in organic and pharmaceutical chemistry. Their synthesis, however, is limited by the behaviour of common boron starting materials as archetypal Lewis acids such that common routes to organoboranes rely on the reactivity of boron as an electrophile. While the realization of convenient sources of nucleophilic boryl anions would open up a wealth of opportunity for the development of new routes to organoboranes, the synthesis of current candidates is generally limited by a need for highly reducing reaction conditions. Here, we report a simple synthesis of a magnesium boryl through the heterolytic activation of the B-B bond of bis(pinacolato)diboron, which is achieved by treatment of an easily generated magnesium diboranate complex with 4-dimethylaminopyridine. The magnesium boryl is shown to act as an unambiguous nucleophile through its reactions with iodomethane, benzophenone and N,N'-di-isopropyl carbodiimide and by density functional theory.

  6. Aquisição de tempos de vida de fosforescência com resolução de fase e sua aplicação ao estudo de relaxações em polímeros Phosphorescence lifetime in polymer relaxation studies: phase resolution method

    Directory of Open Access Journals (Sweden)

    M. Talhavini

    1998-06-01

    Full Text Available We describe in this work a simple experimental set up to perform time dependent luminescence experiments in time scales from mili-seconds to seconds, based on the phase resolution of the emission signal. This system is composed by modulation of a continuous light source with an external chopper controlled by a lock-in amplifier. We exemplified the utility of the system in studies of phosphorecence emission using benzophenone dissolved in polystyrene and since the phosphorescence intensity and lifetime are temperature-dependent processes, we also studied polymer relaxation processes in the temperature range from 20 to 400K. A software that drives the spectrofluorimeter and controls both the cryosystem and the lock-in amplifier was developed.

  7. Laboratory evaluation of Clusia fluminensis extracts and their isolated compounds against Dysdercus peruvianus and Oncopeltus fasciatus

    Directory of Open Access Journals (Sweden)

    Rodrigo C. Duprat

    Full Text Available ABSTRACT The effects of the hexanic extracts of the fruits and flowers of Clusia fluminensis Planch. & Triana, Clusiaceae, as well as their main constituents, the triterpene lanosterol and the benzophenone clusianone, were evaluated on hemipterans Dysdercus peruvianus and Oncopeltus fasciatus. The topical treatments of insects with the hexanic extracts significantly affected the survival of O. fasciatus, but not that of D. peruvianus. Concomitantly, extracts delayed the development of both hemipterans. Moreover, isolated lanosterol significantly reduced both the survival and development of O. fasciatus and D. peruvianus, while clusianone only reduce the survival of D. peruvianus and marginally inhibited the development of both insects. The results show the specific activity of lanosterol and clusianone against the two evaluated insect species and indicate the potential of compounds derived from C. fluminensis for the development of specific biopesticides for the control of agricultural pests. Subsequent work will examine the mode of action of lanosterol and clusianone isolates from C. fluminensis.

  8. Study on the natural pigments present in the Hulls of Garcinia Mangostana Linn

    International Nuclear Information System (INIS)

    San Dar Aung; Aye Aye Tun; San San Aye; Maung Maung Htay

    2005-09-01

    Garcinia mangostana Linn,(Family; Guttiferae) is known to be a rich source of bioactive molecules including flavonoids, benzophenones and lactones. A variety of xanthones have been isolated from mangosteen plants and fruits include the hull, rind heartwood and flesh. The fruit hull is used as an astringent and also used against cholera, dysentery and diarrhoea in traditional medicinal system. Petroleum ether extraction of the dried and powered fruit hulls followed by column chromatographic separation afforded two compounds, namely, gartanin (1) (0.48% in yield, mp 146-152 ) and mangostin (2) (0.97% in yield, mp (179-180). The structures of these two compounds have been identified by UV, FT-IR, NMR and EIMS. These identifications were confirmed by comparison of melting point values with reported data in the literature

  9. Controlled UV-C light-induced fusion of thiol-passivated gold nanoparticles.

    Science.gov (United States)

    Pocoví-Martínez, Salvador; Parreño-Romero, Miriam; Agouram, Said; Pérez-Prieto, Julia

    2011-05-03

    Thiol-passivated gold nanoparticles (AuNPs) of a relatively small size, either decorated with chromophoric groups, such as a phthalimide (Au@PH) and benzophenone (Au@BP), or capped with octadecanethiol (Au@ODCN) have been synthesized and characterized by NMR and UV-vis spectroscopy as well as transmission electron microscopy (TEM). These NPs were irradiated in chloroform at different UV-wavelengths using either a nanosecond laser (266 and 355 nm, ca. 12 mJ/pulse, 10 ns pulse) or conventional lamps (300 nm lamp illumination. Remarkably, laser excitation at 266 nm induced a fast (minutes time-scale) increase in the size of the NPs, producing huge spherical nanocrystals, while lamp-irradiation at UV-C wavelengths brought about nanonetworks of partially fused NPs with a larger diameter than the native NPs.

  10. Investigation of the structure of photosynthetic reaction centers. Progress report, June 1, 1981-April 1, 1982

    International Nuclear Information System (INIS)

    van Willigen, H.

    1982-04-01

    The investigation is concerned with the application of Electron Nuclear Double Resonance (ENDOR) and Electron Nuclear Triple Resonance (TRIPLE) in the study of the photo excited triplet state of photosynthetic resonance methods hyperfine interactions between unpaired electrons and nuclear spins can be measured, giving an insight in the electronic and geometric structure of paramagnetic systems. During this initial phase of the project, research has focused on the following areas. (1) Instrumental aspects associated with the application of ENDOR and TRIPLE on the photo excited triplets randomly oriented in solid solution. (2) Exploration of the conditions required for these studies employing ground state triplet systems. (3) Study of photo excited triplet states of model systems such as naphthylene, zinc and magnesium tetraphenyl-porphyrin in polymethylmethacrylate or polycrystalline benzophenone. Progress made in these areas is discussed

  11. Identification of suspected hazardous chemical contaminants in recycled pastry packaging.

    Science.gov (United States)

    Ahmadkhaniha, Reza; Rastkari, Noushin

    2017-01-01

    The safe use of recycled paper and cardboard material for food packaging applications is     an important area of investigation. Therefore, the aim of this study was to determine which hazardous chemi- cal pollutants were found in paper and cardboard samples used for pastry packaging, and to measure the migration of pollutants over time into the pastries. In this study, the presence of some organic pollutants in common confectionery packaging, and the effects of storage time and type of pastry on pollutant migration, were investigated. The results of the study indicate that harmful compounds such as benzophenone, pentachlorophenol, bis(2-ethylhexyl) phthalate and dibutyl phthalate are present at high concentrations in most recycled boxes used for pastry packaging. Since the migration of some of the hazardous compounds from the packaging materials into the pastries under normal conditions was indicated, it is recommended that the procedure for preparing pastry packaging materials should be reconsidered and improved.

  12. A new screening method for flunitrazepam in vodka and tequila by fluorescence spectroscopy.

    Science.gov (United States)

    Leesakul, Nararak; Pongampai, Sirintip; Kanatharana, Proespichaya; Sudkeaw, Pravit; Tantirungrotechai, Yuthana; Buranachai, Chittanon

    2013-01-01

    A new screening method for flunitrazepam in colourless alcoholic beverages based on a spectroscopic technique is proposed. Absorption and steady-state fluorescence of flunitrazepam and its protonated form with various acids were investigated. The redshift of the wavelength of maximum absorption was distinctively observed in protonated flunitrazepam. An emissive fluorescence at 472 nm was detected in colourless spirits (vodka and tequila) at room temperature. 2-M perchloric acid was the most appropriated proton source. By using electron ionization mass spectrometry and time-dependent density functional theory calculations, the possible structure of protonated flunitrazepam was identified to be 2-nitro-N-methylacridone, an acridone derivative as opposed to 2-methylamino-5-nitro-2'-fluorobenzophenone, a benzophenone derivative. Copyright © 2012 John Wiley & Sons, Ltd.

  13. Personal care product use as a predictor of urinary concentrations of certain phthalates, parabens, and phenols in the HERMOSA study.

    Science.gov (United States)

    Berger, Kimberly P; Kogut, Katherine R; Bradman, Asa; She, Jianwen; Gavin, Qi; Zahedi, Rana; Parra, Kimberly L; Harley, Kim G

    2018-01-09

    Use of personal care products, such as makeup, soaps, and sunscreen, may expose adolescent girls to potential endocrine disruptors, including phthalates, parabens, and other phenols. We evaluated the relationship between recent self-reported personal care product use and concentrations for urinary metabolites of phthalates, parabens, triclosan, and benzophenone-3 (BP-3) in 100 Latina adolescents. Girls who reported using makeup every day vs. rarely/never had higher urinary concentrations of monoethyl phthalate (MEP) (102.2 ng/mL vs. 52.4 ng/mL, P-value: 0.04), methyl paraben (MP) (120.5 ng/mL vs. 13.4 ng/mL, P-value value personal care product use is associated with higher exposure to certain phthalates, parabens, and other phenols in urine. This may be especially relevant in adolescent girls who have high use of personal care products during a period of important reproductive development.

  14. Recent Advances on Endocrine Disrupting Effects of UV Filters

    Directory of Open Access Journals (Sweden)

    Jiaying Wang

    2016-08-01

    Full Text Available Ultraviolet (UV filters are used widely in cosmetics, plastics, adhesives and other industrial products to protect human skin or products against direct exposure to deleterious UV radiation. With growing usage and mis-disposition of UV filters, they currently represent a new class of contaminants of emerging concern with increasingly reported adverse effects to humans and other organisms. Exposure to UV filters induce various endocrine disrupting effects, as revealed by increasing number of toxicological studies performed in recent years. It is necessary to compile a systematic review on the current research status on endocrine disrupting effects of UV filters toward different organisms. We therefore summarized the recent advances on the evaluation of the potential endocrine disruptors and the mechanism of toxicity for many kinds of UV filters such as benzophenones, camphor derivatives and cinnamate derivatives.

  15. Evaluation of fungal- and photo-degradation as potential treatments for the removal of sunscreens BP3 and BP1

    International Nuclear Information System (INIS)

    Gago-Ferrero, Pablo; Badia-Fabregat, Marina; Olivares, Alba; Piña, Benjamin; Blánquez, Paqui; Vicent, Teresa; Caminal, Gloria; Díaz-Cruz, M. Silvia

    2012-01-01

    Photodecomposition might be regarded as one of the most important abiotic factors affecting the fate of UV absorbing compounds in the environment and photocatalysis has been suggested as an effective method to degrade organic pollutants. However, UV filters transformation appears to be a complex process, barely addressed to date. The white rot fungus Trametes versicolor is considered as a promising alternative to conventional aerobic bacterial degradation, as it is able to metabolise a wide range of xenobiotics. This study focused on both degradation processes of two widely used UV filters, benzophenone-3 (BP3) and benzophenone-1 (BP1). Fungal treatment resulted in the degradation of more than 99% for both sunscreens in less than 24 h, whereas photodegradation was very inefficient, especially for BP3, which remained unaltered upon 24 h of simulated sunlight irradiation. Analysis of metabolic compounds generated showed BP1 as a minor by-product of BP3 degradation by T. versicolor while the main intermediate metabolites were glycoconjugate derivatives. BP1 and BP3 showed a weak, but significant estrogenic activity (EC50 values of 0.058 mg/L and 12.5 mg/L, respectively) when tested by recombinant yeast assay (RYA), being BP1 200-folds more estrogenic than BP3. Estrogenic activity was eliminated during T. versicolor degradation of both compounds, showing that none of the resulting metabolites possessed significant estrogenic activity at the concentrations produced. These results demonstrate the suitability of this method to degrade both sunscreen agents and to eliminate estrogenic activity. - Highlights: ► Fungus T. versicolor is able to degrade totally BP3 and BP1 in few hours in a fluidised bed bioreactor. ► BP3 is not degraded under simulated sunlight. ► Glycoconjugates have been identified as the main intermediate metabolites. ► Decrease in endocrine activity was found in both photodegradation and biodegradation.

  16. Occurrence and profiles of organic sun-blocking agents in surface waters and sediments in Japanese rivers and lakes

    Energy Technology Data Exchange (ETDEWEB)

    Kameda, Yutaka, E-mail: kameda.yutaka@pref.saitama.lg.jp [Center for Environmental Science in Saitama, Kamitanadare 914, Kazo 347-0115 (Japan); Kimura, Kumiko; Miyazaki, Motonobu [Saitama City Institute of Health Science and Research, Suzuya 7-5-12, Chuo-ku, Saitama 338-0013 (Japan)

    2011-06-15

    Sun-blocking agents including eight UV filters (UVF) and 10 UV light stabilizers (UVLS) were measured in water and sediment collected from 22 rivers, four sewage treatment plant effluents (STPE) and three lakes in Japan. Total sun blocking agents levels ranged from N.D. to 4928 ng/L and from 2.0 to 3422 {mu}g/kg dry wt in surface water and in sediment, respectively. Benzyl salicylate, benzophenone-3, 2-ethyl hexyl-4-methoxycinnamte (EHMC) and octyl salicylate were dominant in surface water receiving wastewater effluents and STPE, although UV-328, benzophenone and EHMC were dominant in other surface water except background sites. Three UVF and nine UVLS were observed from all sediment and their compositions showed similar patterns with UV-328 and UV-234 as the most prevalent compounds. Homosalate, octocrylene, UV-326, UV-327, UV-328 and UV-234 were significantly correlated with Galaxolide in sediments. Concentrations of UV-327 and UV-328 also had strong correlation between those of UV-326 in sediment. - Highlights: > Total sun-blocking agents levels ranged from N.D. to 4928 ng/L in surface water from 29 sampling sites. > The maximum concentration of total sun-blocking agents was 3422 {mu}g/kg dry wt. in sediment. > Residential wastewaters and STPE were considered to be potential sources of UVLS in river and lakes. > Most of sun-blocking agents in sediment were significantly correlated with HHCB. > UV-326 had a strong linear correlation between UV-327 as well as UV-328 in all sediment. - Occurrence of eight UV filters and 10 UV light stabilizers in surface water and sediment were investigated and characterized their compositions in water and sediment.

  17. Fabrication of an Open Microfluidic Device for Immunoblotting.

    Science.gov (United States)

    Abdel-Sayed, Philippe; Yamauchi, Kevin A; Gerver, Rachel E; Herr, Amy E

    2017-09-19

    Given the wide adoption of polydimethylsiloxane (PDMS) for the rapid fabrication of microfluidic networks and the utility of polyacrylamide gel electrophoresis (PAGE), we develop a technique for fabrication of PAGE molecular sieving gels in PDMS microchannel networks. In developing the fabrication protocol, we trade-off constraints on materials properties of these two polymer materials: PDMS is permeable to O 2 and the presence of O 2 inhibits the polymerization of polyacrylamide. We present a fabrication method compatible with performing PAGE protein separations in a composite PDMS-glass microdevice, that toggles from an "enclosed" microchannel for PAGE and blotting to an "open" PA gel lane for immunoprobing and readout. To overcome the inhibitory effects of O 2 , we coat the PDMS channel with a 10% benzophenone solution, which quenches the inhibiting effect of O 2 when exposed to UV, resulting in a PAGE-in-PDMS device. We then characterize the PAGE separation performance. Using a ladder of small-to-mid mass proteins (Trypsin Inhibitor (TI); Ovalbumin (OVA); Bovine Serum Albumin (BSA)), we observe resolution of the markers in TI, with comparable reproducibility to glass microdevice PAGE. We show that benzophenone groups incorporated into the gel through methacrylamide can be UV-activated multiple times to photocapture protein. PDMS microchannel network is reversibly bonded to a glass slide allowing direct access to separated proteins and subsequent in situ diffusion-driven immunoprobing and total protein Sypro red staining. We see this PAGE-in-PDMS fabrication technique as expanding the application and use of microfluidic PAGE without the need for a glass microfabrication infrastructure.

  18. Measurement of Total and Free Urinary Phenol and Paraben Concentrations over the Course of Pregnancy: Assessing Reliability and Contamination of Specimens in the Norwegian Mother and Child Cohort Study.

    Science.gov (United States)

    Guidry, Virginia T; Longnecker, Matthew P; Aase, Heidi; Eggesbø, Merete; Zeiner, Pål; Reichborn-Kjennerud, Ted; Knudsen, Gun P; Bertelsen, Randi J; Ye, Xiaoyun; Calafat, Antonia M; Engel, Stephanie M

    2015-07-01

    Exposures to environmental phenols and parabens may be harmful, especially in utero. Prior studies have demonstrated high within-person variability of urinary concentrations across pregnancy. We sought to measure phenol and paraben biomarker concentrations for the Norwegian Mother and Child Cohort (MoBa) study, assess within-person variability, and investigate any possible external phenol or paraben contamination of specimens. We collected three spot urine samples at approximately 17, 23, and 29 weeks gestation in a hospital setting and added a preservative containing ethyl paraben. We measured urinary concentrations and within-person variability for phenols and parabens in a MoBa sample (n = 45), including a subgroup of 15 participants previously randomly selected for a bisphenol A (BPA) exposure study who had unusually high total BPA concentrations. Additionally, we compared reliability results for total, conjugated, and free concentrations of phenolic compounds. We detected total and free BPA, butyl paraben, propyl paraben, and methyl paraben in 100% of samples, total benzophenone-3 in 95% of samples, and infrequently detected free benzophenone-3 and total and free 2,4-dichlorophenol and 2,5-dichlorophenol. Intraclass correlation coefficients (ICCs) for total, conjugated, and free concentrations ranged from relatively low for BPA to moderate for propyl paraben. ICCs were generally similar overall and by subgroup. Using conjugated concentrations improved reliability estimates only for BPA. Measuring total and free concentrations, an approach that may be useful for future studies, allowed us to identify likely BPA and butyl paraben contamination of archived MoBa urine specimens.

  19. Microwave-optical double resonance spectroscopy. Progress report, February 1, 1976--January 31, 1977

    Energy Technology Data Exchange (ETDEWEB)

    Pratt, D.W.

    1976-11-01

    Zero-field and high-field optical detection of magnetic resonance (ODMR), electron paramagnetic resonance (EPR), and optical spectroscopy experiments have been performed on several systems in order to further basic knowledge of the structure, reactions, and response to radiation of atoms, molecules, and ions in their ground and/or excited electronic states. Particularly noteworthy results for the present contract year include the determination of the complete magnetic and optical properties of the lowest triplet states of 1-chloro, 1-bromo, and 1-iodonaphthalene, the development of a microscopic model for the intramolecular heavy-atom effect in the /sup 3/(..pi..,..pi..*) states of aromatic molecules, a detailed analysis of the angular dependence of the hyperfine and quadrupole structure in triplet 1-bromonaphthalene, observation of proton hyperfine structure in the hf ODMR spectra of short-lived triplet states, a definitive paper on the relative importance of spin delocalization and second-order spin-orbit coupling effects in /sup 3/(n,..pi..*) benzophenone (a phototype photochemical system), a detailed analysis of the level-anticrossing spectra of several triplet state benzophenones which exhibit hyperfine structure in the cross-relaxation region (thus permitting the determination of key magnetic parameters in the complete absence of perturbing microwave or radiofrequency fields), optical detection of ground-state NQR transitions in host crystal molecules, the observation of strong radiofrequency transitions near avoided crossing points in Zeeman energy level diagrams of photoexcited triplet states, the construction of zero-field ODMR, ODENDOR, and hf ODENDOR spectrometers, measurements of the activation parameters for ring interconversions of several free radicals containing five- and six-membered rings, and experimental proof that the triplet state of trimethylenemethane (a key reactive intermediate in organic chemistry) is the ground state.

  20. Development of a fully automated sequential injection solid-phase extraction procedure coupled to liquid chromatography to determine free 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid in human urine

    International Nuclear Information System (INIS)

    Leon, Zacarias; Chisvert, Alberto; Balaguer, Angel; Salvador, Amparo

    2010-01-01

    2-Hydroxy-4-methoxybenzophenone and 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid, commonly known as benzophenone-3 (BZ3) and benzophenone-4 (BZ4), respectively, are substances widely used as UV filters in cosmetic products in order to absorb UV radiation and protect human skin from direct exposure to the deleterious wavelengths of sunlight. As with other UV filters, there is evidence of their percutaneous absorption. This work describes an analytical method developed to determine trace levels of free BZ3 and BZ4 in human urine. The methodology is based on a solid-phase extraction (SPE) procedure for clean-up and pre-concentration, followed by the monitoring of the UV filters by liquid chromatography-ultraviolet spectrophotometry detection (LC-UV). In order to improve not only the sensitivity and selectivity, but also the precision of the method, the principle of sequential injection analysis was used to automate the SPE process and to transfer the eluates from the SPE to the LC system. The application of a six-channel valve as an interface for the switching arrangements successfully allowed the on-line connection of SPE sample processing with LC analysis. The SPE process for BZ3 and BZ4 was performed using octadecyl (C18) and diethylaminopropyl (DEA) modified silica microcolumns, respectively, in which the analytes were retained and eluted selectively. Due to the matrix effects, the determination was based on standard addition quantification and was fully validated. The relative standard deviations of the results were 13% and 6% for BZ3 and BZ4, respectively, whereas the limits of detection were 60 and 30 ng mL -1 , respectively. The method was satisfactorily applied to determine BZ3 and BZ4 in urine from volunteers that had applied a sunscreen cosmetic containing both UV filters.

  1. In-utero exposure to phenols and phthalates and the intelligence quotient of boys at 5 years.

    Science.gov (United States)

    Nakiwala, Dorothy; Peyre, Hugo; Heude, Barbara; Bernard, Jonathan Y; Béranger, Rémi; Slama, Rémy; Philippat, Claire

    2018-02-20

    There are concerns that developmental exposure to endocrine disrupting chemicals such as phenolic compounds and phthalates could affect child cognitive function. Epidemiological studies tackling this question have mainly focused on phthalate metabolites and bisphenol A, but not on the other phenolic compounds. Our study aimed to assess the relationship between in-utero exposure to phthalates, bisphenol A and other phenolic compounds (parabens, triclosan, dichlorophenols and benzophenone-3) and the Intelligence Quotient (IQ) of boys at 5-6 years. In 452 mother-son dyads from the French EDEN cohort, we measured 11 phthalate metabolites and 9 phenolic compounds (4 parabens, benzophenone-3, bisphenol A, 2 dichlorophenols and triclosan) in spot urine samples collected between 22 and 29 gestational weeks. Verbal and performance IQ of children were assessed at 5-6 years by a psychologist using the Wechsler Preschool and Primary Scale of Intelligence (WPPSI). We used adjusted Structural Equation Models (SEM) combined with Benjamini and Hochberg false discovery rate correction to assess the associations between maternal urine phenol and phthalate metabolite concentrations considered simultaneously and the boys' IQ. No phenol or phthalate metabolite concentration was negatively associated with the boys' verbal or performance IQ (uncorrected p-values ≥0.09). Mono(3-carboxypropyl) phthalate tended to be associated with increased verbal IQ (β = 0.136, 95% confidence interval, 0.01; 0.27). This association disappeared after correction for multiple comparison (corrected p-value, 0.71). Our results did not provide evidence of an inverse association between in-utero exposure to phenols or phthalates and verbal and performance IQ among boys. Since phenols and phthalates may have sex-specific effects, these null findings cannot be generalized to girls. Limitations included use of a single spot urine sample to assess exposures and lack of consideration of postnatal exposures.

  2. Development of a fully automated sequential injection solid-phase extraction procedure coupled to liquid chromatography to determine free 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid in human urine

    Energy Technology Data Exchange (ETDEWEB)

    Leon, Zacarias; Chisvert, Alberto; Balaguer, Angel [Departamento de Quimica Analitica, Facultad de Quimica, Universitat de Valencia, Doctor Moliner 50, 46100 Burjassot, Valencia (Spain); Salvador, Amparo, E-mail: amparo.salvador@uv.es [Departamento de Quimica Analitica, Facultad de Quimica, Universitat de Valencia, Doctor Moliner 50, 46100 Burjassot, Valencia (Spain)

    2010-04-07

    2-Hydroxy-4-methoxybenzophenone and 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid, commonly known as benzophenone-3 (BZ3) and benzophenone-4 (BZ4), respectively, are substances widely used as UV filters in cosmetic products in order to absorb UV radiation and protect human skin from direct exposure to the deleterious wavelengths of sunlight. As with other UV filters, there is evidence of their percutaneous absorption. This work describes an analytical method developed to determine trace levels of free BZ3 and BZ4 in human urine. The methodology is based on a solid-phase extraction (SPE) procedure for clean-up and pre-concentration, followed by the monitoring of the UV filters by liquid chromatography-ultraviolet spectrophotometry detection (LC-UV). In order to improve not only the sensitivity and selectivity, but also the precision of the method, the principle of sequential injection analysis was used to automate the SPE process and to transfer the eluates from the SPE to the LC system. The application of a six-channel valve as an interface for the switching arrangements successfully allowed the on-line connection of SPE sample processing with LC analysis. The SPE process for BZ3 and BZ4 was performed using octadecyl (C18) and diethylaminopropyl (DEA) modified silica microcolumns, respectively, in which the analytes were retained and eluted selectively. Due to the matrix effects, the determination was based on standard addition quantification and was fully validated. The relative standard deviations of the results were 13% and 6% for BZ3 and BZ4, respectively, whereas the limits of detection were 60 and 30 ng mL{sup -1}, respectively. The method was satisfactorily applied to determine BZ3 and BZ4 in urine from volunteers that had applied a sunscreen cosmetic containing both UV filters.

  3. Evaluation of fungal- and photo-degradation as potential treatments for the removal of sunscreens BP3 and BP1

    Energy Technology Data Exchange (ETDEWEB)

    Gago-Ferrero, Pablo, E-mail: pablo.gago@idaea.csic.es [Departament de Quimica Ambiental, IDAEA-CSIC, C/ Jordi Girona 18-26, 08034 Barcelona (Spain); Badia-Fabregat, Marina, E-mail: marina.badia@uab.cat [Departament d' Enginyeria Quimica, Escola d' Enginyeria, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Olivares, Alba, E-mail: esalba.olivares@idaea.csic.es [Departament de Quimica Ambiental, IDAEA-CSIC, C/ Jordi Girona 18-26, 08034 Barcelona (Spain); Pina, Benjamin, E-mail: benjami.pina@idaea.csic.es [Departament de Quimica Ambiental, IDAEA-CSIC, C/ Jordi Girona 18-26, 08034 Barcelona (Spain); Blanquez, Paqui, E-mail: paqui.blanquez@uab.cat [Departament d' Enginyeria Quimica, Escola d' Enginyeria, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Vicent, Teresa, E-mail: teresa.vicent@uab.cat [Departament d' Enginyeria Quimica, Escola d' Enginyeria, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Caminal, Gloria, E-mail: gloria.caminal@uab.cat [Unitat de Biocatalisi Aplicada associada al IQAC (CSIC-UAB). Escola d' Enginyeria, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Diaz-Cruz, M. Silvia, E-mail: silvia.diaz@idaea.csic.es [Departament de Quimica Ambiental, IDAEA-CSIC, C/ Jordi Girona 18-26, 08034 Barcelona (Spain); and others

    2012-06-15

    Photodecomposition might be regarded as one of the most important abiotic factors affecting the fate of UV absorbing compounds in the environment and photocatalysis has been suggested as an effective method to degrade organic pollutants. However, UV filters transformation appears to be a complex process, barely addressed to date. The white rot fungus Trametes versicolor is considered as a promising alternative to conventional aerobic bacterial degradation, as it is able to metabolise a wide range of xenobiotics. This study focused on both degradation processes of two widely used UV filters, benzophenone-3 (BP3) and benzophenone-1 (BP1). Fungal treatment resulted in the degradation of more than 99% for both sunscreens in less than 24 h, whereas photodegradation was very inefficient, especially for BP3, which remained unaltered upon 24 h of simulated sunlight irradiation. Analysis of metabolic compounds generated showed BP1 as a minor by-product of BP3 degradation by T. versicolor while the main intermediate metabolites were glycoconjugate derivatives. BP1 and BP3 showed a weak, but significant estrogenic activity (EC50 values of 0.058 mg/L and 12.5 mg/L, respectively) when tested by recombinant yeast assay (RYA), being BP1 200-folds more estrogenic than BP3. Estrogenic activity was eliminated during T. versicolor degradation of both compounds, showing that none of the resulting metabolites possessed significant estrogenic activity at the concentrations produced. These results demonstrate the suitability of this method to degrade both sunscreen agents and to eliminate estrogenic activity. - Highlights: Black-Right-Pointing-Pointer Fungus T. versicolor is able to degrade totally BP3 and BP1 in few hours in a fluidised bed bioreactor. Black-Right-Pointing-Pointer BP3 is not degraded under simulated sunlight. Black-Right-Pointing-Pointer Glycoconjugates have been identified as the main intermediate metabolites. Black-Right-Pointing-Pointer Decrease in endocrine activity

  4. Ketoprofen removal by O{sub 3} and O{sub 3}/UV processes: Kinetics, transformation products and ecotoxicity

    Energy Technology Data Exchange (ETDEWEB)

    Illés, Erzsébet, E-mail: erzsebet.illes@energia.mta.hu [Environmental Chemistry Research Group Institute of Chemistry, University of Szeged, 6723 Szeged, Tisza Lajos krt. 103 (Hungary); Radiation Chemistry Department, Centre for Energy Research, Hungarian Academy of Sciences, 1121 Budapest, Konkoly Thege M. út 29-33 (Hungary); Szabó, Emese, E-mail: emese.szabo@chem.u-szeged.hu [Environmental Chemistry Research Group Institute of Chemistry, University of Szeged, 6723 Szeged, Tisza Lajos krt. 103 (Hungary); Takács, Erzsébet, E-mail: erzsebet.takacs@energia.mta.hu [Radiation Chemistry Department, Centre for Energy Research, Hungarian Academy of Sciences, 1121 Budapest, Konkoly Thege M. út 29-33 (Hungary); Wojnárovits, László, E-mail: laszlo.wojnarovits@energia.mta.hu [Radiation Chemistry Department, Centre for Energy Research, Hungarian Academy of Sciences, 1121 Budapest, Konkoly Thege M. út 29-33 (Hungary); Dombi, András, E-mail: dombia@chem.uszeged.hu [Environmental Chemistry Research Group Institute of Chemistry, University of Szeged, 6723 Szeged, Tisza Lajos krt. 103 (Hungary); Gajda-Schrantz, Krisztina, E-mail: sranc@chem.u-szeged.hu [Environmental Chemistry Research Group Institute of Chemistry, University of Szeged, 6723 Szeged, Tisza Lajos krt. 103 (Hungary); Department of Inorganic and Analytical Chemistry, University of Szeged, 6720 Szeged, Dóm tér 7 (Hungary); EMPA, Laboratory for High Performance Ceramics, Überlandstrasse 129, 8600 Dübendorf (Switzerland)

    2014-02-01

    Ozonation (O{sub 3}) and its combination with ultraviolet radiation (O{sub 3}/UV) were used to decompose ketoprofen (KET). Depending on the initial KET concentration, fourteen to fifty time's faster KET degradation was achieved using combined O{sub 3}/UV method compared to simple ozonation. Using both methods, formation of four major aromatic transformation products were observed: 3-(1-hydroxyethyl)benzophenone, 3-(1-hydroperoxyethyl) benzophenone, 1-(3-benzoylphenyl) ethanone and 3-ethylbenzophenone. In the combined treatment the degradation was mainly due to the direct effect of UV light, however, towards the end of the treatment, O{sub 3} highly contributed to the mineralization of small carboxylic acids. High (∼ 90%) mineralization degree was achieved using the O{sub 3}/UV method. Toxicity tests performed using representatives of three trophic levels of the aquatic ecosystems (producers, consumers and decomposers) Pseudokirchneriella subcapitata green algae, Daphnia magna zooplanktons and Vibrio fischeri bacteria showed that under the used experimental conditions the transformation products have significantly higher toxicity towards all the test organisms, than KET itself. The bacteria and the zooplanktons showed higher tolerance to the formed products than algae. The measured toxicity correlates well with the concentration of the aromatic transformation products, therefore longer treatments than needed for complete degradation of KET are strongly suggested, in order to avoid possible impact of aromatic transformation products on the aquatic ecosystem. - Highlights: • Ketoprofen degradation is significantly faster using O{sub 3}/UV compared to ozonation. • The presence of O{sub 3} enhances the overall mineralization. • Formation of four major aromatic by-products was observed. • The main step in the decomposition is the decarboxylation. • Degradation products have higher toxicity than ketoprofen itself.

  5. Effect of nuclear spin on chemical reactions and internal molecular rotation

    International Nuclear Information System (INIS)

    Sterna, L.L.

    1980-12-01

    Part I of this dissertation is a study of the magnetic isotope effect, and results are presented for the separation of 13 C and 12 C isotopes. Two models are included in the theoretical treatment of the effect. In the first model the spin states evolve quantum mechanically, and geminate recombination is calculated by numerically integrating the collision probability times the probability the radical pair is in a singlet state. In the second model the intersystem crossing is treated via first-order rate constants which are average values of the hyperfine couplings. Using these rate constants and hydrodynamic diffusion equations, an analytical solution, which accounts for all collisions, is obtained for the geminate recombination. The two reactions studied are photolysis of benzophenone and toluene and the photolytic decomposition of dibenzylketone (1,3-diphenyl-2-propanone). No magnetic isotope effect was observed in the benzophenone reaction. 13 C enrichment was observed for the dibenzylketone reaction, and this enrichment was substantially enhanced at intermediate viscosities and low temperatures. Part II of this dissertation is a presentation of theory and results for the use of Zeeman spin-lattice relaxation as a probe of methyl group rotation in the solid state. Experimental results are presented for the time and angular dependences of rotational polarization, the methyl group magnetic moment, and methyl-methyl steric interactions. The compounds studied are 2,6-dimethylphenol, methyl iodide, 1,4,5,8-tetramethylanthracene, 1,4,5,8-tetramethylnaphthalene, 1,2,4,5-tetramethylbenzene, and 2,3-dimethylmaleicanhydride

  6. Associations between socioeconomic status and environmental toxicant concentrations in adults in the USA: NHANES 2001-2010.

    Science.gov (United States)

    Tyrrell, Jessica; Melzer, David; Henley, William; Galloway, Tamara S; Osborne, Nicholas J

    2013-09-01

    Low level chronic exposure to toxicants is associated with a range of adverse health effects. Understanding the various factors that influence the chemical burden of an individual is of critical importance to public health strategies. We investigated the relationships between socioeconomic status (SES) and bio-monitored chemical concentration in five cross-sectional waves of the U.S. National Health and Nutrition Examination Survey (NHANES). We utilised adjusted linear regression models to investigate the association between 179 toxicants and the poverty income ratio (PIR) for five NHANES waves. We then selected a subset of chemicals associated with PIR in 3 or more NHANES waves and investigated potential mediating factors using structural equation modelling. PIR was associated with 18 chemicals in 3 or more NHANES waves. Higher SES individuals had higher burdens of serum and urinary mercury, arsenic, caesium, thallium, perfluorooctanoic acid, perfluorononanoic acid, mono(carboxyoctyl) phthalate and benzophenone-3. Inverse associations were noted between PIR and serum and urinary lead and cadmium, antimony, bisphenol A and three phthalates (mono-benzyl, mono-isobutyl, mono-n-butyl). Key mediators included fish and shellfish consumption for the PIR, mercury, arsenic, thallium and perfluorononanoic acid associations. Sunscreen use was an important mediator in the benzophenone-3/PIR relationship. The association between PIR and cadmium or lead was partially mediated by smoking, occupation and diet. These results provide a comprehensive analysis of exposure patterns as a function of socioeconomic status in US adults, providing important information to guide future public health remediation measures to decrease toxicant and disease burdens within society. © 2013.

  7. Distribution and seasonal occurrence of UV filters in rivers and wastewater treatment plants in Korea.

    Science.gov (United States)

    Ekpeghere, Kalu Ibe; Kim, Un-Jung; O, Sung-Hee; Kim, Hee-Young; Oh, Jeong-Eun

    2016-01-15

    The occurrence and distribution of eight UV filters benzophenone (BP), benzophenone-3 (BP-3), ethylhexyl methoxy cinnamate (EHMC), 4-methylbenzylidene camphor (4-MBC), 2-ethylhexyl 4-dimethylaminobenzoate (OD-PABA), 2-ethylhexyl salicylate (EHS), isoamyl benzoate, and benzyl cinnamate in eleven sites among three rivers, five sewage treatment plants (STPs), and four wastewater treatment plants (WWTPs) located in different parts of Korea was investigated. The total concentrations of UV filters in the three sampled seasons were 62.9-412 ng L(-1) (river), 417-5055 ng L(-1) (STP influent), 108-2201 ng L(-1) (STP effluent), 122-4154 ng L(-1) (WWTP influent), and 120-849 ng L(-1) (WWTP effluent). The concentration of the target pollutants in the influent of the treatment systems was directly proportional to the resident population density. A seasonal increase of >27% was observed in the total concentration of the UV filters in the rivers and influents of the treatment plants (TPs) during summer. BP, BP-3, EHMC, 4-MBC, and EHS were the most dominant, showing a distinct distribution pattern that was dependent on the effectiveness of the treatment process and properties of each compound. The concentrations of the UV filters were higher in the TPs influents than in the rivers, and the most dominant UV filters in the rivers were those with low removal rate. Although biological treatment processes favored the removal of the UV filter compounds in the TPs, complete removal was not achieved before discharge into the rivers. Copyright © 2015. Published by Elsevier B.V.

  8. The effect of UV-filters on the viability of neuroblastoma (SH-SY5Y) cell line.

    Science.gov (United States)

    Broniowska, Żaneta; Pomierny, Bartosz; Smaga, Irena; Filip, Małgorzata; Budziszewska, Bogusława

    2016-05-01

    Topical application of cosmetic products, containing ultraviolet filters (UV filters) are recommended as a protection against sunburns and in order to reduce the risk of skin cancer. However, some UV filters can be absorbed through skin and by consuming contaminated food. Among the chemical UV filters, benzophenone-3 (BP-3), 3-(4-methylbenzylidene)camphor (4-MBC) and 2-ethylhexyl-4-methoxycinnamate (OMC) are absorbed through the skin to the greatest extent. So far, these lipophilic compounds were demonstrated to influence the gonadal and thyroid hormone function, but their effect on central nervous system cells has not been investigated, yet. In the present study, we investigated the effect of some UV filters on cell viability and caspase-3 activity in SH-SY5Y cells. It has been found that benzophenone-2 (BP-2), BP-3, 4-methylbenzophenone (4-MBP) and OMC present in the culture medium for 72h in high concentration (10(-5) and 10(-4)M) and 4-MBC only 10(-4)M produced a significant cytotoxic effect, as determined both by the MTT reduction test and LDH release assay. In contrast to necrotic changes, all tested UV filters increased caspase-3 activity in much lower concentrations (from 10(-8) to 10(-7)M). Proapoptotic properties of the test compounds were positively verified by Hoechst staining. The obtained results indicated that UV filters adversely affected the viability of nerve cells, most likely by enhancing the process of apoptosis. The most potent effect was exerted by BP-3 and 4-MBC and at concentrations that may be reached in vivo. Since human exposure to UV filters is significant these compound should be taken into consideration as one of the possible factors involved in pathogenesis of neurodegenerative diseases. Copyright © 2016 Elsevier Inc. All rights reserved.

  9. Simultaneous analysis and monitoring of 16 UV filters in cosmetics by high-performance liquid chromatography.

    Science.gov (United States)

    Kim, Dojung; Kim, Sangseop; Kim, Seol-A; Choi, Myoengsin; Kwon, Kyoung-Jin; Kim, Mijeong; Kim, Dong-Sup; Kim, Seung-Hee; Choi, Bo-Kyung

    2012-01-01

    Sixteen UV filters were simultaneously analyzed using the high-performance liquid chromatographic method. They were drometrizole (USAN Drometrizole), 4-methylbenzylidene camphor (USAN Enzacamene), menthyl anthranilate (USAN Menthyl anthranilate), benzophenone-3 (USAN Oxybenzone), benzophenone-8 (USAN Dioxybenzone), butyl methoxydibenzoylmethane (USAN Avobenzone), ethylhexyl triazone (USAN Octyl triazone), octocrylene (USAN Octocrylene), ethylhexyl dimethyl p-aminobenzoic acid (USAN Padimate O), ethylhexyl methoxycinnamate (USAN Octinoxate), p-aminobenzoic acid (USAN Aminobenzoic acid), 2-phenylbenzimidazole-5-sulfonic acid (USAN Ensulizole), isoamyl p-methoxycinnamate (USAN Amiloxate), and recent UV filters such as diethylhexyl butamidotriazone (USAN Iscotrizinol), methylene bis-benzotriazolyl tetramethylbutylphenol (USAN Bisoctrizole), and terephthalylidene dicamphor sulfonic acid (USAN Ecamsule). Separation of the UV filters was carried out in a C(18) column with a gradient of methanol-phosphate buffer, and the UV detection was at 300, 320, or 360 nm without any interference. The limits of detection were between 0.08 and 1.94 μg/ml, and the limits of quantitation were between 0.24 and 5.89 μg/ml. The extracting solvent for the UV filters was methanol, except for ethylhexyl triazone and methylene bis-benzotriazolyl tetramethylbutylphenol, which were prepared with tetrahydrofuran. The recoveries from spiked samples were between 94.90% and 116.54%, depending on the matrixes used. The developed method was applied to 23 sunscreens obtained from local markets, and the results were acceptable to their own criteria and to maximum authorized concentrations. Consequently, these results would provide a simple extracting method and a simultaneous determination for various UV filters, which can improve the quality control process as well as the environmental monitoring of sunscreens.

  10. Leishmanicidal and Cholinesterase Inhibiting Activities of Phenolic Compounds from Allanblackia monticola and Symphonia globulifera

    Directory of Open Access Journals (Sweden)

    Norbert Sewald

    2007-07-01

    Full Text Available In a preliminary antiprotozoal screening of several Clusiaceae species, the methanolic extracts of Allanblackia monticola and Symphonia globulifera showed high in vitro leishmanicidal activity. Further bioguided phytochemical investigation led to the isolation of four benzophenones: guttiferone A (1, garcinol (2, cambogin (3 and guttiferone F (4, along with three xanthones: allanxanthone A (5, xanthone V1 (6 and globulixanthone C (7 as active constituents. Compounds 1 and 6 were isolated from S. globulifera leaves, while compounds 2-5 were obtained from A. monticola fruits. Guttiferone A (1 and F (4 showed particulary strong leishmanicidal activity in vitro, with IC50 values (0.2 μM and 0.16 μM, respectively comparable to that of the reference compound, miltefosine (0.46 μM. Although the leishmanicidal activity is promising, the cytotoxicity profile of these compounds prevent at this state further in vivo biological evaluation. In addition, all the isolated compounds were tested in vitro for their anticholinesterase properties. The four benzophenones showed potent anticholinesterase properties towards acetylcholinesterase (AChE and butylcholinesterase (AChE. For AChE, the IC50 value (0.66 μM of garcinol (2 was almost equal to that of the reference compound galanthamine (0.50 μM. Furthermore, guttiferone A (1 and guttiferone F (4 (IC50 = 2.77 and 3.50 μM, respectively were more active than galanthamine (IC50 = 8.5 against BChE.

  11. Inhibition of radical reactions for an improved potassium tert-butoxide-promoted (11) C-methylation strategy for the synthesis of α-(11) C-methyl amino acids.

    Science.gov (United States)

    Suzuki, Chie; Kato, Koichi; Tsuji, Atsushi B; Zhang, Ming-Rong; Arano, Yasushi; Saga, Tsuneo

    2015-03-01

    α-(11) C-Methyl amino acids are useful tools for biological imaging studies. However, a robust procedure for the labeling of amino acids has not yet been established. In this study, the (11) C-methylation of Schiff-base-activated α-amino acid derivatives has been optimized for the radiosynthesis of various α-(11) C-methyl amino acids. The benzophenone imine analog of methyl 2-amino butyrate was (11) C-methylated with [(11) C]methyl iodide following its initial deprotonation with potassium tert-butoxide (KOtBu). The use of an alternative base such as tetrabutylammonium fluoride, triethylamine, and 1,8-diazabicyclo[5.4.0]undec-7-ene did not result in the (11) C-methylated product. Furthermore, the KOtBu-promoted (11) C-methylation of the Schiff-base-activated amino acid analog was enhanced by the addition of 1,2,4,5-tetramethoxybenzene or 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and inhibited by the addition of 1,10-phenanthroline. These results suggest that inhibition of radical generation induced by KOtBu improves the α-(11) C-methylation of the Schiff-base-activated amino acids. The addition of a mixture of KOtBu and TEMPO to a solution of Schiff-base-activated amino acid ester and [(11) C]methyl iodide provided optimal results, and the tert-butyl ester and benzophenone imine groups could be readily hydrolyzed to give the desired α-(11) C-methyl amino acids with a high radiochemical conversion. This strategy could be readily applied to the synthesis of other α-(11) C-methyl amino acids. Copyright © 2015 John Wiley & Sons, Ltd.

  12. Urinary levels of triclosan and parabens are associated with aeroallergen and food sensitization

    Science.gov (United States)

    Savage, Jessica H.; Matsui, Elizabeth C.; Wood, Robert A.; Keet, Corinne A.

    2013-01-01

    Background Endocrine-disrupting compounds (EDCs) have immune-modulating effects. We were interested in determining their association with allergic sensitization. Objective To determine the association between EDCs and allergic sensitization and if this relationship depended on the antimicrobial properties of the EDCs and/or gender. Methods Data were obtained from the 2005–2006 National Health and Nutrition Examination Survey in which urinary bisphenol A, triclosan, benzophenone-3, and propyl, methyl, butyl and ethyl paraben, and specific IgE were available on 860 children. Aeroallergen and food sensitization were defined as having at least one positive (≥0.35 kU/L) specific IgE to an aeroallergen or a food. Logistic regression was used to determine the association of EDCs and sensitization. Analyses were adjusted for urinary creatinine, age, ethnicity, and poverty index ratio. Results The odds of aeroallergen sensitization significantly increased with the level of the antimicrobial EDCs triclosan and propyl and butyl paraben (p≤0.04). The odds of food sensitization significantly increased with the level of urinary triclosan among male subjects (odds ratio for 3rd versus 1st tertile 3.9, p=0.02 for trend). There was a significant interaction between gender and triclosan, with males being more likely to be food sensitized with exposure (p=0.03). Similar associations were not identified for the non-antimicrobial EDCs bisphenol A and benzophenone-3 (p>0.2). Conclusions As a group, EDCs are not associated with allergen sensitization. However, levels of the antimicrobial EDCs triclosan and parabens were significantly associated with allergic sensitization. The potential role of antimicrobial EDCs in allergic disease warrants further study as they are commonly used in Western society. PMID:22704536

  13. Rapid determination of nine parabens and seven other environmental phenols in urine samples of German children and adults.

    Science.gov (United States)

    Moos, Rebecca K; Angerer, Jürgen; Wittsiepe, Jürgen; Wilhelm, Michael; Brüning, Thomas; Koch, Holger M

    2014-11-01

    We developed a fast, selective and sensitive on-line LC/LC-MS/MS method for the simultaneous determination of nine parabens and seven environmental phenols in urine. Parabens are widely used as antimicrobial preservatives. Bisphenol A, triclosan, triclocarban, 2-phenylphenol, and benzophenones are used inter alia in disinfectants, sunscreens and in polymers. Some of these substances are suspected endocrine disruptors. Limits of quantification and analytical quality criteria fully met the needs for determining exposure levels occurring in the general population. We analyzed 157 spot urine samples from the general German population (59 females, 39 males and 59 children). For the parabens, we found methyl, ethyl and n-propyl paraben with high detection rates (77-98%), followed by n-butyl (36%), iso-butyl (17%), iso-propyl (3%) and benzyl paraben (3%). We detected no pentyl and heptyl paraben. Urinary concentrations were highest for methyl paraben (median 24.5 μg/L; 95th percentile 379 μg/L) followed by ethyl (1.4 μg/L; 35.2 μg/L) and n-propyl paraben (1.2 μg/L; 68.1 μg/L). Other environmental phenols with high detection rates were BPA (95%), triclosan (45%) and benzophenone 1 and 3 (26%). For most of the parabens/environmental phenols we found higher urinary levels in females than in males or children, probably due to differences in (personal care) product use. However, high levels (in the mg/L range) were also observed in children. Exposure to the above substances is occurring worldwide. Differences between countries do seem to exist and might be caused by different product compositions or different use habits. Human metabolism data is urgently needed to extrapolate from urinary biomarker levels to doses actually taken up. Copyright © 2014 Elsevier GmbH. All rights reserved.

  14. Simultaneous determination of the UV-filters benzyl salicylate, phenyl salicylate, octyl salicylate, homosalate, 3-(4-methylbenzylidene) camphor and 3-benzylidene camphor in human placental tissue by LC-MS/MS. Assessment of their in vitro endocrine activity.

    Science.gov (United States)

    Jiménez-Díaz, I; Molina-Molina, J M; Zafra-Gómez, A; Ballesteros, O; Navalón, A; Real, M; Sáenz, J M; Fernández, M F; Olea, N

    2013-10-01

    UV-filters are widely used in many personal care products and cosmetics. Recent studies indicate that some organic UV-filters can accumulate in biota and act as endocrine disruptors, but there are few studies on the occurrence and fate of these compounds in humans. In the present work, a new liquid chromatography-tandem mass spectrometry (LC-MS/MS) method to assess the presence of six UV-filters in current use (benzyl salicylate, phenyl salicylate, octyl salicylate, homosalate, 3-(4-methylbenzylidene) camphor, and 3-benzylidene camphor) in human placental tissue is proposed. The method involves the extraction of the analytes from the samples using ethyl acetate, followed by a clean-up step using centrifugation prior to their quantification by LC-MS/MS using an atmospheric pressure chemical ionization (APCI) interface. Bisphenol A-d16 was used as surrogate for the determination of benzyl salicylate, phenyl salicylate, octyl salicylate and homosalate in negative mode and benzophenone-d10, was used as surrogate for the determination of 3-(4-methylbenzylidene) camphor and 3-benzylidene camphor in positive mode. The found limits of detection ranged from 0.4 to 0.6ngg(-1) and the limits of quantification ranged from 1.3 to 2.0ngg(-1), while variability was under 13.7%. Recovery rates for spiked samples ranged from 97% to 104%. Moreover, the interactions of these compounds with the human estrogen receptor alpha (hERα) and androgen receptor (hAR), using two in vitro bioassays based on reporter gene expression and cell proliferation assessment, were also investigated. All tested compounds, except benzyl salicylate and octyl salicylate, showed estrogenic activity in the E-Screen bioassay whereas only homosalate and 3-(4-methylbenzylidene) camphor were potent hAR antagonists. Although free salicylate derivatives and free camphor derivatives were not detected in the human placenta samples analyzed, the observed estrogenic and anti-androgenic activities of some of these

  15. Estrogenic activity of ternary UV filter mixtures in fish (Pimephales promelas) - An analysis with nonlinear isobolograms

    International Nuclear Information System (INIS)

    Kunz, Petra Y.; Fent, Karl

    2009-01-01

    Numerous estrogenic compounds are present in aquatic environments, but currently it is not well understood how compounds that differ in maxima and slope of their individual dose-response curves contribute to the overall mixture effect. In order to better understand such interactions we investigated 3 commonly used UV filters, for their estrogenic mixture activity and analysed their joint effects by using the concentration addition (CA) concept. Thereby, we extended the method of isoboles for analysis of 3 compounds that differ in maxima and slopes of their dose-response curves. 3-Benzylidene camphor (3BC), benzophenone-1 (BP1) and benzophenone-2 (BP2) are estrogenic in fish and act as pure- or partial estrogen receptor α agonists. First we exposed juvenile fathead minnows for 14 days to six concentrations of each UV filter alone to determine vitellogenin (VTG) induction curves, calculate equi-effective mixture concentrations and predict mixture effects. For 3BC, BP1 and BP2 significant VTG-induction occurred at 420, 2668, and 4715 μg/L, respectively. BP2 displayed a full dose-response curve, whereas 3BC and BP1 showed submaximal activity of 70 and 78%, respectively. Second, we exposed fish to 6 equi-effective mixtures (EC-NOEC, EC1, EC5, EC10, EC20, EC30) of these UV filters. Significant VTG-induction occurred at EC5 and higher. Submaximal activity of 67% as compared to the control EE2 (100 ng/L) was reached. The curves for the observed and predicted mixture activity agreed for mixture levels (EC10 to EC30), however, at EC-NOEC, EC1 and EC5, lower activity was observed than predicted by CA. Detailed isobolographic analysis indicate additivity at EC10 to EC30, and antagonism at low levels (EC-NOEC to EC5). Our data show for the first time, that for compounds with differences in maxima and slope, considerably more mixture combinations are additive than previously thought. This should be taken into account for hazard and risk assessment of UV filters and

  16. Additive estrogenic effects of mixtures of frequently used UV filters on pS2-gene transcription in MCF-7 cells

    International Nuclear Information System (INIS)

    Heneweer, Marjoke; Muusse, Martine; Berg, Martin van den; Sanderson, J. Thomas

    2005-01-01

    In order to protect consumers from ultraviolet (UV) radiation and enhance light stability of the product, three to eight UV filters are usually added to consumer sunscreen products. High lipophilicity of the UV filters has been shown to cause bioaccumulation in fish and humans, leading to environmental levels of UV filters that are similar to those of PCBs and DDT. In this paper, estrogen-regulated pS2 gene transcription in the human mammary tumor cell line MCF-7 was used as a measure of estrogenicity of four individual UV filters. Since humans are exposed to more than one UV filter at a time, an equipotent binary mixture of 2-hydroxy-4-methoxy-benzophenone (BP-3) and its metabolite 2,4-dihydroxy benzophenone (BP-1), as well as an equipotent multi-component mixture of BP-1, BP-3, octyl methoxy cinnamate (OMC) and 3-(4-methylbenzylidene) camphor (4-MBC), were also evaluated for their ability to induce pS2 gene transcription in order to examine additivity. An estrogen receptor-mediated mechanism of action was expected for all UV filters. Therefore, our null-hypothesis was that combined estrogenic responses, measured as increased pS2 gene transcription in MCF-7 cells after exposure to mixtures of UV filters, are additive, according to a concentration-addition model. Not all UV filters produced a full concentration-response curve within the concentration range tested (100 nM-1 μM). Therefore, instead of using EC 50 values for comparison, the concentration at which each compound caused a 50% increase of basal pS2 gene transcription was defined as the C50 value for that compound and used to calculate relative potencies. For comparison, the EC 50 value of a compound is the concentration at which the compound elicits an effect that is 50% of its maximal effect. Individual UV filters increased pS2 gene transcription concentration-dependently with C50 values of 0.12 μM, 0.5 μM, 1.9 μM, and 1.0 μM for BP-1, BP-3, 4-MBC and OMC, respectively. Estradiol (E2) had a C50

  17. Variability and exposure classification of urinary phenol and paraben metabolite concentrations in reproductive-aged women.

    Science.gov (United States)

    Pollack, Anna Z; Perkins, Neil J; Sjaarda, Lindsey; Mumford, Sunni L; Kannan, Kurunthachalam; Philippat, Claire; Wactawski-Wende, Jean; Schisterman, Enrique F

    2016-11-01

    Human exposure to phenols and parabens is widespread. Within-person variability of urinary concentrations in healthy women is not well characterized. To characterize the variability of urinary phenol and paraben concentrations across two months and evaluate the ability of a single spot urine sample to characterize exposure. 143 women provided 509 spot urine samples collected across two months of study (3-5 samples/woman). We measured urinary concentrations of 8 phenols: bisphenol A (BPA), benzophenone-3 (BP-3), benzophenone-1 (BP-1), 2,4-dichlorophenol (2,4-DCP), 2,5-dichlorophenol (2,5-DCP), 2,4,5-trichlorophenol (2,4,5-TCP), 2,4,6-trichlorophenol (2,4,6-TCP), triclosan (TCS); and 8 parabens and their metabolites (benzyl (BzP), butyl (BuP), ethyl (EtP), heptyl (HeP), methyl (MeP), propyl (PrP), 4-hydroxybenzoic acid (4-HB), 3,4-dihydroxybenzoic acid (3,4-DHB)). Biomarker variability was characterized using the intraclass correlation coefficient (ICC) and surrogate category analyses were conducted. ICCs ranged from very low for BPA (0.04) to moderate for BP-3, BP-1, TCS, BzP, and MeP (0.66, 0.58, 0.55, 0.54, and 0.62, respectively). Surrogate analyses suggested that BP-1, BP-3, TCS, 2,4-DCP, BuP, and PrP may be characterized by a single spot sample (sensitivity range 0.76-0.86) but that additional samples were necessary for BPA, HeP, 4-HB, and 3,4-DHB (sensitivity range 0.47-0.61). Urinary phenol and paraben metabolite concentrations were variable across two months in healthy women but the degree of reliability differed by the specific biomarker. A small number of samples may sufficiently characterize typical concentrations for BP-3, BP-1, TCS, BuP, and PrP; but additional biospecimens may be necessary to characterize exposure for other compounds, including BPA. Copyright © 2016 Elsevier Inc. All rights reserved.

  18. Assessment of the in vivo genotoxicity of 2-hydroxy 4-methoxybenzophenone.

    Science.gov (United States)

    Robison, S H; Odio, M R; Thompson, E D; Aardema, M J; Kraus, A L

    1994-01-01

    The genotoxic potential of 2-hydroxy 4-methoxy-benzophenone (benzophenone-3, Bz-3), a commonly used sunscreen, has been evaluated previously with in vitro systems. Data from Salmonella studies (with and without activation) have been predominantly negative, but two reports have shown weakly positive results in a single bacterial strain under conditions of metabolic activation. In addition, Bz-3 has been reported to induce chromosome aberrations and equivocal results for sister chromatid exchange in Chinese hamster ovary (CHO) cells. We used the Drosophila somatic mutation and recombination test (SMART) and in vivo cytogenetics in rat bone marrow to define the potential for in vivo expression of this in vitro activity. For the SMART assay, larva from a mating of "multiple wing hair" (mwh) females with heterozygous "flare" (flr) males were exposed to 0, 3000, or 3500 ppm Bz-3 or 25 ppm dimethylnitrosamine (DMN, positive control) for 72 hr. A recombination between the mwh and flr genes produces twin wing spots, while events such as deletions produce single spots. None of the Bz-3-treated larva produced flies with significantly more single or multiple wing spots than controls. In contrast, DMN-treated larva produced flies with significantly more single or multiple wing spots than controls. The in vivo cytogenetic assay in rat bone marrow cells was conducted to evaluate the clastogenicity of Bz-3. Sprague-Dawley rats were treated by oral gavage with a single administration of 0.0, 0.5, 1.67, or 5 gm/kg Bz-3 or a single dose of 5 gm/kg/day Bz-3 for 5 consecutive days. Cyclophosphamide (CP) was the positive control and was administered at 20 mg/kg with both treatment regimens. Colchicine growth-arrested bone marrow cells were collected 8 and 12 hr after the single treatment and 12hr after the last daily treatment. Under either treatment protocol none of the Bz-3 concentrations caused any significant increase in chromosomal aberrations. Results from these two studies

  19. The light activated alkylation of glycine

    International Nuclear Information System (INIS)

    Knowles, H.S.

    2001-04-01

    The work contained in this thesis focuses on the light-initiated alkylation of the α-centre of glycine compounds. The elaboration of the glycines in this manner represents a versatile, clean and cost effective alternative to ionic routes to higher α-amino acids. Preliminary investigations demonstrated that a range of nitrogen protecting groups were compatible with the radical alkylation. A variety of solvents could also be used although solvents with easily removable hydrogen atoms were found to interfere with the alkylation. Furthermore, a number of photo-initiators were investigated and the use of di-tert-butyl peroxide was found to afford the desired phenylalanine products in up to 27% yield (54% based on recovered starting material) when toluene was used as the alkylating agent. A range of different precursor concentrations was investigated and it was found that the optimum concentration of the glycine precursor was 0.13 mol dm -3 ; the phenylalanine yields were reduced when the concentration was less than this value. Owing to the poor UV absorption by di-tert-butyl peroxide, benzophenone (an effective photosensitiser) was added to the reaction mixture and this was shown to increase the alkylation yields. The ratio of reagents which produced the highest yield of phenylalanine products was found to be 1 : 5 : 5 : 10 for glycine : di-tert-butyl peroxide : benzophenone : toluene. This produced the phenylalanine product in up to 37% yield (57% based on recovered starting material). A number of substituents. (e.g. F, Cl etc.) could be attached to the aromatic ring of the toluene alkylating agent, affording substituted phenylalanines in 5 - 36% under these conditions. The formation of chiral phenylalanine products was probed by reacting glycine precursors bearing chiral auxiliaries. However, low diastereoselectivities were observed; the d.r. ranged from 1 : 1.1 to 1 : 1.5 only when chiral ester and amide protecting groups were used. In the final chapter, the

  20. The Optimum Irradiation Dose in Preservation of Mahkota Dewa (Phaleria macrocarpa (Scheff) Boerl.) As Anticancer Agent

    International Nuclear Information System (INIS)

    Hendig Winarno; Ermin Katrin W; Wisnurahadi; Swasono R Tamat

    2010-01-01

    The purpose of this experiment was to obtain the optimum irradiation dose, in order to preserve and protect the damage of anticancer compounds in mahkota dewa bark. The specimens of mahkota dewa bark were irradiated using 60 Co at the variation doses of 0; 5; 7,5 ; 10; 15; and 20 kGy, respectively at the dose rate of 10 kGy/h. The irradiated and control samples were macerated in n-hexane and ethyl acetate, respectively, then the ethyl acetate extract was then fractionated using chromatography column to obtain 8 fractions. The examination of irradiated and control samples of mahkota dewa bark against microbe contaminants showed that irradiation at doses ≥5 kGy could inhibit the growth of bacteria, mold and yeast and destroyed them. The cytotoxicity test of irradiated ethyl acetate extract of mahkota dewa bark against leukemia L1210 cell showed that irradiation at the dose up to 20 kGy can decreased cytotoxic activities performance, however these IC 50 values lower than 50 μg/ml, which is the cytotoxic activity threshold for extract. The cytotoxic activity test of fraction 6, the most active fraction in mahkota dewa bark, showed that irradiation at the dose up to 20 kGy can also decreased the cytotoxic activities performance, however these IC 50 values was lower than 20 μg/ml, which is the cytotoxic activity threshold for fraction. Analysis of 2,4’-dihydroxy-4 methoxy benzophenone-2-O-β-D-glucopyranoside by high performance liquid chromatography (HPLC) in fraction 6 of irradiated samples showed that the concentration of this compound in irradiated samples significantly decreased, compared to the control sample. Decreasing the concentration of 2,4’-dihydroxy-4 methoxy benzophenone-2-O-β-D-glucopyranoside was not comparable to the cytotoxic activity of ethyl acetate extract or fraction 6, therefore this compound can not be used as marker of irradiation effect on decreasing the cytotoxic activity of the mahkota dewa bark. Irradiation at doses of 5 up to 20 k

  1. Effects of in vivo exposure to UV filters (4-MBC, OMC, BP-3, 4-HB, OC, OD-PABA) on endocrine signaling genes in the insect Chironomus riparius.

    Science.gov (United States)

    Ozáez, Irene; Martínez-Guitarte, José Luis; Morcillo, Gloria

    2013-07-01

    There is increasing evidence indicating that several UV filters might have endocrine disruptive effects. Numerous studies have evaluated hormonal effects in vertebrates, mainly reporting estrogenic and androgenic activities in mammals and fishes. There is only limited knowledge about potential endocrine activity in invertebrate hormonal systems. In this work, the effects on endocrine signaling genes of six frequently used UV filters were investigated in Chironomus riparius, a reference organism in aquatic toxicology. The UV filters studied were: octyl-p-methoxycinnamate (OMC) also called 2-ethylhexyl-4-methoxycinnamate (EHMC); 4-methylbenzylidene camphor (4-MBC); benzophenone-3 (BP-3); 4-hidroxybenzophenone (4-HB); octocrylene (OC); and octyldimethyl-p-aminobenzoate (OD-PABA). After in vivo exposure at different dosages, expression levels of the genes coding for the ecdysone receptor (EcR), the ultraspiracle (usp, ortholog of the RXR) and the estrogen-related receptor (ERR) were quantified by Real Time PCR. The EcR gene was significantly upregulated by 4-MBC, OMC/EHMC and OD-PABA, with a dose-related response following 24h exposure. In contrast, the benzophenones, BP-3 and 4-HB, as well as OC did not alter this gene at the same exposure conditions. The transcription profiles of the usp and ERR genes were not significantly affected, except for BP-3 that inhibited the usp gene at the highest concentration. To our knowledge, this is the first experimental evidence in invertebrates of a direct effect of UV filters on endocrine-related genes, and is consistent with the known effects on vertebrate hormonal receptor genes. The capability of 4-MBC, OMC/EHMC and OD-PABA to stimulate the expression of the ecdysone receptor, a key transcription factor for the ecdysone-genomic response in arthropods, suggests the possibility of a broad and long-term effect on this hormonal pathway. These findings strengthen the need for further research about the ecotoxicological implications

  2. Carboxylate ligands induced structural diversity of zinc(II) coordination polymers based on 3,6-bis(imidazol-1-yl)carbazole: Syntheses, structures and photocatalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Hong-Jian, E-mail: hjcheng@cslg.cn; Tang, Hui-Xiang; Shen, Ya-Li; Xia, Nan-Nan; Yin, Wen-Yu; Zhu, Wei; Tang, Xiao-Yan; Ma, Yun-Sheng; Yuan, Rong-Xin, E-mail: yuanrx@cslg.edu.cn

    2015-12-15

    Solvothermal reactions of Zn(NO{sub 3}){sub 2}·6H{sub 2}O with 3,6-bis(1-imidazolyl)carbazole (3,6-bmcz) and 1,4-benzenedicarboxylic acid (1,4-H{sub 2}bdc), p-phenylenediacetic acid (p-H{sub 2}pda), benzophenone-4,4-dicarboxylic acid (H{sub 2}bpda) afforded three coordination polymers [Zn(1,4-bdc)(3,6-bmcz)]{sub n} (1), {[Zn(p-pda)(3,6-bmcz)]·1.5H_2O}{sub n} (2) and {[Zn(bpda)(3,6-bmcz)]·0.25H_2O}{sub n} (3). Complexes 1–3 were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. Complex 1 shows 3D structure with 2D nets inclined polycatenation. Complexes 2 and 3 possess an extended 3D supramolecular architecture based on their respective 2D layers through hydrogen-bonding interactions and the π···π stacking interactions. The solid state luminescent and optical properties of 1–3 at ambient temperature were also investigated. A comparative study on their photocatalytic activity toward the degradation of methylene blue in polluted water was explored. - Graphical abstract: Reactions of Zn(NO{sub 3}){sub 2} and 3,6-(1-imidazolyl)carbazole with 1,4-benzenedicarboxylic acid, p-phenylenediacetic acid or benzophenone-4,4-dicarboxylic acid afforded three coordination polymers with different topologies and photocatalytic activity. - Highlights: • Reactions of 1,4-H{sub 2}bdc, p-H{sub 2}pda or H{sub 2}bpda with 3,6-bmcz and Zn(II) gave three CPs. • Complex 1 is a 3D entanglement. • Complex 2 or 3 is a 3D supramolecular structure based on different 2D layers. • Complex 2 exhibited good catalytic activity of methylene blue photodegradation.

  3. Reactivity of cosmetic UV filters towards skin proteins: model studies with Boc-lysine, Boc-Gly-Phe-Gly-Lys-OH, BSA and gelatin.

    Science.gov (United States)

    Stiefel, C; Schwack, W

    2014-12-01

    Organic UV filters are used as active ingredients in most sunscreens and also in a variety of daily care products. Their good (photo) stability is of special interest to guarantee protective function and to prevent interactions with the human skin. Due to the mostly electrophilic character of the UV filters, reactions with nucleophilic protein moieties like lysine side chains are conceivable. Prior studies showed that the UV filters octocrylene (OCR), butyl methoxydibenzoylmethane (BM-DBM), ethylhexyl salicylate (EHS), ethylhexyl methoxycinnamate (EHMC), benzophenone-3 (BP-3), ethylhexyl triazone (EHT) and dibenzoylmethane (DBM) were able to covalently bind to an HPTLC amino phase and the amino acid models ethanolamine and butylamine after slightly heating and/or radiation. Boc-protected lysine, the tetrapeptide Boc-Gly-Phe-Gly-Lys-OH, bovine serum albumin (BSA) and porcine gelatin were used as more complex models to determine the reactivity of the mentioned UV filters towards skin proteins under thermal or UV irradiation conditions. After gentle heating at 37°C, benzophenone imines were identified as reaction products of BP-3 and OCR with Boc-lysine and the tetrapeptide, whereas DBM and BM-DBM yielded enamines. For EHMC, a Michael-type reaction occurred, which resulted in addition of Boc-lysine or the tetrapeptide to the conjugated double bond. Ester aminolysis of EHS and EHT mainly afforded the corresponding amides. Reactions of the UV filters with BSA changed the UV spectrum of BSA, generally associated with an increase of the absorption strength in the UVA or UVB range. For all protein models, the UV filters showed an increasing reactivity in the order EHT < EHMC < EHS < BP-3 < OCR < DBM < BM-DBM. Especially the UV absorbers BM-DBM, OCR and BP-3, which are seen as common allergens or photoallergens, showed a high reactivity towards the different skin protein models. As the formation of protein adducts is recognized as important key element in the induction of

  4. Variability and exposure classification of urinary phenol and paraben metabolite concentrations in reproductive-aged women

    Science.gov (United States)

    Pollack, Anna Z.; Perkins, Neil J.; Sjaarda, Lindsey; Mumford, Sunni L.; Kannan, Kurunthachalam; Philippat, Claire; Wactawski-Wende, Jean; Schisterman, Enrique F.

    2016-01-01

    Background Human exposure to phenols and parabens is widespread. Within-person variability of urinary concentrations in healthy women is not well characterized. Objectives To characterize the variability of urinary phenol and paraben concentrations across two months and evaluate the ability of a single spot urine sample to characterize exposure. Methods 143 women provided 509 spot urine samples collected across two months of study (3–5 samples/woman). We measured urinary concentrations of 8 phenols: bisphenol A (BPA), benzophenone-3 (BP-3), benzophenone-1 (BP-1), 2,4-dichlorophenol (2,4-DCP), 2,5-dichlorophenol (2,5-DCP), 2,4,5-trichlorophenol (2,4,5-TCP), 2,4,6-trichlorophenol (2,4,6-TCP), triclosan (TCS); and 8 parabens and their metabolites (benzyl (BzP), butyl (BuP), ethyl (EtP), heptyl (HeP), methyl (MeP), propyl (PrP), 4-hydro-xybenzoic acid (4-HB), 3,4-dihydroxybenzoic acid (3,4-DHB)). Biomarker variability was characterized using the intraclass correlation coefficient (ICC) and surrogate category analyses were conducted. Results ICCs ranged from very low for BPA (0.04) to moderate for BP-3, BP-1, TCS, BzP, and MeP (0.66, 0.58, 0.55, 0.54, and 0.62, respectively). Surrogate analyses suggested that BP-1, BP-3, TCS, 2,4-DCP, BuP, and PrP may be characterized by a single spot sample (sensitivity range 0.76–0.86) but that additional samples were necessary for BPA, HeP, 4-HB, and 3,4-DHB (sensitivity range 0.47–0.61). Conclusions Urinary phenol and paraben metabolite concentrations were variable across two months in healthy women but the degree of reliability differed by the specific biomarker. A small number of samples may sufficiently characterize typical concentrations for BP-3, BP-1, TCS, BuP, and PrP; but additional biospecimens may be necessary to characterize exposure for other compounds, including BPA. PMID:27567355

  5. Measurement of Total and Free Urinary Phenol and Paraben Concentrations over the Course of Pregnancy: Assessing Reliability and Contamination of Specimens in the Norwegian Mother and Child Cohort Study

    Science.gov (United States)

    Longnecker, Matthew P.; Aase, Heidi; Eggesbø, Merete; Zeiner, Pål; Reichborn-Kjennerud, Ted; Knudsen, Gun P.; Bertelsen, Randi J.; Ye, Xiaoyun; Calafat, Antonia M.; Engel, Stephanie M.

    2015-01-01

    Background Exposures to environmental phenols and parabens may be harmful, especially in utero. Prior studies have demonstrated high within-person variability of urinary concentrations across pregnancy. Objectives We sought to measure phenol and paraben biomarker concentrations for the Norwegian Mother and Child Cohort (MoBa) study, assess within-person variability, and investigate any possible external phenol or paraben contamination of specimens. Methods We collected three spot urine samples at approximately 17, 23, and 29 weeks gestation in a hospital setting and added a preservative containing ethyl paraben. We measured urinary concentrations and within-person variability for phenols and parabens in a MoBa sample (n = 45), including a subgroup of 15 participants previously randomly selected for a bisphenol A (BPA) exposure study who had unusually high total BPA concentrations. Additionally, we compared reliability results for total, conjugated, and free concentrations of phenolic compounds. Results We detected total and free BPA, butyl paraben, propyl paraben, and methyl paraben in 100% of samples, total benzophenone-3 in 95% of samples, and infrequently detected free benzophenone-3 and total and free 2,4-dichlorophenol and 2,5-dichlorophenol. Intraclass correlation coefficients (ICCs) for total, conjugated, and free concentrations ranged from relatively low for BPA to moderate for propyl paraben. ICCs were generally similar overall and by subgroup. Conclusions Using conjugated concentrations improved reliability estimates only for BPA. Measuring total and free concentrations, an approach that may be useful for future studies, allowed us to identify likely BPA and butyl paraben contamination of archived MoBa urine specimens. Citation Guidry VT, Longnecker MP, Aase H, Eggesbø M, Zeiner P, Reichborn-Kjennerud T, Knudsen GP, Bertelsen RJ, Ye X, Calafat AM, Engel SM. 2015. Measurement of total and free urinary phenol and paraben concentrations over the course of

  6. Determination of household and industrial chemicals, personal care products and hormones in leafy and root vegetables by liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Aparicio, Irene; Martín, Julia; Abril, Concepción; Santos, Juan Luis; Alonso, Esteban

    2018-01-19

    A multiresidue method has been developed for the determination of emerging pollutants in leafy and root vegetables. Selected compounds were 6 perfluoroalkyl compounds (5 perfluorocarboxylic acids and perfluorooctanesulfonic acid), 3 non-ionic surfactants (nonylphenol and nonylphenolethoxylates), 8 anionic surfactants (4 alkylsulfates and 4 linear alkylbenzene sulfonates), 4 preservatives (parabens), 2 biocides (triclosan and triclocarban), 2 plasticizers (bisphenol A and di-(2-ethylhexyl)phthalate), 6 UV-filters (benzophenones) and 4 hormones. The method is based on ultrasound-assisted extraction, clean-up by dispersive solid-phase extraction (d-SPE) and liquid chromatography-tandem mass spectrometry analysis. Due to the diversity of the physico-chemical properties of the target compounds, and to better evaluate the influence of sample treatment variables in extraction efficiencies, Box-Behnken design was applied to optimize extraction solvent volume, number of extraction cycles and d-SPE sorbent amount. Linearity (R 2 ) higher than 0.992, accuracy (expressed as relative recoveries) in the range from 81 to 126%, precision (expressed as relative standard deviation) lower than 19% and limits of detection between 0.025 and 12.5ngg -1 dry weight were achieved. The method was applied to leafy vegetables (lettuce, spinach and chard) and root vegetables (carrot, turnip and potato) from a local market. The highest concentrations corresponded to the surfactants reaching levels up to 114ngg -1 (dry weight), in one of the lettuce samples analyzed. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Occurrence and spatial distribution of microplastics in sediments from Norderney

    International Nuclear Information System (INIS)

    Dekiff, Jens H.; Remy, Dominique; Klasmeier, Jörg; Fries, Elke

    2014-01-01

    The spatial distribution of small potential microplastics (SPM) ( 1 mm) was also examined. Small microparticles were extracted from 36 one kg sediment samples and analysed by visual microscopic inspection and partly by thermal desorption pyrolysis gas chromatography/mass spectrometry. The smallest particle size that could be analysed with this method was estimated to be 100 μm. The mean number of SPM at the three sampling sites (n = 12) was 1.7, 1.3 and 2.3 particles per kg dry sediment, respectively. SPM were identified as polypropylene, polyethylene, polyethylene terephthalate, polyvinylchloride, polystyrene and polyamide. The organic plastic additives found were benzophenone, 1,2-benzenedicarboxylic acid, dimethyl phthalate, diethylhexyl phthalate, dibutyl phthalate, diethyl phthalate, phenol and 2,4-di-tert-butylphenol. Particles were distributed rather homogenously and the occurrence of SPM did not correlate with that of VPD. -- Highlights: • The small-scale variability of small potential microplastics (<1 mm) occurrence in beach sediments was studied. • Within 500 m, small potential microplastics (<1 mm) were distributed rather homogeneously in investigated beach sediments. • The occurrence of small potential microplastics (<1 mm) did not correlate with that of visible plastic debris. • Procedural contamination of sediments by fibres (blank) constitutes an analytical problem. • These findings must be considered when setting up standardized monitoring protocols. -- On a small scale within 500 m, small microplastics are distributed rather homogeneously in sediments from the North Sea island of Norderney

  8. Magnetic Composite Thin Films of FexOy Nanoparticles and Photocrosslinked Dextran Hydrogels

    International Nuclear Information System (INIS)

    Brunsen, Annette; Utech, Stefanie; Maskos, Michael; Knoll, Wolfgang; Jonas, Ulrich

    2012-01-01

    Magnetic hydrogel composites are promising candidates for a broad field of applications from medicine to mechanical engineering. Here, surface-attached composite films of magnetic nanoparticles (MNP) and a polymeric hydrogel (HG) were prepared from magnetic iron oxide nanoparticles and a carboxymethylated dextran with photoreactive benzophenone substituents. A blend of the MNP and the dextran polymer was prepared by mixing in solution, and after spin-coating and drying the blend film was converted into a stable MNP–HG composite by photocrosslinking through irradiation with UV light. The bulk composite material shows strong mobility in a magnetic field, imparted by the MNPs. By utilizing a surface layer of a photoreactive adhesion promoter on the substrates, the MNP–HG films were covalently immobilized during photocrosslinking. The high stability of the composite was documented by rinsing experiments with UV–Vis spectroscopy, while surface plasmon resonance and optical waveguide mode spectroscopy was employed to investigate the swelling behavior in dependence of the nanoparticle concentration, the particle type, and salt concentration. - Highlights: ► blending of iron oxide nanoparticles with photocrosslinkable carboxymethyldextran. ► UV irradiation of blend yields surface-attached, magnetic hydrogel films. ► film characterization by surface plasmon resonance/optical waveguide spectroscopy. ► swelling decreases with increasing nanoparticle content. ► swelling decreases with increasing NaCl salt concentration in the aqueous medium.

  9. Inhibition of HIF-1{alpha} activity by BP-1 ameliorates adjuvant induced arthritis in rats

    Energy Technology Data Exchange (ETDEWEB)

    Shankar, J. [Department of Microbiology and Immunology, University of Illinois at Chicago, Chicago (United States); Thippegowda, P.B., E-mail: btprabha@uic.edu [Department of Pharmacology, (M/C 868), College of Medicine, University of Illinois at Chicago, 835 S. Wolcott Ave., Chicago, IL 60612 (United States); Kanum, S.A. [Department of Chemistry, Yuvaraj' s College, University of Mysore, Mysore (India)

    2009-09-18

    Rheumatoid arthritis (RA) is a chronic inflammatory, angiogenic disease. Inflamed synovitis is a hallmark of RA which is hypoxic in nature. Vascular endothelial growth factor (VEGF), one of the key regulators of angiogenesis, is overexpressed in the pathogenesis of RA. VEGF expression is regulated by hypoxia-inducible factor-1{alpha} (HIF-1{alpha}), a master regulator of homeostasis which plays a pivotal role in hypoxia-induced angiogenesis. In this study we show that synthetic benzophenone analogue, 2-benzoyl-phenoxy acetamide (BP-1) can act as a novel anti-arthritic agent in an experimental adjuvant induced arthritis (AIA) rat model by targeting VEGF and HIF-1{alpha}. BP-1 administered hypoxic endothelial cells and arthritic animals clearly showed down regulation of VEGF expression. Further, BP-1 inhibits nuclear translocation of HIF-1{alpha}, which in turn suppresses transcription of the VEGF gene. These results suggest a further possible clinical application of the BP-1 derivative as an anti-arthritic agent in association with conventional chemotherapeutic agents.

  10. Selective determination of dimenhydrinate in presence of six of its related substances and potential impurities using a direct GC/MS method

    Directory of Open Access Journals (Sweden)

    Tarek S. Belal

    2016-01-01

    Full Text Available A novel simple, direct and selective gas chromatography–mass spectrometry (GC/MS procedure was developed for the determination of the antihistamine drug dimenhydrinate (DMH in presence of six of its related substances and potential impurities, namely, diphenylmethane, diphenylmethanol, benzophenone, orphenadrine, caffeine and 8-chlorocaffeine. The method involved resolution of the underivatized compounds using a trifluoropropylmethyl polysiloxane (Rtx-200 capillary column and the mass spectrometric detection was carried out in the electron-impact (EI mode. Excellent baseline separation of DMH and the cited related substances was achieved in less than 15 min. Quantification of the parent drug DMH was based on measuring its peak area. The reliability and analytical performance of the proposed method were validated with respect to linearity, range, precision, accuracy, specificity, robustness, detection and quantification limits. Calibration curve of DMH was linear over the range 50–500 μg/mL with determination coefficient (R2 = 0.9982. The proposed method was successfully applied for the assay of DMH in tablets dosage form with recoveries >96.80%.

  11. Testing of the abiotic degradation of chemicals in the atmosphere: the smog chamber approach

    Energy Technology Data Exchange (ETDEWEB)

    Kloepffer, W.H.; Haag, F.; Kohl, E.G.; Frank, R.

    1988-06-01

    Methods for measuring the hydroxyl-, ozone-, and direct photochemical reactivity of a substance in one specially designed medium size smog chamber are described. Rate coefficients for the reaction of OH with n-hexane, n-heptane, ethene, ethyne, chloroform, trichloroethene, methanol, 2-propanol, benzene, o-xylene, 1,4-dichlorobenzene, 1,2,4-trichlorobenzene, p-chloroaniline, naphthalene, acenaphthene, 1,4-dichloronaphthalene, biphenyl, and fluorenone are given and discussed. An upper limit of 5 X 10(-13) cm3/sec is given for the sum penta- and hexa-chlorobiphenyls (PCB). Rate coefficients for the ozone reaction are given for beta-pinene, limonene, delta 3-carene, cineol, vinyl chloride and 1,3-butadiene. In cases where the literature data are available for comparison, the rate coefficients (kappa OH and kappa O3) reported here compare favorably with the best data reported. The direct photochemical reactivity has been shown to be measurable if the chamber is cleaned carefully. Preliminary results on benzophenone are reported. The methods described here, except that of direct photochemical reactivity, are in agreement with those proposed to OECD. Moreover, part of the Draft OECD Test Guideline (Berlin, 1987) on Photochemical-Oxidative Degradation in the Atmosphere is based on work described here and on closely related work in other laboratories.

  12. Cuban and Brazilian red propolis: botanical origin and comparative analysis by high-performance liquid chromatography-photodiode array detection/electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Piccinelli, Anna Lisa; Lotti, Cinzia; Campone, Luca; Cuesta-Rubio, Osmany; Campo Fernandez, Mercedes; Rastrelli, Luca

    2011-06-22

    Chemical composition of propolis depends on the specificity of the local flora at the site of collection and thus on the geographic and climatic characteristics of this place. This paper describes a comparative analysis of Cuban red propolis (CRP), Brazilian red propolis (BRP), and Dalbergia ecastophyllum exudates (DEE) by high-performance liquid chromatography with diode-array detection and tandem mass spectrometry. The aim of this study was to investigate the overall chemical profile and the botanical origin of red propolis and to suggest similarities and differences between samples collected in different tropical regions. Isoliquiritigenin (1), liquiritigenin and naringenin (2 and 17), isoflavones (3-4 and 16), isoflavans (5-7 and 18), and pterocarpans (8-13) were detected in CRP, BRP, and DEE, whereas polyisoprenylated benzophenones (PPBs) guttiferone E/xanthochymol (14a,b) and oblongifolin A (15) were detected only in BRP. Pigments responsible for the red color of DEE and red propolis were also identified as two C30 isoflavans, the new retusapurpurin B (19) and retusapurpurin A (20). PPBs and pigments were isolated and unambiguously characterized by 1D and 2D NMR analysis. These results show that red propolis samples from different tropical zones have a similar chemical composition. DEE is the main red propolis source, but the presence of PPBs in BRP suggests the contribution of different botanical sources for Brazilian samples. This chemical information is important for quality control of red propolis and its commercial products and for biological study.

  13. Polypropylene non-woven meshes with conformal glycosylated layer for lectin affinity adsorption: the effect of side chain length.

    Science.gov (United States)

    Ye, Xiang-Yu; Huang, Xiao-Jun; Xu, Zhi-Kang

    2014-03-01

    The unique characteristics of polypropylene non-woven meshes (PPNWMs), like random network of overlapped fibers, multiple connected pores and overall high porosity, make them high potentials for use as separation or adsorption media. Meanwhile, carbohydrates can specifically recognize certain lectin through multivalent interactions. Therefore glycosylated PPNWMs, combing the merits of both, can be regarded as superior affinity membranes for lectin adsorption and purification. Here, we describe a versatile strategy for the glycosylation of PPNWMs. Two hydrophilic polymers with different side chain length, poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(oligo(ethylene glycol) methacrylate) (POEGMA), were first conformally tethered on the polypropylene fiber surface by a modified plasma pretreatment and benzophenone (BP) entrapment UV irradiation process. Then glucose ligands were bound through the reaction between the hydroxyl group and acetyl glucose. Chemical changes of the PPNWMs surface were monitored by FT-IR/ATR. SEM pictures show that conformal glucose ligands can be achieved through the modified process. After deprotection, the glycosylated PPNWMs became superhydrophilic and had high specific recognition capability toward Concanavalin A (Con A). Static Con A adsorption experiments were further performed and the results indicate that fast adsorption kinetics and high binding capacity can be accomplished at the same time. We also found that increasing the side chain length of polymer brushes had positive effect on protein binding capacity due to improved chain mobility. Model studies suggest a multilayer adsorption behavior of Con A. Copyright © 2013 Elsevier B.V. All rights reserved.

  14. Observation of excited state charge transfer with fs/ps-CARS

    International Nuclear Information System (INIS)

    Blom, Alex Jason

    2009-01-01

    Excited state charge transfer processes are studied using the fs/ps-CARS probe technique. This probe allows for multiplexed detection of Raman active vibrational modes. Systems studied include Michler's Ketone, Coumarin 120, 4-dimethylamino-4(prime)-nitrostilbene, and several others. The vibrational spectrum of the para di-substituted benzophenone Michler's Ketone in the first excited singlet state is studied for the first time. It is found that there are several vibrational modes indicative of structural changes of the excited molecule. A combined experimental and theoretical approach is used to study the simplest 7-amino-4-methylcoumarin, Coumarin 120. Vibrations observed in FTIR and spontaneous Raman spectra are assigned using density functional calculations and a continuum solvation model is used to predict how observed modes are affected upon inclusion of a solvent. The low frequency modes of the excited state charge transfer species 4-dimethylamino-4(prime)-nitrostilbene are studied in acetonitrile. Results are compared to previous work on this molecule in the fingerprint region. Finally, several partially completed projects and their implications are discussed. These include the two photon absorption of Coumarin 120, nanoconfinement in cyclodextrin cavities and sensitization of titania nanoparticles

  15. Manganese peroxidase h4 isozyme mediated degradation and detoxification of triarylmethane dye malachite green: optimization of decolorization by response surface methodology.

    Science.gov (United States)

    Saravanakumar, Thiyagarajan; Palvannan, Thayumanavan; Kim, Dae-Hyuk; Park, Seung-Moon

    2013-11-01

    A cDNA encoding for manganese peroxidase isozyme H4 (MnPH4), isolated from Phanerochaete chrysosporium, was expressed in Pichia pastoris, under the control of alcohol oxidase I promoter. The recombinant MnPH4 was efficiently secreted onto media supplemented with hemin at a maximum concentration of 500 U/L, after which purified rMnPH4 was used to decolorize the triarylmethane dye malachite green (MG). Response surface methodology (RSM) was employed to optimize three different operational parameters for the decolorization of MG. RSM showed that the optimized variables of enzyme (0.662 U), MnSO4 (448 μM), and hydrogen peroxide (159 μM) decolorized 100 mg/L of MG completely at 3 h. Additionally, UV-VIS spectra, high-performance liquid chromatography, gas chromatography-mass spectrometry, and liquid chromatography-electrospray ionization/mass spectrometry analysis confirmed the degradation of MG by the formation of main metabolites 4-dimethylamino-benzophenone hydrate, N, N-dimethylaniline (N,N-dimethyl-benzenamine), and methylbenzaldehyde. Interestingly, it was found that rMnPH4 mediates hydroxyl radical attack on the central carbon of MG. Finally, rMnPH4 degraded MG resulted in the complete removal of its toxicity, which was checked under in vitro conditions.

  16. Electrochemical degradation of crystal violet with BDD electrodes: effect of electrochemical parameters and identification of organic by-products.

    Science.gov (United States)

    Palma-Goyes, Ricardo E; Guzmán-Duque, Fernando L; Peñuela, Gustavo; González, Ignacio; Nava, Jose L; Torres-Palma, Ricardo A

    2010-09-01

    This paper explores the applicability of electrochemical oxidation on a triphenylmethane dye compound model, hexamethylpararosaniline chloride (or crystal violet, CV), using BDD anodes. The effect of the important electrochemical parameters: current density (2.5-15 m A cm(-2)), dye concentration (33-600 mg L(-1)), sodium sulphate concentration (7.1-50.0 g L(-1)) and initial pH (3-11) on the efficiency of the electrochemical process was evaluated. The results indicated that while the current density was lower than the limiting current density, no side products (hydrogen peroxide, peroxodisulphate, ozone and chlorinated oxidizing compounds) were generated and the degradation, through OH radical attack, occurred with high efficiency. Analysis of intermediates using GC-MS investigation identified several products: N-methylaniline, N,N-dimethylaniline, 4-methyl-N,N-dimethylaniline, 4-methyl-N-methylaniline, 4-dimethylaminophenol, 4-dimethylaminobenzoic acid, 4-(N,N-dimethylamino)-4'-(N',N'-dimethylamino) diphenylmethane, 4-(4-dimethylaminophenyl)-N,N-dimethylaniline, 4-(N,N-dimethylamino)-4'-(N',N'-dimethylamino) benzophenone. The presence of these aromatic structures showed that the main CV degradation pathway is related to the reaction of CV with the OH radical. Under optimal conditions, practically 100% of the initial substrate and COD were eliminated in approximately 35 min of electrolysis; indicating that the early CV by-products were completely degraded by the electrochemical system. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

  17. Octocrylene, an emerging photoallergen.

    Science.gov (United States)

    Avenel-Audran, Martine; Dutartre, Hervé; Goossens, An; Jeanmougin, Michel; Comte, Christelle; Bernier, Claire; Benkalfate, Lamia; Michel, Maryse; Ferrier-Lebouëdec, Marie Christine; Vigan, Martine; Bourrain, Jean Luc; Outtas, Omar; Peyron, Jean Louis; Martin, Ludovic

    2010-07-01

    Octocrylene is a new emerging photoallergen. We report and discuss 50 cases of photoallergic contact dermatitis from octocrylene use and/or positive photopatch test reactions to this UV filter and draw attention to the unexpected association in adults with a history of photoallergic contact dermatitis from ketoprofen. Patients were divided in 3 groups: group A comprised 11 children; group B, 28 adults with a history of photoallergy from sunscreen products; and group C, 14 adults systematically tested with octocrylene because of a history of photoallergy from ketoprofen. All patients but 3 in group C had positive test reactions to octocrylene. Ten of 11 children in group A and 9 of 28 adults in group B had positive patch test reactions to octocrylene. One child in group A, the other 19 adults in group B, and 11 of 14 adults in group C had positive photopatch test reactions to octocrylene. All adults in group C and 24 of 28 adults in group B had a history of photoallergy from ketoprofen and positive patch test or photopatch test reactions to other allergens that are often positive in patients with photoallergy from ketoprofen, especially fragrance components. Octocrylene appears to be a strong allergen leading to contact dermatitis in children and mostly photoallergic contact dermatitis in adults with an often-associated history of photoallergy from ketoprofen. Patients with photoallergy from ketoprofen frequently have positive photopatch test reactions to octocrylene. These patients need to be informed of sunscreen products not containing octocrylene, benzophenone-3, or fragrances.

  18. Roles of free radicals in type 1 phototherapeutic agents: aromatic amines, sulfenamides, and sulfenates.

    Science.gov (United States)

    Lin, Tien-Sung; Rajagopalan, Raghavan; Shen, Yuefei; Park, Sungho; Poreddy, Amruta R; Asmelash, Bethel; Karwa, Amolkumar S; Taylor, John-Stephen A

    2013-07-03

    Detailed analyses of the electron spin resonance (ESR) spectra, cell viability, and DNA degradation studies are presented for the photolyzed Type I phototherapeutic agents: aromatic amines, sulfenamides, and sulfenates. The ESR studies provided evidence that copious free radicals can be generated from these N-H, N-S, and S-O containing compounds upon photoirradiation with UV/visible light. The analyses of spectral data allowed us to identify the free radical species. The cell viability studies showed that these agents after exposure to light exert cytotoxicity to kill cancer cells (U937 leukemia cell lines HTC11, KB, and HT29 cell lines) in a dosage- and time-dependent manner. We examined a possible pathway of cell death via DNA degradation by a plasmid cleavage assay for several compounds. The effects of photosensitization with benzophenone in the presence of oxygen were examined. The studies indicate that planar tricyclic amines and sulfenamides tend to form π-electron delocalized aminyl radicals, whereas nonplanar ones tend to yield nitroxide radicals resulting from the recombination of aminyl radicals with oxygen. The ESR studies coupled with the results of cell viability measurements and DNA degradation reveal that planar N-centered radicals can provide higher potency in cell death and allow us to provide some insights on the reaction mechanisms. We also found the formation of azatropylium cations possessing high aromaticity derived from azepines can facilitate secondary electron transfer to form toxic O2(•-) radicals, which can further exert oxidative stress and cause cell death.

  19. Sunscreens in human plasma and urine after repeated whole-body topical application

    DEFF Research Database (Denmark)

    Janjua, N.R.; Kongshoj, B.; Andersson, A.M.

    2008-01-01

    Background The three chemical ultraviolet absorbers benzophenone-3 (BP-3), octyl-methoxycinnamate (OMC) and 3-(4-methylbenzylidene) camphor (4-MBC) are commercially used in sunscreens worldwide. Apart from sun protection, they may possess endocrine-disrupting effects in animals and in vitro...... the first application, all three sunscreens were detectable in plasma. The maximum median plasma concentrations were 187 ng/mL BP-3, 16 ng/mL 4-MBC and 7 ng/mL OMC for females and 238 ng/mL BP-3, 18 ng/mL 4-MBC and 16 ng/mL OMC for men. In the females, urine levels of 44 ng/mL BP-3 and 4 ng/mL of 4-MBC...... and 6 ng/mL OMC were found, and in the males, urine levels of 81 ng/mL BP-3, 4 ng/mL of 4-MBC and OMC were found. In plasma, the 96-h median concentrations were higher compared with the 24-h concentrations for 4-MBC and OMC in men and for BP-3 and 4-MBC in females Udgivelsesdato: 2008/4...

  20. A comparative study of alumina-supported Ni catalysts prepared by photodeposition and impregnation methods on the catalytic ozonation of 2,4-dichlorophenoxyacetic acid

    Energy Technology Data Exchange (ETDEWEB)

    Rodríguez, Julia L., E-mail: ozliliana@yahoo.com.mx [Lab. Ing. Química Ambiental. ESIQIE–Instituto Politécnico Nacional (Mexico); Valenzuela, Miguel A. [Lab.Catálisis y Materiales. ESIQIE–Instituto Politécnico Nacional. Zacatenco (Mexico); Tiznado, Hugo [Centro de Nanociencias y Nanotecnología. CNyN Universidad Nacional Autónoma de México (Mexico); Poznyak, Tatiana [Lab. Ing. Química Ambiental. ESIQIE–Instituto Politécnico Nacional (Mexico); Chairez, Isaac [Departamento de Bioprocesos, UPIBI- Instituto Politécnico Nacional (Mexico); Magallanes, Diana [Lab. Ing. Química Ambiental. ESIQIE–Instituto Politécnico Nacional (Mexico)

    2017-02-15

    The heterogeneous catalytic ozonation on unsupported and supported oxides has been successfully tested for the removal of several refractory compounds in aqueous solution. In this work, alumina-supported nickel catalysts prepared by photodeposition and impregnation methods were compared in the catalytic ozonation of 2,4-dichlorophenoxyacetic acid (2,4-D). The catalysts were characterized by high-resolution electron microscopy and X-ray photoelectron spectroscopy. The photochemical decomposition of Ni acetylacetonate to produce Ni(OH){sub 2}, NiO, and traces of Ni° deposited on alumina was achieved in the presence of benzophenone as a sensitizer. A similar surface composition was found with the impregnated catalyst after its reduction with hydrogen at 500 °C and exposed to ambient air. Results indicated a higher initial activity and maleic acid (byproduct) concentration with the photodeposited catalyst (1 wt% Ni) compared to the impregnated catalyst (3 wt% Ni). These findings suggest the use of the photodeposition method as a simple and reliable procedure for the preparation of supported metal oxide/metal catalysts under mild operating conditions.

  1. Ionic liquid based multifunctional double network gel

    Science.gov (United States)

    Ahmed, Kumkum; Higashihara, Tomoya; Arafune, Hiroyuki; Kamijo, Toshio; Morinaga, Takashi; Sato, Takaya; Furukawa, Hidemitsu

    2015-04-01

    Gels are a promising class of soft and wet materials with diverse application in tissue engineering and bio-medical purpose. In order to accelerate the development of gels, it is required to synthesize multi-functional gels of high mechanical strength, ultra low surface friction and suitable elastic modulus with a variety of methods and new materials. Among many types of gel ionic gel made from ionic liquids (ILs) could be used for diverse applications in electrochemical devices and in the field of tribology. IL, a promising materials for lubrication, is a salt with a melting point lower than 100 °C. As a lubricant, ILs are characterized by an extremely low vapor pressure, high thermal stability and high ion conductivity. In this work a novel approach of making double network DN ionic gel using IL has been made utilizing photo polymerization process. A hydrophobic monomer Methyl methacrylate (MMA) has been used as a first network and a hydrophobic IL monomer, N,N-diethyl-N-(2-mthacryloylethyl)-N-methylammonium bistrifluoromethylsulfonyl)imide (DEMM-TFSI) has been used as a second network using photo initiator benzophenon and crosslinker triethylene glycol dimethacrylate (TEGDMA). The resulting DN ionic gel shows transparency, flexibility, high thermal stability, good mechanical toughness and low friction coefficient value which can be a potential candidate as a gel slider in different mechanical devices and can open a new area in the field of gel tribology.

  2. Durability and degradation analysis of hydrocarbon ionomer membranes in polymer electrolyte fuel cells accelerated stress evaluation

    Science.gov (United States)

    Shimizu, Ryo; Tsuji, Junichi; Sato, Nobuyuki; Takano, Jun; Itami, Shunsuke; Kusakabe, Masato; Miyatake, Kenji; Iiyama, Akihiro; Uchida, Makoto

    2017-11-01

    The chemical durabilities of two proton-conducting hydrocarbon polymer electrolyte membranes, sulfonated benzophenone poly(arylene ether ketone) (SPK) semiblock copolymer and sulfonated phenylene poly(arylene ether ketone) (SPP) semiblock copolymer are evaluated under accelerated open circuit voltage (OCV) conditions in a polymer electrolyte fuel cell (PEFC). Post-test characterization of the membrane electrodes assemblies (MEAs) is carried out via gel permeation chromatography (GPC) and nuclear magnetic resonance (NMR) spectroscopy. These results are compared with those of the initial MEAs. The SPP cell shows the highest OCV at 1000 h, and, in the post-test analysis, the SPP membrane retains up to 80% of the original molecular weight, based on the GPC results, and 90% of the hydrophilic structure, based on the NMR results. The hydrophilic structure of the SPP membrane is more stable after the durability evaluation than that of the SPK. From these results, the SPP membrane, with its simple hydrophilic structure, which does not include ketone groups, is seen to be significantly more resistant to radical attack. This structure leads to high chemical durability and thus impedes the chemical decomposition of the membrane.

  3. Transition-metal-free chemo- and regioselective vinylation of azaallyls

    Science.gov (United States)

    Li, Minyan; Gutierrez, Osvaldo; Berritt, Simon; Pascual-Escudero, Ana; Yeşilçimen, Ahmet; Yang, Xiaodong; Adrio, Javier; Huang, Georgia; Nakamaru-Ogiso, Eiko; Kozlowski, Marisa C.; Walsh, Patrick J.

    2017-10-01

    Direct C(sp3)-C(sp2) bond formation under transition-metal-free conditions offers an atom-economical, inexpensive and environmentally benign alternative to traditional transition-metal-catalysed cross-coupling reactions. A new chemo- and regioselective coupling protocol between 3-aryl-substituted-1,1-diphenyl-2-azaallyl derivatives and vinyl bromides has been developed. This is the first transition-metal-free cross-coupling of azaallyls with vinyl bromide electrophiles and delivers allylic amines in excellent yields (up to 99%). This relatively simple and mild protocol offers a direct and practical strategy for the synthesis of high-value allylic amine building blocks that does not require the use of transition metals, special initiators or photoredox catalysts. Radical clock experiments, electron paramagnetic resonance studies and density functional theory calculations point to an unprecedented substrate-dependent coupling mechanism. Furthermore, an electron paramagnetic resonance signal was observed when the N-benzyl benzophenone ketimine was subjected to silylamide base, supporting the formation of radical species upon deprotonation. The unique mechanisms outlined herein could pave the way for new approaches to transition-metal-free C-C bond formations.

  4. Organic polar pollutants in surface waters of inland seas.

    Science.gov (United States)

    Orlikowska, Anna; Fisch, Kathrin; Schulz-Bull, Detlef E

    2015-12-30

    Available data about contamination by polar substances are mostly reported for rivers and near-shore waters and only limited studies exists about their occurrence in marine waters. We present concentrations and distribution of several polar pesticides and UV-filters in surface waters of three inland seas, the Baltic, Black and Mediterranean Sea. Many of the investigated compounds were below detection limits, however, those found in off-shore waters raise a concern about their persistence and possible adverse effect on the ecosystem. Despite a longstanding EU-wide ban we were able to detect atrazine in the Mediterranean and the Baltic Sea. Concentrations in the Black Sea were substantially higher. Runoff from agricultural and urban areas was the main transport route to marine ecosystems for investigated compounds, though irgarol in Mediterranean waters was attributed to intense maritime traffic. 2-Phenylbenzimidazole-5-sulfonic acid was the only UV-filter detected in marine waters, while benzophenone-4 was observed in the estuaries. Occurrence of UV-filters was seasonal. Copyright © 2015 Elsevier Ltd. All rights reserved.

  5. The CDC fourth national report on human exposure to environmental chemicals: what it tells us about our toxic burden and how it assist environmental medicine physicians.

    Science.gov (United States)

    Crinnion, Walter J

    2010-07-01

    The Centers for Disease Control (CDC) conducts ongoing assessments of the levels of environmental chemicals in the U.S. population. This ongoing study utilizes lab samples from the individuals who are part of the National Health and Nutrition Examination Survey (NHANES). The NHANES samples from the years 1999-2000, 2001-2002, and 2003-2004 (each representing about 2,400 individuals) were used for the CDC's national reports. In the CDC Fourth National Report on Human Exposure to Environmental Chemicals ("the fourth report") complete data from the above sample years were included. Each year additional chemicals are measured; the fourth report contains information on 75 previously untested compounds, for a total of 212 compounds measured. In the fourth report, blood and urinary levels of eight different forms of arsenic are reported. The fourth report, for the first time, also includes levels of solvents (30 different compounds) and provides adult rather than juvenile values for mercury. In the majority of individuals tested, acrylamides, cotinine, trihalomethanes, bisphenol A, phthalates, chlorinated pesticides, triclosan, organophosphate pesticides, pyrethroids, heavy metals, aromatic hydrocarbons, polybrominated diphenyl ethers, benzophenone from sunblock, perfluorocarbons from non-stick coatings, and a host of polychlorinated biphenyls and solvents were found. This review provides many of the ranges for xenobiotic toxins so a clinician can identify a patient's current exposure and toxic load compared to the national averages and monitor the effectiveness of prescribed treatments.

  6. Interferometrically stable, enclosed, spinning sample cell for spectroscopic experiments on air-sensitive samples.

    Science.gov (United States)

    Baranov, Dmitry; Hill, Robert J; Ryu, Jisu; Park, Samuel D; Huerta-Viga, Adriana; Carollo, Alexa R; Jonas, David M

    2017-01-01

    In experiments with high photon flux, it is necessary to rapidly remove the sample from the beam and to delay re-excitation until the sample has returned to equilibrium. Rapid and complete sample exchange has been a challenge for air-sensitive samples and for vibration-sensitive experiments. Here, a compact spinning sample cell for air and moisture sensitive liquid and thin film samples is described. The principal parts of the cell are a copper gasket sealed enclosure, a 2.5 in. hard disk drive motor, and a reusable, chemically inert glass sandwich cell. The enclosure provides an oxygen and water free environment at the 1 ppm level, as demonstrated by multi-day tests with sodium benzophenone ketyl radical. Inside the enclosure, the glass sandwich cell spins at ≈70 Hz to generate tangential speeds of 7-12 m/s that enable complete sample exchange at 100 kHz repetition rates. The spinning cell is acoustically silent and compatible with a ±1 nm rms displacement stability interferometer. In order to enable the use of the spinning cell, we discuss centrifugation and how to prevent it, introduce the cycle-averaged resampling rate to characterize repetitive excitation, and develop a figure of merit for a long-lived photoproduct buildup.

  7. Description of exposure profiles for seven environmental chemicals in a US population using recursive partition mixture modeling (RPMM).

    Science.gov (United States)

    Przybyla, Jennifer; Kile, Molly; Smit, Ellen

    2017-12-21

    Biomonitoring studies have shown that humans are exposed to numerous environmental chemicals. Previous work provides limited insights into the dynamic relationship between different chemicals within a population. The objective of this study is to develop an analytical method identifying exposure profiles of seven common environmental chemicals and determine how exposure profiles differ by sociodemographic groups and National Health and Nutrition Examination Survey (NHANES) 2003-2012 cycle year. We used recursive partition mixture modeling (RPMM) to define classes of the population with similar exposure profiles of lead, cadmium, 2,4-dichlorophenol, 2,5-dichlorophenol, bisphenol A (BPA), triclosan, and benzophenone-3 in individuals aged ≥6 years. Additionally, quasibinomial logistic regression was used to examine the association between each class and selected demographic characteristics. Eight exposure profiles were identified. Individuals who clustered together and had the highest chemical exposures were more likely to be older, to be Non-Hispanic Black (NHB) or Other Hispanic (OH), more likely to live below the poverty line, more likely to be male, and more likely to have participated in the earlier NHANES cycle (2003-2004). The developed method described the dynamic relationship between chemicals and shows that this relationship is different for subpopulations based on their sociodemographic characteristics.

  8. Distribution, variability, and predictors of urinary concentrations of phenols and parabens among pregnant women in Puerto Rico.

    Science.gov (United States)

    Meeker, John D; Cantonwine, David E; Rivera-González, Luis O; Ferguson, Kelly K; Mukherjee, Bhramar; Calafat, Antonia M; Ye, Xiaoyun; Anzalota Del Toro, Liza V; Crespo-Hernández, Noé; Jiménez-Vélez, Braulio; Alshawabkeh, Akram N; Cordero, José F

    2013-04-02

    Puerto Rico has higher rates of a range of endocrine-related diseases and disorders compared to the United States. However, little is known to date about human exposures to known or potential endocrine disrupting chemicals (EDCs) in Puerto Rico. We recruited 105 pregnant women in Northern Puerto Rico who provided urine samples and questionnaire data at three times (18 ± 2, 22 ± 2, and 26 ± 2 weeks) during gestation. We measured the urinary concentrations of five phenols and three parabens: 2,4-dichlorophenol (24-DCP), 2,5-dichlorophenol (25-DCP), benzophenone-3 (BP-3), bisphenol A (BPA), triclosan (TCS), butyl paraben (B-PB), methyl paraben (M-PB), and propyl paraben (P-PB). The frequent detection of these chemicals suggests that exposure is highly prevalent among these Puerto Rican pregnant women. Urinary concentrations of TCS, BP-3, and 25-DCP were higher than among women of reproductive age in the US general population, while concentrations of BPA, 24-DCP, and parabens were similar. Intraclass correlation coefficients (ICC) varied widely between biomarkers; BPA had the lowest ICC (0.24) and BP-3 had the highest (0.62), followed by 25-DCP (0.49) and TCS (0.47). We found positive associations between biomarker concentrations with self-reported use of liquid soap (TCS), sunscreen (BP-3), lotion (BP-3 and parabens), and cosmetics (parabens). Our results can inform future epidemiology studies and strategies to reduce exposure to these chemicals or their precursors.

  9. Microwave-optical double resonance spectroscopy. Progress report, February 1, 1975--January 31, 1976

    International Nuclear Information System (INIS)

    Pratt, D.W.

    1975-01-01

    Zero-field and high-field optical detection of magnetic resonance (ODMR), electron paramagnetic resonance (EPR), and optical spectroscopy experiments were performed on several systems in order to further basic knowledge of the structure, reactions, and response to radiation of atoms, molecules, and ions. Results on the following studies are reported: the direct observation of level anticrossing and mixing effects in excited molecular triplet states; anomalous zero-field splittings in the lowest triplet state of 1-iodonaphthalene; evidence for second-order spin-orbit coupling and spin delocalization effects in the lowest triplet state of benzophenone; direct observation of the optical absorption spectra of reactive free radicals at room temperature; measurements of the activation and thermodynamic parameters of several cyclohexenyl and cyclohexanonyl radicals; complete analyses of the level anticrossing and cross relaxation spectra of oriented molecular triplet states; solutions to the spin Hamiltonian for S = 1, I = 5/2 systems in both zero-field and high-field, an improvement by a factor of ten in the resolution of ODMR experiments in high field; and measurements of the optical and magnetic resonance properties of a series of halogenated naphthalenes in their lowest triplet states

  10. Animal model for evaluation of topical photoprotection against ultraviolet A (320-380 nm) radiation

    International Nuclear Information System (INIS)

    Chew, S.; DeLeo, V.A.; Harber, L.C.

    1987-01-01

    Recent studies reporting UVA (ultraviolet A radiation 320-380 nm) as an integral part of the cumulative sun-induced damage in human skin have prompted an interest in developing effective UVA photoprotective agents. The development of such compounds has been impeded by the absence of a clinically relevant animal model for evaluating their efficacy. This report describes the development and use of such a laboratory animal system. Selected concentrations of oxybenzone (2-hydroxy-4-methoxybenzophenone) in vehicle (0.1% to 6%) or vehicle alone were applied to the depilated dorsal skin of 30 Hartley strain female albino guinea pigs. The skin was irradiated with solar simulated UVA from a xenon light source. Acute radiation-induced damage was assayed by erythema grading and inhibition of [ 3 H]thymidine incorporation into epidermal DNA. Data from erythema grading studies indicated that a significant degree of photoprotection was achieved with 6%, 3%, and 1% solutions of benzophenone compared with the control vehicle; the 6% solution was significantly more photoprotective than the 3% and 1% solutions. A 6% solution afforded significant photoprotection when assayed by [ 3 H]thymidine incorporation

  11. Green Synthesis of Gold Nanoparticles Using Aqueous Extract of Garcinia mangostana Fruit Peels

    Directory of Open Access Journals (Sweden)

    Kar Xin Lee

    2016-01-01

    Full Text Available The synthesis of gold nanoparticles (Au-NPs is performed by the reduction of aqueous gold metal ions in contact with the aqueous peel extract of plant, Garcinia mangostana (G. mangostana. An absorption peak of the gold nanoparticles is observed at the range of 540–550 nm using UV-visible spectroscopy. All the diffraction peaks at 2θ = 38.48°, 44.85°, 66.05°, and 78.00° that index to (111, (200, (220, and (311 planes confirm the successful synthesis of Au-NPs. Mostly spherical shape particles with size range of 32.96 ± 5.25 nm are measured using transmission electron microscopy (TEM. From the FTIR results, the peaks obtained are closely related to phenols, flavonoids, benzophenones, and anthocyanins which suggest that they may act as the reducing agent. This method is environmentally safe without the usage of synthetic materials which is highly potential in biomedical applications.

  12. [Effect of Environmental Factors on the Ecotoxicity of Pharmaceuticals and Personal Care Products].

    Science.gov (United States)

    Sugihara, Kazumi

    2018-01-01

     In recent years, pharmaceuticals and personal care products (PPCPs) have emerged as significant pollutants of aquatic environments and have been detected at levels in the range of ng/L to μg/L. The source of PPCPs is humans and livestock that have been administered pharmaceuticals and subsequently excreted them via urine and feces. Unlike agricultural chemicals, the environmental dynamics of PPCPs is not examined and they would undergo structural transformation by environmental factors, e.g., sunlight, microorganisms and treatments in sewage treatment plants (STPs). Processing at STPs can remove various PPCPs; however, they are not removed completely and some persist in the effluents. In this study, we examined the degradation of 9 pharmaceuticals (acetaminophen, amiodarone, dapsone, dexamethasone, indomethacin, raloxifene, phenytoin, naproxen, and sulindac) by sunlight or UV, and investigated the ecotoxicological variation of degradation products. Sunlight (UVA and UVB) degraded most pharmaceuticals, except acetaminophen and phenytoin. Similar results were obtained with UVB and UVA. All the pharmaceuticals were photodegraded by UVC, which is used for sterilization in STPs. Ecotoxicity assay using the luminescent bacteria test (ISO11348) indicated that UVC irradiation increased the toxicity of acetaminophen and phenytoin significantly. The photodegraded product of acetaminophen was identified as 1-(2-amino-5-hydroxyphenyl)ethanone and that of phenytoin as benzophenone, and the authentic compounds showed high toxicity. Photodegraded products of PPCPs are a concern in ecotoxicology.

  13. Solvent-assisted dispersive solid-phase extraction: A sample preparation method for trace detection of diazinon in urine and environmental water samples.

    Science.gov (United States)

    Aladaghlo, Zolfaghar; Fakhari, Alireza; Behbahani, Mohammad

    2016-09-02

    In this research, a sample preparation method termed solvent-assisted dispersive solid-phase extraction (SA-DSPE) was applied. The used sample preparation method was based on the dispersion of the sorbent into the aqueous sample to maximize the interaction surface. In this approach, the dispersion of the sorbent at a very low milligram level was received by inserting a solution of the sorbent and disperser solvent into the aqueous sample. The cloudy solution created from the dispersion of the sorbent in the bulk aqueous sample. After pre-concentration of the diazinon, the cloudy solution was centrifuged and diazinon in the sediment phase dissolved in ethanol and determined by gas chromatography-flame ionization detector. Under the optimized conditions (pH of solution=7.0, Sorbent: benzophenone, 2%, Disperser solvent: ethanol, 500μL, Centrifuge: centrifuged at 4000rpm for 3min), the method detection limit for diazinon was 0.2, 0.3, 0.3 and 0.3μgL(-1) for distilled water, lake water, waste water and urine sample, respectively. Furthermore, the pre-concentration factor was 363.8, 356.1, 360.7 and 353.38 in distilled water, waste water, lake water and urine sample, respectively. SA-DSPE was successfully used for trace monitoring of diazinon in urine, lake and waste water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Preparation and characterization of novel thermoset polyimide and polyimide-peo doped with LiCF3SO3

    Directory of Open Access Journals (Sweden)

    M. H. Ugur

    2014-02-01

    Full Text Available This paper deals with the synthesis and characterization of a new type of anhydrous ionic conducting lithium doped membranes consist of polyimide (PI, poly (ethylene oxide (PEO and lithium trifluoromethanesulfonate (LiCF3SO3 for solid polymer electrolyte (SPE. For this purpose, different molar ratios of lithium salt (Li-salt solution are added into poly (amic acid (PAA intermediate prepared from the reaction of 3,3',4,4'-benzophenon tetracarboxylic dianhydride (BTDA and 4,4'-oxydianiline (ODA. PEO is incorporated into PAA since it forms more stable complexes and possess high ionic conductivities. Then, Li-salt containing PAA solutions are imidized by thermal process. The effect of interaction between host polymer and Li-salt is characterized by FT-IR (Fourier Transform Infrared spectroscopy and SEM (scanning electron micrsocopy. The conductivities of Li-salt and PEO containing PI composite membranes are in the range of 10–7–10–5 S•cm–1. The conductivity increases with incorporation of PEO. Thermogravimetric analysis results reveal that the PI/PEO/LiCF3SO3 composite polymer electrolyte membranes are thermally stable up to 500°C.

  15. An advanced dielectric continuum approach for treating solvation effects: Time correlation functions. I. Local treatment

    Science.gov (United States)

    Basilevsky, M. V.; Parsons, D. F.; Vener, M. V.

    1998-01-01

    A local continuum solvation theory, exactly treating electrostatic matching conditions on the boundary of a cavity occupied by a solute particle, is extended to cover time-dependent solvation phenomena. The corresponding integral equation is solved with a complex-valued frequency-dependent dielectric function ɛ(ω), resulting in a complex-valued ω-dependent reaction field. The inverse Fourier transform then produces the real-valued solvation energy, presented in the form of a time correlation function (TCF). We applied this technique to describe the solvation TCF for a benzophenone anion in Debye (acetonitrile) and two-mode Debye (dimethylformamide) solvents. For the Debye solvent the TCF is described by two exponential components, for the two-mode Debye solvent, by three. The overall dynamics in each case is longer than that given by the simple continuum model. We also consider a steady-state kinetic regime and the corresponding rate constant for adiabatic electron-transfer reactions. Here the boundary effect introduced within a frequency-dependent theory generates only a small effect in comparison with calculations made within the static continuum model.

  16. Analysis of UV filters in tap water and other clean waters in Spain.

    Science.gov (United States)

    Díaz-Cruz, M Silvia; Gago-Ferrero, Pablo; Llorca, Marta; Barceló, Damià

    2012-03-01

    The present paper describes the development of a method for the simultaneous determination of five hormonally active UV filters namely benzophenone-3 (BP3), 3-(4-methylbenzylidene) camphor (4MBC), 2-ethylhexyl 4-(dimethylamino) benzoate (OD-PABA), 2-ethylhexyl 4-methoxycinnamate (EHMC) and octocrylene (OC) by means of solid-phase extraction and gas chromatography-electron impact ionization-mass spectrometry. Under optimized conditions, this methodology achieved low method limits of detection (needed for clean waters, especially drinking water analysis), between 0.02 and 8.42 ng/L, and quantitative recovery rates higher than 73% in all cases. Inter- and intraday precision for all compounds were lower than 7% and 11%, respectively. The optimized methodology was applied to perform the first survey of UV absorbing compounds in tap water from the metropolitan area and the city of Barcelona (Catalonia, Spain). In addition, other types of clean water matrices (mineral bottled water, well water and tap water treated with an ion-exchange resin) were investigated as well. Results evidenced that all the UV filters investigated were detected in the water samples analyzed. The compounds most frequently found were EHMC and OC. Maximum concentrations reached in tap water were 290 (BP3), 35 (4MBC), 110 (OD-PABA), 260 (EHMC), and 170 ng/L (OC). This study constitutes the first evidence of the presence of UV filter residues in tap water in Europe.

  17. [Safety verification for reuse of PET and glass bottles].

    Science.gov (United States)

    Hayashi, Eiichi; Imai, Toshio; Niimi, Hiroji

    2011-01-01

    In order to verify the safety associated with reusing PET and glass bottles, a challenge test was conducted with five surrogate contaminants: 1,1,1-trichloroethane, chlorobenzene, toluene, benzophenone and phenyl cyclohexane. Bottles were filled with a cocktail solution of these contaminants and stored at 50 °C for 7 days, then washed with water and alkaline solutions. Material and migration tests were conducted at each step. The material test results showed that 430-1,440 µg/g of the contaminants were retained after water washing, and that even after washing with a 3.5% NaOH solution, 225-925 µg/g of the contaminants were retained. The migration tests revealed that 0.095-7.35 µg/mL of the contaminants were eluted. Similar tests were conducted with a soft drink ingredient, limonene. The results revealed that 48 µg/g of limonene was retained even after washing with NaOH solution, and that 0.16 µg/mL of limonene was eluted. Conversely, no contaminants were eluted from glass bottles after washing with the NaOH solution. Thus, from the viewpoint of safety and the preservation of content quality, PET bottles are not considered suitable for reuse when compared with glass bottles.

  18. In Silico Identification and in Vitro Activity of Novel Natural Inhibitors of Trypanosoma brucei Glyceraldehyde-3-phosphate-dehydrogenase

    Directory of Open Access Journals (Sweden)

    Fabian C. Herrmann

    2015-09-01

    Full Text Available As part of our ongoing efforts to identify natural products with activity against pathogens causing neglected tropical diseases, we are currently performing an extensive screening of natural product (NP databases against a multitude of protozoan parasite proteins. Within this project, we screened a database of NPs from a commercial supplier, AnalytiCon Discovery (Potsdam, Germany, against Trypanosoma brucei glyceraldehyde-3-phosphate dehydrogenase (TbGAPDH, a glycolytic enzyme whose inhibition deprives the parasite of energy supply. NPs acting as potential inhibitors of the mentioned enzyme were identified using a pharmacophore-based virtual screening and subsequent docking of the identified hits into the active site of interest. In a set of 700 structures chosen for the screening, 13 (1.9% were predicted to possess significant affinity towards the enzyme and were therefore tested in an in vitro enzyme assay using recombinant TbGAPDH. Nine of these in silico hits (69% showed significant inhibitory activity at 50 µM, of which two geranylated benzophenone derivatives proved to be particularly active with IC50 values below 10 µM. These compounds also showed moderate in vitro activity against T. brucei rhodesiense and may thus represent interesting starting points for further optimization.

  19. In Silico Identification and in Vitro Activity of Novel Natural Inhibitors of Trypanosoma brucei Glyceraldehyde-3-phosphate-dehydrogenase.

    Science.gov (United States)

    Herrmann, Fabian C; Lenz, Mairin; Jose, Joachim; Kaiser, Marcel; Brun, Reto; Schmidt, Thomas J

    2015-09-03

    As part of our ongoing efforts to identify natural products with activity against pathogens causing neglected tropical diseases, we are currently performing an extensive screening of natural product (NP) databases against a multitude of protozoan parasite proteins. Within this project, we screened a database of NPs from a commercial supplier, AnalytiCon Discovery (Potsdam, Germany), against Trypanosoma brucei glyceraldehyde-3-phosphate dehydrogenase (TbGAPDH), a glycolytic enzyme whose inhibition deprives the parasite of energy supply. NPs acting as potential inhibitors of the mentioned enzyme were identified using a pharmacophore-based virtual screening and subsequent docking of the identified hits into the active site of interest. In a set of 700 structures chosen for the screening, 13 (1.9%) were predicted to possess significant affinity towards the enzyme and were therefore tested in an in vitro enzyme assay using recombinant TbGAPDH. Nine of these in silico hits (69%) showed significant inhibitory activity at 50 µM, of which two geranylated benzophenone derivatives proved to be particularly active with IC50 values below 10 µM. These compounds also showed moderate in vitro activity against T. brucei rhodesiense and may thus represent interesting starting points for further optimization.

  20. Biocontrol evaluation of extracts and a major component, clusianone, from Clusia fluminensisPlanch. & Triana againstAedes aegypti

    Directory of Open Access Journals (Sweden)

    Maria C Anholeti

    2015-08-01

    Full Text Available Studies evaluated the effects of hexanic extracts from the fruits and flowers ofClusia fluminensis and the main component of the flower extract, a purified benzophenone (clusianone, against Aedes aegypti. The treatment of larvae with the crude fruit or flower extracts from C. fluminensis did not affect the survival ofAe. aegypti (50 mg/L, however, the flower extracts significantly delayed development of Ae. aegypti. In contrast, the clusianone (50 mg/L isolate from the flower extract, representing 54.85% of this sample composition, showed a highly significant inhibition of survival, killing 93.3% of the larvae and completely blocking development of Ae. aegypti. The results showed, for the first time, high activity of clusianone against Ae. aegypti that both killed and inhibited mosquito development. Therefore, clusianone has potential for development as a biopesticide for controlling insect vectors of tropical diseases. Future work will elucidate the mode of action of clusianone isolated from C. fluminensis.

  1. Secondary Metabolites from the Culture of the Marine Sponge-Associated Fungi Talaromyces tratensis and Sporidesmium circinophorum.

    Science.gov (United States)

    Buttachon, Suradet; May Zin, War War; Dethoup, Tida; Gales, Luís; Pereira, José A; Silva, Artur M S; Kijjoa, Anake

    2016-06-01

    Wortmin (1), meso-1,4-bis(4-methoxybenzyl)-2,3-butanediol (2), and a new isocoumarin derivative tratenopyrone (3) were isolated from the marine sponge-associated fungus Talaromyces tratensis KUFA 0091. A new diphenyl ether derivative, circinophoric acid (4), was isolated, together with the previously reported anthraquinones catenarin and physcion, the benzophenone monomethylsoluchrin, and β-ergosterol-5,8-endoperoxide, from the marine sponge-associated fungus Sporidesmium circinophorum KUFA 0043. The structures of the new compounds were established based on an extensive analysis of 1D and 2D NMR spectra, and, in the case of compounds 2-4, also by X-ray analysis. All of the isolated compounds were tested for their antibacterial activity against Gram-positive and Gram-negative bacteria, and multidrug-resistant isolates from the environment, as well as for their anti-quorum sensing based on the pigment production of Chromobacterium violaceum ATCC 31523. None of the compounds exhibited either antibacterial (MIC > 256 µg/mL) or anti-quorum sensing activities. The compounds were also inactive in the antifungal (MIC > 512 µg/mL) and cancer cell line (GI50 > 150 µM) assays. Georg Thieme Verlag KG Stuttgart · New York.

  2. Margin of safety for two UV filters estimated by in vitro permeation studies mimicking consumer habits: Effects of skin shaving and sunscreen reapplication.

    Science.gov (United States)

    Hojerová, Jarmila; Peráčková, Zuzana; Beránková, Martina

    2017-05-01

    Sunscreens are intended to work on the skin. To be both efficient and safe, the lowest possible percutaneous permeation of UV filters should occur. The potential for systemic absorption of Benzophenone-3 (BP3, 10%) and Ethylhexyl Triazone (EHT, 5%) in a silicone-based water-in-oil emulsion was assessed in vitro using a full-thickness porcine-ear skin mimicking in-use conditions. The estimated Systemic Exposure Dose (SED) after the sunscreen application at 1.0 mg/cm 2 for 6 h (i) on the face; (ii) on the whole-body skin, was (i) 136 and 30; (ii) 4200 and 933 μg/kg_bw/d for BP3 and EHT, respectively. Reapplication does not mean the double risk; the SED values were only 1.40-1.37-fold greater. Skin shaving increased BP3 and EHT bioavailability 1.38 and 1.80-fold, respectively. Margin of Safety values were estimated according to guidelines applicable for European Union. For three realistic exposure scenarios, MoS of 48, 34 and 34 for BP3 in the sunscreen applied on the whole-body indicate some concerns regarding the safety for consumers (MoSfilters should be focused on their specific physico-chemical properties. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Zeolite encapsulated Fe-porphyrin for catalytic oxidation with iodobenzene diacetate (PhI(OAc)2)

    International Nuclear Information System (INIS)

    Karimipour, G.; Rezaei, M.; Ashouri, D.

    2013-01-01

    meso-Tetrakis(3-pyridyl)porphyrin ato iron(III) chloride encapsulated on NaY Zeolite [Fe(T-3-PyP)-NaY] was synthesized as a heterogeneous ship-in-a-bottle type catalyst and characterized by Fourier transform infrared, atomic absorption, diffused reflectance UV-Vis, X-ray diffraction and scanning electron microscopy analysis. The catalytic activity of Fe(T-3-PyP-NaY was examined for the epoxidation of cyclohexene by PhI(OAc) 2 in CH 3 CN/H 2 O (5:1) and compared to that of Fe(T-3-PyP) as a homogeneous catalyst. We found that the heterogeneous catalyst Fe(T-3-PyP-NaY was stable and reusable for several times, and provided a mild condition and exhibited high activity and selectivity in the oxidation of alkenes to epoxides (16-94%). As representative examples for the use of Fe(T-3-PyP-NaY/ PhI(OAc) 2 in organic oxidations, oxidation of 4-nitro benzylalcohol to 4-nitrobenzaldehyde (97%), oxidative dehydrogenation of diethyl 4-(2,6-dichlorophenyl)-2,6-dimethyl-1,4-dihydro-3,5-pyridinedicarboxylate to the corresponding pyridine (100%), diphenylacetic acid to benzophenone (64%) was achieved. (Author)

  4. Zeolite encapsulated Fe-porphyrin for catalytic oxidation with iodobenzene diacetate (PhI(OAc){sub 2})

    Energy Technology Data Exchange (ETDEWEB)

    Karimipour, G.; Rezaei, M.; Ashouri, D. [Yasouj University, Department of Chemistry, 75918-74831 Yasouj (Iran, Islamic Republic of)

    2013-07-01

    meso-Tetrakis(3-pyridyl)porphyrin ato iron(III) chloride encapsulated on NaY Zeolite [Fe(T-3-PyP)-NaY] was synthesized as a heterogeneous ship-in-a-bottle type catalyst and characterized by Fourier transform infrared, atomic absorption, diffused reflectance UV-Vis, X-ray diffraction and scanning electron microscopy analysis. The catalytic activity of Fe(T-3-PyP-NaY was examined for the epoxidation of cyclohexene by PhI(OAc){sub 2} in CH{sub 3}CN/H{sub 2}O (5:1) and compared to that of Fe(T-3-PyP) as a homogeneous catalyst. We found that the heterogeneous catalyst Fe(T-3-PyP-NaY was stable and reusable for several times, and provided a mild condition and exhibited high activity and selectivity in the oxidation of alkenes to epoxides (16-94%). As representative examples for the use of Fe(T-3-PyP-NaY/ PhI(OAc){sub 2} in organic oxidations, oxidation of 4-nitro benzylalcohol to 4-nitrobenzaldehyde (97%), oxidative dehydrogenation of diethyl 4-(2,6-dichlorophenyl)-2,6-dimethyl-1,4-dihydro-3,5-pyridinedicarboxylate to the corresponding pyridine (100%), diphenylacetic acid to benzophenone (64%) was achieved. (Author)

  5. Evolution of Chemical Diversity in a Group of Non-Reduced Polyketide Gene Clusters: Using Phylogenetics to Inform the Search for Novel Fungal Natural Products

    Directory of Open Access Journals (Sweden)

    Kurt Throckmorton

    2015-09-01

    Full Text Available Fungal polyketides are a diverse class of natural products, or secondary metabolites (SMs, with a wide range of bioactivities often associated with toxicity. Here, we focus on a group of non-reducing polyketide synthases (NR-PKSs in the fungal phylum Ascomycota that lack a thioesterase domain for product release, group V. Although widespread in ascomycete taxa, this group of NR-PKSs is notably absent in the mycotoxigenic genus Fusarium and, surprisingly, found in genera not known for their secondary metabolite production (e.g., the mycorrhizal genus Oidiodendron, the powdery mildew genus Blumeria, and the causative agent of white-nose syndrome in bats, Pseudogymnoascus destructans. This group of NR-PKSs, in association with the other enzymes encoded by their gene clusters, produces a variety of different chemical classes including naphthacenediones, anthraquinones, benzophenones, grisandienes, and diphenyl ethers. We discuss the modification of and transitions between these chemical classes, the requisite enzymes, and the evolution of the SM gene clusters that encode them. Integrating this information, we predict the likely products of related but uncharacterized SM clusters, and we speculate upon the utility of these classes of SMs as virulence factors or chemical defenses to various plant, animal, and insect pathogens, as well as mutualistic fungi.

  6. Carboxylate ligands induced structural diversity of zinc(II) coordination polymers based on 3,6-bis(imidazol-1-yl)carbazole: Syntheses, structures and photocatalytic properties

    Science.gov (United States)

    Cheng, Hong-Jian; Tang, Hui-Xiang; Shen, Ya-Li; Xia, Nan-Nan; Yin, Wen-Yu; Zhu, Wei; Tang, Xiao-Yan; Ma, Yun-Sheng; Yuan, Rong-Xin

    2015-12-01

    Solvothermal reactions of Zn(NO3)2·6H2O with 3,6-bis(1-imidazolyl)carbazole (3,6-bmcz) and 1,4-benzenedicarboxylic acid (1,4-H2bdc), p-phenylenediacetic acid (p-H2pda), benzophenone-4,4-dicarboxylic acid (H2bpda) afforded three coordination polymers [Zn(1,4-bdc)(3,6-bmcz)]n (1), {[Zn(p-pda)(3,6-bmcz)]·1.5H2O}n (2) and {[Zn(bpda)(3,6-bmcz)]·0.25H2O}n (3). Complexes 1-3 were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. Complex 1 shows 3D structure with 2D nets inclined polycatenation. Complexes 2 and 3 possess an extended 3D supramolecular architecture based on their respective 2D layers through hydrogen-bonding interactions and the π···π stacking interactions. The solid state luminescent and optical properties of 1-3 at ambient temperature were also investigated. A comparative study on their photocatalytic activity toward the degradation of methylene blue in polluted water was explored.

  7. Design of UV-absorbing PVDF membrane via surface-initiated AGET ATRP

    Science.gov (United States)

    Dong, Li; Liu, Xiangdong; Xiong, Zhengrong; Sheng, Dekun; Zhou, Yan; Lin, Changhong; Yang, Yuming

    2018-03-01

    Herein, PVDF membranes with excellent UV-absorbing property were first synthesized through grafting the polymerizable low-molecular-weight organic UV-absorber 2-hydroxy-4-(3-methacryloxy-2-hydroxylpropoxy) benzophenone (BPMA) onto α-bromoester-functionalized PVDF membranes via the surface-initiated activator generated by electron transfer atom transfer radical polymerization (SI-AGET ATRP). The surface initiators were immobilized by the reaction between 2-bromoisobutyryl bromide (BIBB) and the hydroxylated PVDF membranes. PVDF-g-PBPMA membranes with different grafting densities were obtained by tuning the polymerization time and the modified membranes were characterized by 1H-NMR, FT-IR, XPS, SEM, UV-vis Spectrophotometer, TGA and DSC. The experimental results indicated that PBPMA chains were successfully introduced onto PVDF membranes. Most importantly, the PVDF-g-PBPMA membranes exhibited outstanding UV-shielding property. UV-vis transmittance spectra showed that most UV light below 360 nm could be absorbed by PVDF-g-PBPMA membranes and the whole UV light region (200-400 nm) can be blocked with the reaction time increased.

  8. A Novel Photosynthesis of Carboxymethyl Starch-Stabilized Silver Nanoparticles

    Directory of Open Access Journals (Sweden)

    M. A. El-Sheikh

    2014-01-01

    Full Text Available The water soluble photoinitiator (PI 4-(trimethyl ammonium methyl benzophenone chloride is used for the first time in the synthesis of silver nanoparticles (AgNPs. A new green synthesis method involves using PI/UV system, carboxymethyl starch (CMS, silver nitrate, and water. A mechanism of the reduction of silver ions to AgNPs by PI/UV system as well as by the newly born aldehydic groups was proposed. The synthesis process was assessed by UV-vis spectra and TEM of AgNPs colloidal solution. The highest absorbance was obtained using CMS, PI and AgNO3 concentrations of 10 g/L, 1 g/L, and 1 g/L, respectively; 40°C; 60 min; pH 7; and a material : liquor ratio 1 : 20. AgNPs so-obtained were stable in aqueous solution over a period of three weeks at room temperature (~25°C and have round shape morphology. The sizes of synthesized AgNPs were in the range of 1–21 nm and the highest counts % of these particles were for particles of 6–10 and 1–3 nm, respectively.

  9. Comparison between solid phase microextraction (SPME) and hollow fiber liquid phase microextraction (HFLPME) for determination of extractables from post-consumer recycled PET into food simulants.

    Science.gov (United States)

    Oliveira, Éder Costa; Echegoyen, Yolanda; Cruz, Sandra Andrea; Nerin, Cristina

    2014-09-01

    Hollow fiber liquid phase microextraction (HFLPME) and solid phase microextraction (SPME) methods for pre-concentration of contaminants (toluene, benzophenone, tetracosane and chloroform) in food simulants were investigated. For HFLPME 1-heptanol, 2-octanone and dibutyl-ether were studied as extracting solvents. Analysis by gas chromatography coupled to mass spectrometry (GC-MS), flame ionization (GC-FID) and electron capture detectors (GC-ECD) were carried out. In addition, the methods were employed to evaluate the safety in use of a PET material after the recycling process (comprising washing, extrusion and solid state polymerization (SSP)) through extractability studies of the contaminants using 10% (v/v) ethanol in deionized water and 3% (w/v) acetic acid in deionized water as food simulants in different conditions: 10 days at 40°C and 2h at 70°C. The HFLPME preconcentration method provided increased sensitivity when compared to the SPME method and allowed to analyze concentration levels below 10 µg surrogate per kg food simulant. The results of the extractability studies showed considerable reductions after the extrusion and SSP processes and indicated the compliance with regulations for using recycled PET in contact with food. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Evaluation of sub-critical water as an extraction fluid for model contaminants from recycled PET for reuse as food packaging material.

    Science.gov (United States)

    Santos, Amélia S F; Agnelli, José A M; Manrich, Sati

    2010-04-01

    Recycling of plastics for food-contact packaging is an important issue and research into meaningful and cost-effective solutions is in progress. In this paper, the use of sub-critical water was evaluated as an alternative way of purifying poly(ethylene terephthalate) (PET) flakes for direct food contact applications. The effects of temperature, pressure and flow rate were assessed on the extraction efficiency of two of the most challenging classes of contaminants (toluene and benzophenone) from PET by sub-critical water using a first-order fractional experimental design. Extraction yield was quantified using GC/FID. The most important parameter was flow rate, indicating that the decrease in sub-critical water polarity with temperature was insufficient to eliminate partition effects. Temperature was also important, but only for the optimization of toluene extraction. These results may be explained by the poor solubility of higher molar mass compounds in sub-critical water compared to lower molar mass compounds under the same conditions, and the small decrease in dielectric constant with temperature under the experimental conditions evaluated. As cleaning efficiency is low and PET is very susceptible to hydrolysis, which limits the use of higher temperatures vis-à-vis physical recycling, the proposed extraction is unsuitable for a standalone super-clean process but may be a step in the process.

  11. Magnetic Composite Thin Films of Fe{sub x}O{sub y} Nanoparticles and Photocrosslinked Dextran Hydrogels

    Energy Technology Data Exchange (ETDEWEB)

    Brunsen, Annette, E-mail: brunsen@mpip-mainz.mpg.de [Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz (Germany); Department of Chemistry, Technical University Darmstadt, Petersenstr. 22, 64287 Darmstadt (Germany); Utech, Stefanie, E-mail: utech@uni-mainz.de [Johannes Gutenberg University Mainz, Institute of Physical Chemistry, Jakob-Welder-Weg 11, 55099 Mainz (Germany); Institut fuer Mikrotechnik Mainz GmbH (IMM), Carl-Zeiss-Str. 18-20, 55129 Mainz, German (Germany); Maskos, Michael, E-mail: maskos@uni-mainz.de [Institut fuer Mikrotechnik Mainz GmbH (IMM), Carl-Zeiss-Str. 18-20, 55129 Mainz, German (Germany); Knoll, Wolfgang, E-mail: Wolfgang.Knoll@ait.ac.at [Austrian Institute of Technology, Tech Gate Vienna, Donau-City-Str. 1, 1220 Wien (Austria); Jonas, Ulrich, E-mail: jonas@mpip-mainz.mpg.de [Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz (Germany) and Macromolecular Chemistry, Department Chemistry - Biology, University of Siegen, Adolf-Reichwein-Str. 2, 57076 Siegen (Germany) and Foundation for Research and Technology - Hellas - FORTH, Institute of Electronic Structure and Laser (IESL), Bio-Organic Materials Chemistry Laboratory - BOMCLab, Nikolaou Plastira 100, Vassilika Vouton, 71110 Heraklion, Crete (Greece)

    2012-04-15

    Magnetic hydrogel composites are promising candidates for a broad field of applications from medicine to mechanical engineering. Here, surface-attached composite films of magnetic nanoparticles (MNP) and a polymeric hydrogel (HG) were prepared from magnetic iron oxide nanoparticles and a carboxymethylated dextran with photoreactive benzophenone substituents. A blend of the MNP and the dextran polymer was prepared by mixing in solution, and after spin-coating and drying the blend film was converted into a stable MNP-HG composite by photocrosslinking through irradiation with UV light. The bulk composite material shows strong mobility in a magnetic field, imparted by the MNPs. By utilizing a surface layer of a photoreactive adhesion promoter on the substrates, the MNP-HG films were covalently immobilized during photocrosslinking. The high stability of the composite was documented by rinsing experiments with UV-Vis spectroscopy, while surface plasmon resonance and optical waveguide mode spectroscopy was employed to investigate the swelling behavior in dependence of the nanoparticle concentration, the particle type, and salt concentration. - Highlights: Black-Right-Pointing-Pointer blending of iron oxide nanoparticles with photocrosslinkable carboxymethyldextran. Black-Right-Pointing-Pointer UV irradiation of blend yields surface-attached, magnetic hydrogel films. Black-Right-Pointing-Pointer film characterization by surface plasmon resonance/optical waveguide spectroscopy. Black-Right-Pointing-Pointer swelling decreases with increasing nanoparticle content. Black-Right-Pointing-Pointer swelling decreases with increasing NaCl salt concentration in the aqueous medium.

  12. Functionalized polymer film surfaces via surface-initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Hu, Y.; Li, J.S.; Yang, W.T.; Xu, F.J.

    2013-01-01

    The ability to manipulate and control the surface properties of polymer films, without altering the substrate properties, is crucial to their wide-spread applications. In this work, a simple one-step method for the direct immobilization of benzyl chloride groups (as the effective atom transfer radical polymerization (ATRP) initiators) on the polymer films was developed via benzophenone-induced coupling of 4-vinylbenzyl chloride (VBC). Polyethylene (PE) and nylon films were selected as examples of polymer films to illustrate the functionalization of film surfaces via surface-initiated ATRP. Functional polymer brushes of (2-dimethylamino)ethyl methacrylate, sodium 4-styrenesulfonate, 2-hydroxyethyl methacrylate and glycidyl methacrylate, as well as their block copolymer brushes, have been prepared via surface-initiated ATRP from the VBC-coupled PE or nylon film surfaces. With the development of a simple approach to the covalent immobilization of ATRP initiators on polymer film surfaces and the inherent versatility of surface-initiated ATRP, the surface functionality of polymer films can be precisely tailored. - Highlights: ► Atom transfer radical polymerization initiators were simply immobilized. ► Different functional polymer brushes were readily prepared. ► Their block copolymer brushes were also readily prepared

  13. A comparative study of alumina-supported Ni catalysts prepared by photodeposition and impregnation methods on the catalytic ozonation of 2,4-dichlorophenoxyacetic acid

    International Nuclear Information System (INIS)

    Rodríguez, Julia L.; Valenzuela, Miguel A.; Tiznado, Hugo; Poznyak, Tatiana; Chairez, Isaac; Magallanes, Diana

    2017-01-01

    The heterogeneous catalytic ozonation on unsupported and supported oxides has been successfully tested for the removal of several refractory compounds in aqueous solution. In this work, alumina-supported nickel catalysts prepared by photodeposition and impregnation methods were compared in the catalytic ozonation of 2,4-dichlorophenoxyacetic acid (2,4-D). The catalysts were characterized by high-resolution electron microscopy and X-ray photoelectron spectroscopy. The photochemical decomposition of Ni acetylacetonate to produce Ni(OH) 2 , NiO, and traces of Ni° deposited on alumina was achieved in the presence of benzophenone as a sensitizer. A similar surface composition was found with the impregnated catalyst after its reduction with hydrogen at 500 °C and exposed to ambient air. Results indicated a higher initial activity and maleic acid (byproduct) concentration with the photodeposited catalyst (1 wt% Ni) compared to the impregnated catalyst (3 wt% Ni). These findings suggest the use of the photodeposition method as a simple and reliable procedure for the preparation of supported metal oxide/metal catalysts under mild operating conditions.

  14. Computational modelling of polymers

    Science.gov (United States)

    Celarier, Edward A.

    1991-01-01

    Polymeric materials and polymer/graphite composites show a very diverse range of material properties, many of which make them attractive candidates for a variety of high performance engineering applications. Their properties are ultimately determined largely by their chemical structure, and the conditions under which they are processed. It is the aim of computational chemistry to be able to simulate candidate polymers on a computer, and determine what their likely material properties will be. A number of commercially available software packages purport to predict the material properties of samples, given the chemical structures of their constituent molecules. One such system, Cerius, has been in use at LaRC. It is comprised of a number of modules, each of which performs a different kind of calculation on a molecule in the programs workspace. Particularly, interest is in evaluating the suitability of this program to aid in the study of microcrystalline polymeric materials. One of the first model systems examined was benzophenone. The results of this investigation are discussed.

  15. Insertion, reduction, and carbon-carbon coupling induced by monomeric aluminum hydride compounds bearing substituted pyrrolyl ligands.

    Science.gov (United States)

    Lin, Che-Yu; Tsai, Chia-Fu; Chen, Hsing-Jen; Hung, Chen-Hsiung; Yu, Ru-Ching; Kuo, Pei-Cheng; Lee, Hon Man; Huang, Jui-Hsien

    2006-04-03

    A monomeric aluminum hydride complex bearing substituted pyrrolyl ligands, AlH[C(4)H(3)N(CH(2)NMe(2))-2](2) (1), was synthesized and structurally characterized. To further confirm the presence of Al--H bonds, the compound AlD[C(4)H(3)N(CH(2)NMe(2))-2](2) ([D]1) was synthesized by reacting LiAlD(4) with [C(4)H(4)N(CH(2)NMe(2))-2]. Compound 1 and [D]1 react with phenyl isothiocyanate yielding Al[C(4)H(3)N(CH(2)NMe(2))-2](2)[eta(3)-SCHNPh] (2) and Al[C(4)H(3)N(CH(2)NMe(2))-2](2)[eta(3)-SCDNPh] ([D]2) by insertion. The reactions of 1 with 9-fluorenone and benzophenone generated the unusual aluminum alkoxide complexes 3 and 4, respectively, through intramolecular proton abstraction and C-C coupling. A mechanistic study shows that 9-fluorenone coordinates to [D]1 and releases one equivalent of HD followed by C-C coupling and hydride transfer to yield the final product. Reduction of benzil with 1 affords aluminum enediolate complex 5 in moderate yield. Mechanistic studies also showed that the benzil was inserted into the aluminum hydride bond of [D]1 through hydroalumination followed by proton transfer to generate the final product [D]5. All new complexes have been characterized by (1)H and (13)C NMR spectroscopy and X-ray crystallography.

  16. Photoaffinity labeling of myosin subfragment-one-with 3'(2')-O-(4-benzoyl)benzoyl adenosine 5'-triphosphate

    International Nuclear Information System (INIS)

    Mahmood, R.

    1985-01-01

    The photoaffinity analogue 3'(2')-O-(4-benzoyl)benzoyl adenosine 5'-triphosphate (Bz 2 ATP) contains the photoreactive benzophenone group esterified at the 2' or 3' hydroxyl groups of ribose. MgBz 2 ADP has a single binding site on skeletal myosin chymotryptic subfragment-one (SF 1 ) with a binding constant of 3.2 x 10 5 M -1 . Bz 2 ATP is also a substrate for the ATPase activity of SF 1 in the presence of different cations. The irradiation of SF 1 with [ 3 H]Bz 2 ATP photoinactivates the ATPase activity with concomitant incorporation of the analogue into the enzyme. Polyacrylamide gel electrophoresis of photolabeled SF 1 after milk trypsin digestion shows that all three tryptic peptides, 25 K, 50K, and 20 K, and both light chains are labeled. The presence of ATP during irradiation reduces labeling of the 50 K peptide only indicating that the other peptides are non-specifically labeled. To reduce the non-specific labeling [ 3 H]Bz 2 ATP is trapped on SF 1 by cross-linking the two reactive thiols, SH 1 and SH 2 , by N,N'-p-phenylene dimaleimide or Co(II)/Co(III) phenanthroline complexes. The Co(II)/Co(III) phenanthroline modified [ 14 C]Bz 2 ATP-SF 1 , after proteolytic digestion, yields five labeled peptides which were purified by gel filtration and high performance liquid chromatography

  17. Continental bottled water assessment by stir bar sorptive extraction followed by gas chromatography-tandem mass spectrometry (SBSE-GC-MS/MS).

    Science.gov (United States)

    Guart, Albert; Calabuig, Ignacio; Lacorte, Silvia; Borrell, Antonio

    2014-02-01

    This study was aimed to determine the presence of 69 organic contaminants in 77 representative bottled waters collected from 27 countries all over the world. All water samples were contained in polyethylene terephthalate bottles. Target compounds were (1) environmental contaminants (including 13 polycyclic aromatic hydrocarbons (PAHs), 31 pesticides including organochlorine (OCPs), organophosphorus, and pyrethroids; 7 polychlorinated biphenyls (PCBs); and 7 triazines) and (2) plasticizers (including 6 phthalates and 5 other compounds). Samples were analyzed by stir bar sorptive extraction followed by gas chromatography-tandem mass spectrometry. PAHs, OCPs, PCBs, and triazines, which are indicators of groundwater pollution, were not detected in most of the samples, except for naphthalene (0.005-0.202 μg/L, n = 16). On the other hand, plastic components were detected in 77 % of the samples. Most frequently detected compounds were dimethyl phthalate and benzophenone at concentrations of 0.005-0.125 (n = 41) and 0.014-0.921 (n = 32), respectively. Levels detected are discussed in terms of contamination origin and geographical distribution. Target compounds were detected at low concentrations. Results obtained showed the high quality of bottled water in the different countries around the world.

  18. Observation of excited state charge transfer with fs/ps-CARS

    Energy Technology Data Exchange (ETDEWEB)

    Blom, Alex Jason [Iowa State Univ., Ames, IA (United States)

    2009-01-01

    Excited state charge transfer processes are studied using the fs/ps-CARS probe technique. This probe allows for multiplexed detection of Raman active vibrational modes. Systems studied include Michler's Ketone, Coumarin 120, 4-dimethylamino-4'-nitrostilbene, and several others. The vibrational spectrum of the para di-substituted benzophenone Michler's Ketone in the first excited singlet state is studied for the first time. It is found that there are several vibrational modes indicative of structural changes of the excited molecule. A combined experimental and theoretical approach is used to study the simplest 7-amino-4-methylcoumarin, Coumarin 120. Vibrations observed in FTIR and spontaneous Raman spectra are assigned using density functional calculations and a continuum solvation model is used to predict how observed modes are affected upon inclusion of a solvent. The low frequency modes of the excited state charge transfer species 4-dimethylamino-4{prime}-nitrostilbene are studied in acetonitrile. Results are compared to previous work on this molecule in the fingerprint region. Finally, several partially completed projects and their implications are discussed. These include the two photon absorption of Coumarin 120, nanoconfinement in cyclodextrin cavities and sensitization of titania nanoparticles.

  19. Potential external contamination with bisphenol A and other ubiquitous organic environmental chemicals during biomonitoring analysis: an elusive laboratory challenge.

    Science.gov (United States)

    Ye, Xiaoyun; Zhou, Xiaoliu; Hennings, Ryan; Kramer, Joshua; Calafat, Antonia M

    2013-03-01

    Biomonitoring studies are conducted to assess internal dose (i.e., body burden) to environmental chemicals. However, because of the ubiquitous presence in the environment of some of these chemicals, such as bisphenol A (BPA), external contamination during handling and analysis of the biospecimens collected for biomonitoring evaluations could compromise the reported concentrations of such chemicals. We examined the contamination with the target analytes during analysis of biological specimens in biomonitoring laboratories equipped with state-of-the-art analytical instrumentation. We present several case studies using the quantitative determination of BPA and other organic chemicals (i.e., benzophenone-3, triclosan, parabens) in human urine, milk, and serum to identify potential contamination sources when the biomarkers measured are ubiquitous environmental contaminants. Contamination with target analytes during biomonitoring analysis could result from solvents and reagents, the experimental apparatus used, the laboratory environment, and/or even the analyst. For biomonotoring data to be valid-even when obtained from high-quality analytical methods and good laboratory practices-the following practices must be followed to identify and track unintended contamination with the target analytes during analysis of the biological specimens: strict quality control measures including use of laboratory blanks; replicate analyses; engineering controls (e.g., clean rooms, biosafety cabinets) as needed; and homogeneous matrix-based quality control materials within the expected concentration ranges of the study samples.

  20. Energy Effectiveness of Direct UV and UV/H2O2 Treatment of Estrogenic Chemicals in Biologically Treated Sewage

    Directory of Open Access Journals (Sweden)

    Kamilla M. S. Hansen

    2012-01-01

    Full Text Available Continuous exposure of aquatic life to estrogenic chemicals via wastewater treatment plant effluents has in recent years received considerable attention due to the high sensitivity of oviparous animals to disturbances of estrogen-controlled physiology. The removal efficiency by direct UV and the UV/H2O2 treatment was investigated in biologically treated sewage for most of the estrogenic compounds reported in wastewater. The investigated compounds included parabens, industrial phenols, sunscreen chemicals, and steroid estrogens. Treatment experiments were performed in a flow through setup. The effect of different concentrations of H2O2 and different UV doses was investigated for all compounds in an effluent from a biological wastewater treatment plant. Removal effectiveness increased with H2O2 concentration until 60 mg/L. The treatment effectiveness was reported as the electrical energy consumed per unit volume of water treated required for 90% removal of the investigated compound. It was found that the removal of all the compounds was dependent on the UV dose for both treatment methods. The required energy for 90% removal of the compounds was between 28 kWh/m3 (butylparaben and 1.2 kWh/m3 (estrone for the UV treatment. In comparison, the UV/H2O2 treatment required between 8.7 kWh/m3 for bisphenol A and benzophenone-7 and 1.8 kWh/m3 for ethinylestradiol.

  1. Urinary biomarkers of exposure to 57 xenobiotics and its association with oxidative stress in a population in Jeddah, Saudi Arabia.

    Science.gov (United States)

    Asimakopoulos, Alexandros G; Xue, Jingchuan; De Carvalho, Bruno Pereira; Iyer, Archana; Abualnaja, Khalid Omer; Yaghmoor, Soonham Sami; Kumosani, Taha Abdullah; Kannan, Kurunthachalam

    2016-10-01

    Oxidative stress arises from excessive free radicals in the body and is a trigger for numerous diseases, such as cancer and atherosclerosis. Elevated exposure to environmental chemicals can contribute to oxidative stress. The association between exposure to xenobiotics and oxidative stress, however, has rarely been studied. In this study, urinary concentrations of 57 xenobiotics (antimicrobials, parabens, bisphenols, benzophenones, and phthalates metabolites) were determined in a population from Jeddah, Saudi Arabia, to delineate association with the oxidative stress biomarker, 8-hydroxy-2'-deoxyguanosine (8OHDG). We collected 130 urine samples and analyzed for 57 xenobiotics using liquid chromatography-tandem mass spectrometry (LC/MS/MS) methods. The association between unadjusted and creatinine- or specific gravity-adjusted concentrations of xenobiotics and 8OHDG was examined by Pearson correlations and multiple regression analysis. High concentrations of mCPP (a metabolite of di-n-octyl phthalate; DnOP) and mCMHP (a metabolite of diethylhexyl phthalate; DEHP) were found in urine. In addition, the concentrations of bisphenol S (BPS) were higher than those of bisphenol A (BPA). The concentrations of metabolites of DEHP, phthalic acid, BPA, BPS, and methyl-protocatechuic acid were significantly associated with 8OHDG. This is the first biomonitoring study to report exposure of the Saudi population to a wide range of environmental chemicals and provides evidence that environmental chemical exposures contribute to oxidative stress. Copyright © 2015 Elsevier Inc. All rights reserved.

  2. Inhibitors of Testosterone Biosynthetic and Metabolic Activation Enzymes

    Directory of Open Access Journals (Sweden)

    Leping Ye

    2011-12-01

    Full Text Available The Leydig cells of the testis have the capacity to biosynthesize testosterone from cholesterol. Testosterone and its metabolically activated product dihydrotestosterone are critical for the development of male reproductive system and spermatogenesis. At least four steroidogenic enzymes are involved in testosterone biosynthesis: Cholesterol side chain cleavage enzyme (CYP11A1 for the conversion of cholesterol into pregnenolone within the mitochondria, 3β-hydroxysteroid dehydrogenase (HSD3B, for the conversion of pregnenolone into progesterone, 17α-hydroxylase/17,20-lyase (CYP17A1 for the conversion of progesterone into androstenedione and 17β-hydroxysteroid dehydrogenase (HSD17B3 for the formation of testosterone from androstenedione. Testosterone is also metabolically activated into more potent androgen dihydrotestosterone by two isoforms 5α-reductase 1 (SRD5A1 and 2 (SRD5A2 in Leydig cells and peripheral tissues. Many endocrine disruptors act as antiandrogens via directly inhibiting one or more enzymes for testosterone biosynthesis and metabolic activation. These chemicals include industrial materials (perfluoroalkyl compounds, phthalates, bisphenol A and benzophenone and pesticides/biocides (methoxychlor, organotins, 1,2-dibromo-3-chloropropane and prochloraz and plant constituents (genistein and gossypol. This paper reviews these endocrine disruptors targeting steroidogenic enzymes.

  3. Assumed non-persistent environmental chemicals in human adipose tissue; matrix stability and correlation with levels measured in urine and serum.

    Science.gov (United States)

    Artacho-Cordón, F; Arrebola, J P; Nielsen, O; Hernández, P; Skakkebaek, N E; Fernández, M F; Andersson, A M; Olea, N; Frederiksen, H

    2017-07-01

    The aim of this study was to (1) optimize a method for the measurement of parabens and phenols in adipose tissue, (2) evaluate the stability of chemical residues in adipose tissue samples, and (3) study correlations of these compounds in urine, serum, and adipose tissue. Samples were obtained from adults undergoing trauma surgery. Nine phenols and seven parabens were determined by isotope diluted TurboFlow-LC-MS/MS. The analytical method showed good accuracy and precision. Limits of detection (LOD) for parabens and phenols ranged from 0.05 to 1.83ng/g tissue. Good recovery rates were found, even when biological samples remained defrosted up to 24h. Benzophenone-3 (BP-3; range of values: 70% of adipose tissue samples, while bisphenol-A (BPA; 40% of adipose tissue samples. In general, levels were similar between adipose tissue and serum, while a correlation between adipose tissue and urine was only found for BP-3. In conclusion, adipose tissue samples in this study were found to contain environmental chemicals considered to be non-persistent, whose levels were weakly or not at all correlated with the urine burden. Therefore, adipose tissue may potentially provide additional information to that obtained from other biological matrices. Further investigations are warranted to explore whether adipose tissue might be a suitable matrix for assessment of the consequences for human health of mid/long-term exposure to these chemicals. Copyright © 2017 Elsevier Inc. All rights reserved.

  4. Novel thermally cross-linked polyimide membranes for ethanol dehydration via pervaporation

    KAUST Repository

    Xu, Sheng

    2015-12-01

    © 2015 Elsevier B.V. In this work, two novel carboxyl-containing polyimides, 2,2\\'-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride-4,4\\'-diaminodiphenylmethane/3,5-diaminobenzoic acid (6FDA-MDA/DABA, FMD) and 3,3\\',4,4\\'-benzophenone tetracarboxylic dianhydride-4,4\\'-diaminodiphenylmethane/3,5-diaminobenzoic acid (BTDA-MDA/DABA, BMD), are synthesized via chemical and thermal imidization methods, respectively, and employed as pervaporation membranes for ethanol dehydration. Chemical structures of the two polyimides are examined by FTIR and TGA to confirm the successful synthesis. A post thermal treatment of the polyimide membranes with the temperature range of 250 to 400. °C is applied, and its effects on the membrane morphology and separation performance are studied and characterized by FTIR, TGA, WXRD, solubility and sorption test. It is believed that the thermal treatment of the carboxyl-containing polyimide membrane at a relative low temperature only leads to the physical annealing, while it may cause the decarboxylation-induced cross-linking at a higher temperature. In addition, the operation temperature in pervaporation is also varied and shown to be an important factor to affect the final membrane performance. Performance benchmarking shows that the developed polyimide membranes both have superior pervaporation performance to most other flat-sheet dense membranes. This work is believed to shed useful insights on polyimide membranes for pervaporation applications.

  5. BK/TD models for analyzing in vitro impedance data on cytotoxicity.

    Science.gov (United States)

    Teng, S; Barcellini-Couget, S; Beaudouin, R; Brochot, C; Desousa, G; Rahmani, R; Pery, A R R

    2015-06-01

    The ban of animal testing has enhanced the development of new in vitro technologies for cosmetics safety assessment. Impedance metrics is one such technology which enables monitoring of cell viability in real time. However, analyzing real time data requires moving from static to dynamic toxicity assessment. In the present study, we built mechanistic biokinetic/toxicodynamic (BK/TD) models to analyze the time course of cell viability in cytotoxicity assay using impedance. These models account for the fate of the tested compounds during the assay. BK/TD models were applied to analyze HepaRG cell viability, after single (48 h) and repeated (4 weeks) exposures to three hepatotoxic compounds (coumarin, isoeugenol and benzophenone-2). The BK/TD models properly fit the data used for their calibration that was obtained for single or repeated exposure. Only for one out of the three compounds, the models calibrated with a single exposure were able to predict repeated exposure data. We therefore recommend the use of long-term exposure in vitro data in order to adequately account for chronic hepatotoxic effects. The models we propose here are capable of being coupled with human biokinetic models in order to relate dose exposure and human hepatotoxicity. Copyright © 2015 The Authors. Published by Elsevier Ireland Ltd.. All rights reserved.

  6. Endocrine disruptors induce cytochrome P450 by affecting transcriptional regulation via pregnane X receptor

    International Nuclear Information System (INIS)

    Mikamo, Eriko; Harada, Shingo; Nishikawa, Jun-ichi; Nishihara, Tsutomu

    2003-01-01

    Pregnane X receptor (PXR) is a nuclear receptor that regulates the expression of genes for cytochrome P450 3A (CYP3A), multidrug resistance 1 (MDR1), and organic anion-transporting peptide 2 (OATP2). These genes control the metabolism (CYP3A subfamily) and aspects of the pharmacokinetics (MDR1 and OATP2) of both endogenous and xenobiotic compounds. Since PXR is important in understanding the actions of endocrine disruptors (EDs), we determined the ability of suspected EDs to interact with PXR. In our study, 7 of 54 xenobiotics compounds interacted with PXR, including methoxychlor and benzophenone. All of the chemicals activated PXR in vitro and induced CYP3A mRNA in the male rat liver. In addition, CYP2C11 was also induced by some PXR agonists and converted methoxychlor into xenoestrogen. These findings suggest that some EDs affect sex hormone receptor indirectly by induction of metabolic enzyme via PXR, to produce rapidly higher concentrations of effective metabolites, leading to disturbance of the endocrine system

  7. Probing the Catalytic Promiscuity of a Regio- and Stereospecific C-Glycosyltransferase from Mangifera indica.

    Science.gov (United States)

    Chen, Dawei; Chen, Ridao; Wang, Ruishan; Li, Jianhua; Xie, Kebo; Bian, Chuancai; Sun, Lili; Zhang, Xiaolin; Liu, Jimei; Yang, Lin; Ye, Fei; Yu, Xiaoming; Dai, Jungui

    2015-10-19

    The catalytic promiscuity of the novel benzophenone C-glycosyltransferase, MiCGT, which is involved in the biosynthesis of mangiferin from Mangifera indica, was explored. MiCGT exhibited a robust capability to regio- and stereospecific C-glycosylation of 35 structurally diverse druglike scaffolds and simple phenolics with UDP-glucose, and also formed O- and N-glycosides. Moreover, MiCGT was able to generate C-xylosides with UDP-xylose. The OGT-reversibility of MiCGT was also exploited to generate C-glucosides with simple sugar donor. Three aryl-C-glycosides exhibited potent SGLT2 inhibitory activities with IC50  values of 2.6×, 7.6×, and 7.6×10(-7)  M, respectively. These findings demonstrate for the first time the significant potential of an enzymatic approach to diversification through C-glycosidation of bioactive natural and unnatural products in drug discovery. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Polyimides Based on Asymmetric Dianhydrides (II) (a-BPDA vs a-BTDA) for Resin Transfer Molding (RTM)

    Science.gov (United States)

    Chuang, Kathy C.; Criss, Jim M.; Mintz, Eric A.

    2010-01-01

    A new series of low-melt viscosity imide resins (10-20 poise at 280 C) were formulated from asymmetric 2,3,3',4' -benzophenone dianhydride (a-BTDA) and 4-phenylethynylphthalic endcaps, along with 3,4' -oxydianiline, 3,3' -methylenedianiline and 3,3'- diaminobenzophenone, using a solvent-free melt process. a-BTDA RTM resins exhibited higher glass transition temperatures (Tg's = 330-400 C) compared to those prepared by asymmetric 2,3,3',4' -biphenyl dianhydride, (a-BPDA, Tg's = 320-370 C). These low-melt viscosity imide resins were fabricated into polyimide/T650-35 carbon fiber composites by a RTM process. Composites properties of a-BTDA resins, such as open-hole compression and short-beam shear strength, are compared to those of composites made from a-BPDA based resin at room temperature, 288 C and 315 C. These novel, high temperature RTM imide resins exhibit outstanding properties beyond the performance of conventional RTM resins, such as epoxy and BMI resins which have use-temperatures around 177 C and 232 C for aerospace applications.

  9. Synthesis and Characterization of Sulfonated Poly(Phenylene Containing a Non-Planar Structure and Dibenzoyl Groups

    Directory of Open Access Journals (Sweden)

    Hohyoun Jang

    2016-02-01

    Full Text Available Polymers for application as sulfonated polyphenylene membranes were prepared by nickel-catalyzed carbon-carbon coupling reaction of bis(4-chlorophenyl-1,2-diphenylethylene (BCD and 1,4-dichloro-2,5-dibenzoylbenzene (DCBP. Conjugated cis/trans isomer (BCD had a non-planar conformation containing four peripheral aromatic rings that facilitate the formation of π–π interactions. 1,4-Dichloro-2,5-dibenzoylbenzene was synthesized from the oxidation reaction of 2,5-dichloro-p-xylene, followed by Friedel-Crafts reaction with benzene. DCBP monomer had good reactivity in polymerization affecting the activity of benzophenone as an electron-withdrawing group. The polyphenylene was sulfonated using concentrated sulfuric acid. These polymers without any ether linkages on the polymer backbone were protected from nucleophilic attack by hydrogen peroxide, hydroxide anion, and radicals generated by polymer electrolyte membrane fuel cell (PEMFC operation systems. The mole fraction of the sulfonic acid groups was controlled by varying the mole ratio of bis(4-chlorophenyl-1,2-diphenylethylene in the copolymer. In comparison with Nafion 211® membrane, these SBCDCBP membranes showed ion exchange capacity (IEC ranging from 1.04 to 2.07 meq./g, water uptake from 36.5% to 69.4%, proton conductivity from 58.7 to 101.9 mS/cm, and high thermal stability.

  10. In vitro photosensitization initiated by camphorquinone and phenyl propanedione in dental polymeric materials.

    Science.gov (United States)

    Christensen, Terje; Morisbak, Else; Tønnesen, Hanne Hjorth; Bruzell, Ellen M

    2010-09-02

    Documentation is scarce on the photobiological effects of photoinitiators present in dental light curable materials. The aim of this study was to determine cellular effects of the photoinitiators camphorquinone (CQ) and phenyl propanedione (PPD) and to investigate whether these substances produced reactive oxygen species after low and high doses of optical radiation (between 0 and 17J/cm(2)). Rat salivary gland cells in vitro were exposed to visible blue light and/or UVA. Hematoporphyrin (HP), a photosensitizer used in medicine, and the UVA-filter 2-methoxy-4-hydroxy-benzophenone (B-3) were used as reference substances. It was found that PPD produced hydrogen peroxide, but not singlet oxygen, upon light irradiation. CQ produced neither hydrogen peroxide nor singlet oxygen. Cell death by necrosis and apoptosis was induced by irradiation in the presence of CQ, PPD and HP. Doses higher than 6J/cm(2) UVA and blue visible light from a source similar to clinically applied sources, induced apoptosis even in the absence of photosensitizers added. A reciprocity relationship was found between radiant exposure (at constant irradiance) and concentration of photoinitiators. In conclusion, the oral cells under investigation were light sensitive, and the sensitivity increased in presence of photoinitiators. PPD acted by mechanisms that included reactive oxygen species and CQ probably by formation of free radicals. Copyright (c) 2010 Elsevier B.V. All rights reserved.

  11. The effect of camphorquinone (CQ) and CQ-related photosensitizers on the generation of reactive oxygen species and the production of oxidative DNA damage.

    Science.gov (United States)

    Pagoria, Dustin; Lee, Abert; Geurtsen, Werner

    2005-07-01

    Recent evidence suggests that following visible-light (VL) irradiation, CQ and the CQ-related photosensitizers benzil (BZ), benzophenone (BP), and 9-fluorenone (9-F) generate initiating radicals that may indiscriminately react with molecular oxygen forming reactive oxygen species (ROS). The purpose of this investigation was to determine whether VL-irradiated CQ, BZ, BP, and 9-F cause DNA damage due to the generation of ROS in vitro. ROS formation by CQ and CQ-related photosensitizers+/-dimethyl-p-toluidine (DMT) was investigated in a cell-free system with VL irradiation. DNA damage was determined using PhiX-174 RF I supercoiled double-stranded plasmid DNA and ROS quantified with 4-((9-acridinecarbonyl)amino)-2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO-9-AC), a fluorogenic ROS-sensitive probe. VL-irradiated CQ, BZ, BP, and 9-F (+/-DMT) produced significant DNA damage at 0.1, 0.5, and 1.0 mM and in a concentration-dependent manner (p<0.05). TEMPO-9-AC revealed that all investigated VL-irradiated photosensitizers produced significant amounts of ROS with BZ in the presence of DMT generating the most ROS after 30, 60, and 90 min. VL-irradiated CQ, BZ, BP, and 9-F +/-DMT continued to generate significant amounts of ROS 90 min after VL irradiation. As a result, future investigations should evaluate the effect of VL-irradiated photosensitizers in cells and possible protective effects provided by antioxidants.

  12. Direct and ketone-sensitized photoconversion of 1-nitro-9,10-anthraquinone to 1-amino-9,10-anthraquinone mediated by donor radicals

    Energy Technology Data Exchange (ETDEWEB)

    Goerner, Helmut, E-mail: goerner@mpi-muelheim.mpg.de [Max-Planck-Institut fuer Bioanorganische Chemie, D-45413 Muelheim an der Ruhr (Germany); Gruen, Henry [Max-Planck-Institut fuer Bioanorganische Chemie, D-45413 Muelheim an der Ruhr (Germany)

    2010-02-18

    The full photoreduction of 1-nitro-2-R-9,10-anthraquinone (R = H: N1, methyl: N2) was studied in benzene, acetonitrile and acetonitrile-water mixtures in the presence of 2-propanol and triethylamine (TEA). The major photoproduct is the fluorescing 1-amino-2-R-AQ (A1, A2). The quantum yield of full reduction increases with the donor concentration, approaching {Phi}{sub NH{sub 2}}=0.1. The intermediates involved are assigned on the basis of spectral and kinetic characteristics. The short-lived triplet state ({<=}20 ns) of N2 can be intercepted by 2-propanol or TEA, thereby forming the spectroscopically hidden donor radicals and the nitroAQ radicals which absorb at 400 and 540 nm; the latter band is due to the radical anion. The triplet state of N1 was not observed at room temperature, but the radical properties and decay in the nitrosoAQ are similar for N1 and N2. For donors in lower concentrations {Phi}{sub NH{sub 2}} is strongly increased in the presence of benzophenone, acetophenone or acetone, approaching 0.22. The results under direct and sensitized conditions are compared and major dependences and the effects of mixtures of acetonitrile with water are outlined.

  13. Direct and ketone-sensitized photoconversion of 1-nitro-9,10-anthraquinone to 1-amino-9,10-anthraquinone mediated by donor radicals

    International Nuclear Information System (INIS)

    Goerner, Helmut; Gruen, Henry

    2010-01-01

    The full photoreduction of 1-nitro-2-R-9,10-anthraquinone (R = H: N1, methyl: N2) was studied in benzene, acetonitrile and acetonitrile-water mixtures in the presence of 2-propanol and triethylamine (TEA). The major photoproduct is the fluorescing 1-amino-2-R-AQ (A1, A2). The quantum yield of full reduction increases with the donor concentration, approaching Φ NH 2 =0.1. The intermediates involved are assigned on the basis of spectral and kinetic characteristics. The short-lived triplet state (≤20 ns) of N2 can be intercepted by 2-propanol or TEA, thereby forming the spectroscopically hidden donor radicals and the nitroAQ radicals which absorb at 400 and 540 nm; the latter band is due to the radical anion. The triplet state of N1 was not observed at room temperature, but the radical properties and decay in the nitrosoAQ are similar for N1 and N2. For donors in lower concentrations Φ NH 2 is strongly increased in the presence of benzophenone, acetophenone or acetone, approaching 0.22. The results under direct and sensitized conditions are compared and major dependences and the effects of mixtures of acetonitrile with water are outlined.

  14. A highly reactive photobase catalytic system for sol–gel polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Chemtob, Abraham, E-mail: abraham.chemtob@uha.fr [Laboratory of Macromolecular Photochemistry and Engineering, University of Haute-Alsace, ENSCMu, 3 rue Alfred Werner, 68093 Mulhouse Cedex (France); De Paz-Simon, Héloïse; Dietlin, Céline; Croutxé-Barghorn, Céline; Salmi, Hanène; Allonas, Xavier [Laboratory of Macromolecular Photochemistry and Engineering, University of Haute-Alsace, ENSCMu, 3 rue Alfred Werner, 68093 Mulhouse Cedex (France); Chany, Anne-Caroline [Laboratory of Organic and Bioorganic Chemistry, University of Haute Alsace, ENSCMu, 3 rue Alfred Werner, 68093 Mulhouse Cedex (France); Vidal, Loïc; Rigolet, Séverinne [Institute of Mulhouse Material Science, UMR-CNRS 7361, University of Haute-Alsace, 3 rue Alfred Werner 68093, Mulhouse Cedex (France)

    2014-01-01

    In sol–gel polymerization of alkoxysilane precursors, base catalysts are usually employed to introduce textural properties. Herein, we show the feasibility and interest of a photobase-catalyzed sol–gel reaction to afford silicate films. Our inorganic polymerization is solvent-free, single-step and UV activatable with a mixture of α-aminoacetophenone (photobase generator), benzophenone (photosensitizer) and triphenylphosphine (oxygen scavenger). To date, the present tricomponent photolatent system generating N-alkyl morpholine tertiary amines represents one of the most efficient photobase generators reported so far in sol–gel chemistry. A combination of spectroscopic and electron microscopy techniques enabled to investigate the fundamental chemistry underlying alkoxysilane photopolymerization: reaction mechanism, hydrolysis kinetics and siloxane microstructure. Systematic comparison with a photoacid-catalyzed process revealed also the impact of the photocatalyst nature on film texture, morphology and optical properties. - Highlights: • A very efficient UV-driven photobase-catalyzed sol–gel process. • Single-step film formation without transition through a sol. • Comparison of film properties under photoacid and photobase catalysis.

  15. Neurotoxic effect of active ingredients in sunscreen products, a contemporary review.

    Science.gov (United States)

    Ruszkiewicz, Joanna A; Pinkas, Adi; Ferrer, Beatriz; Peres, Tanara V; Tsatsakis, Aristides; Aschner, Michael

    2017-01-01

    Sunscreen application is the main strategy used to prevent the maladies inflicted by ultraviolet (UV) radiation. Despite the continuously increasing frequency of sunscreen use worldwide, the prevalence of certain sun exposure-related pathologies, mainly malignant melanoma, is also on the rise. In the past century, a variety of protective agents against UV exposure have been developed. Physical filters scatter and reflect UV rays and chemical filters absorb those rays. Alongside the evidence for increasing levels of these agents in the environment, which leads to indirect exposure of wildlife and humans, recent studies suggest a toxicological nature for some of these agents. Reviews on the role of these agents in developmental and endocrine impairments (both pathology and related mechanisms) are based on both animal and human studies, yet information regarding the potential neurotoxicity of these agents is scant. In this review, data regarding the neurotoxicity of several organic filters: octyl methoxycinnamate, benzophenone-3 and -4, 4-methylbenzylidene camphor, 3-benzylidene camphor and octocrylene, and two allowed inorganic filters: zinc oxide and titanium dioxide, is presented and discussed. Taken together, this review advocates revisiting the current safety and regulation of specific sunscreens and investing in alternative UV protection technologies.

  16. Designed biocompatible nano-inhibitor based on poly(β-cyclodextrin-ester) for reduction of the DEHP migration from plasticized PVC.

    Science.gov (United States)

    Raeisi, Ahmad; Faghihi, Khalil; Shabanian, Meisam

    2017-10-15

    The easy migration of di(2-ethylhexyl) phthalate (DEHP) from the plasticized PVC (P-PVC) poses a serious threat to human health and the ecosystems. Thus, its control migration from the P-PVC products is very important. In this work, a poly(β-cyclodextrin-ester) network (β-CDP) was synthesized via reaction of β-cyclodextrin with 3,3',4,4'-benzophenone tetracarboxylic dianhydride. As a potential inhibitor for reduction of the DEHP migration, the β-CDP was grafted to Fe 3 O 4 nanoparticles. Poly(β-cyclodextrin-ester) functionalized Fe 3 O 4 nanoparticles (MNP-CDP) has been used in PVC/DEHP system as a reactive nano-inhibitor to reduce DEHP migration. Thermal stability and mechanical properties of obtained films were investigated. DEHP migration tests of the P-PVC films were also carried out by using Gas chromatography. It was found that by incorporating the small amounts of nano-inhibitor in PVC/DEHP system, the migration of DEHP effectively reduced from the P-PVC samples about 65% without any serious changes in mechanical and thermal properties of the P-PVC films. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. An optical fiber coupled streak camera system for multichannel recording of simultaneous emission from a single plasma producing event

    International Nuclear Information System (INIS)

    Tan, T.H.; Williams, A.H.

    1983-01-01

    A streak camera system capable of multichannel sub-nanosecond recording of simultaneous emissions (photons and particles) from a single plasma interaction event (laser or particle beam) has been developed. In this system ultra-fast quenched (benzophenone) plastic scintillator detectors are coupled via optical fibers to a visible streak camera. The use of optical fibers presents two tractive features: miniaturization of detectors permits improved flexibility in placing detectors at the most desirable location and in greater number than can normally be accommodated; and the detectors are insensitive to electromagnetic noise generated both from the interacting plasmas and from the high voltage components associated with the laser or particle beam system. The fibers can be directly routed through vacuum tight couplers at the target chamber wall and brought into direct contact with the photocathode of the camera in most applications. In fusion experiments, however, the fiber florescence and Cerenkov radiation due to the copious emissions of energetic electrons and x-rays can present serious problems in the use of long fibers. Here, short fibers can be used and the visible streak camera is then focused through a glass port of the target chamber onto the open ends of these optical fibers

  18. Fabrication of protein microarrays for alpha fetoprotein detection by using a rapid photo-immobilization process

    Directory of Open Access Journals (Sweden)

    Sirasa Yodmongkol

    2016-03-01

    Full Text Available In this study, protein microarrays based on sandwich immunoassays are generated to quantify the amount of alpha fetoprotein (AFP in blood serum. For chip generation a mixture of capture antibody and a photoactive copolymer consisting of N,N-dimethylacrylamide (DMAA, methacryloyloxy benzophenone (MaBP, and Na-4-styrenesulfonate (SSNa was spotted onto unmodified polymethyl methacrylate (PMMA substrates. Subsequently to printing of the microarray, the polymer and protein were photochemically cross-linked and the forming, biofunctionalized hydrogels simultaneously bound to the chip surface by short UV- irradiation. The obtained biochip was incubated with AFP antigen, followed by biotinylated AFP antibody and streptavidin-Cy5 and the fluorescence signal read-out. The developed microarray biochip covers the range of AFP in serum samples such as maternal serum in the range of 5 and 100 ng/ml. The chip production process is based on a fast and simple immobilization process, which can be applied to conventional plastic surfaces. Therefore, this protein microarray production process is a promising method to fabricate biochips for AFP screening processes. Keywords: Photo-immobilization, Protein microarray, Alpha fetoprotein, Hydrogel, 3D surface, Down syndrome

  19. RMN 13C de chalcones protonées: Factorisation des interactions intramoléculaires

    Science.gov (United States)

    Membrey, François; Doucet, Jean-Pierre

    13C study of protonated para, para' disubstituted chalcones XC 6H 4CHCHC(OH) +C 6H 4Y, shows for the chemical shift of the carbenium center important deviations from a strict additivity of Substituent Induced Shifts observed in the corresponding monosubstituted ions. By collecting the experimental data into sub-populations where only one substituent (X or Y) varies—the other remaining fixed—a network of linear homogeneous correlations (δ/δ) is obtained. Their largely variable slopes indicate that the susceptibility of the carbenium site to the perturbations induced by one of the substituent groups depends on the nature of the other substituent group. The definition of 'Intrinsic Substituent Parameters' (derived from the SCS observed, in these ions, on the aromatic para positions) allows to separate the action of a substituent group on the electronic interaction mechanism and the global perturbation detected on the observation site. For a quantitative evaluation of these interactions, a Factorization Model is proposed, where deviations to additivity of the SCS are expressed as a product of the intrinsic parameters of X and Y groups. This model is successfully applied to 13C spectra of protonated chalcones and benzophenones. The parallelism between these intrinsic group effects and the SCS observed in monosubstituted benzenes points out the prime importance in these cationic systems, of π polarisation effects modulating the electron transfer toward the carbenium center within a concerted π-inductive mesomeric action.

  20. Multi function Finishing and Pigment Printing of UV Cured Cotton/Polyester Fabrics Coated with Plasticized Epoxy Resin/ZnO Formulation

    International Nuclear Information System (INIS)

    Hassan, M.S.; Mousaa, I.M.; Ali, N.M.

    2015-01-01

    Cotton/ Polyester fabrics were coated with epoxy acrylate (EA) formulations plasticized by castor oil (CO), in the presence of benzophenone as initiator, ZnO (antibacterial agent) and pigment printing. Ultra violet (UV) irradiation was used as a curing system. The effect of UV irradiation time and CO percentage on the mechanical and crease recovery properties were investigated. The effect of the coating process on the cross-section feature by using scanning electron microscope (SEM), the antibacterial properties, water retardance, colour difference and the durability for washing of the coated fabrics were also investigated. From the results, it was found that the crease recovery and antibacterial properties were enhanced. Also, the colour durability against multiple washing cycles gave adequate results after application of the investigated coating formulation. The most fitting castor oil per cent was found to be 45%, while the 3% ZnO recorded the best antibacterial and mechanical properties. The pigment per cent that gave the highest durability and adequate colour strength was 0.6%.

  1. The study of the thermal behavior of a new semicrystalline polyimide

    Science.gov (United States)

    Cheng, Stephen Z. D.; Chalmers, Tammy M.

    1992-01-01

    Thermal properties of a new semicrystalline polyimide synthesized from 3,3',4,4' benzophenone tetracarboxylic dianhydride (BTDA) and 2,2 dimethyl 1,2-(4 aminophenoxy) propane (DMDA) were studied. Heat capacities in the solid and liquid states of BTDA-DMDA were measured. The heat capacity increase at the glass transition temperature (T sub g = 230 C) is 145 J/(C mol) for amorphous BTDA-DMDA. The equilibrium heat of fusion of the BTDA-DMDA crystals was obtained using wide angle X ray diffraction and differential scanning calorimetry measurements, and it is 75.8 kJ/mol. Based on the information of crystallinity and the heat capacity increase at T sub g, a rigid amorphous fraction is identified in semicrystalline BTDA-DMDA samples. The rigid amorphous fraction represents an interfacial region between the crystalline and amorphous states. In particular, this fraction increases with the crystallinity of the sample which should be associated with crystal sizes, and therefore, with crystal morphology. It was also found that this polymer has a high temperature crystal phase upon annealing above its original melting temperature. The thermal degradation activation energies are determined to be 154 and 150 kJ/mol in nitrogen and air, respectively.

  2. Gelatin-based microspheres crosslinked with glutaraldehyde and rutin oriented to cosmetics

    Directory of Open Access Journals (Sweden)

    Fabiana Graziola

    Full Text Available ABSTRACT Glutaraldehyde (GTA has been extensively used as a gelatin crosslinking agent, however, new natural ones have been suggested as more biocompatible. Polyphenols are possible candidates and the flavonols, such as rutin (RUT, also exhibit potential synergism with sunscreens and antioxidant agents used in cosmetics. In this work, gelatin microspheres (M0 were obtained and crosslinked with GTA 10 mM (MG or RUT 10 mM (MR, dissolved in acetone:NaOH 0,01M (70:30 v/v. MG exhibited crosslinking extent of 54.4%. Gelatin, M0, MG and MR did not elicit any signs of skin damage, regarding the formation of erythema, the barrier function disruption and negative interference in the stratum corneum hydration. Oily dispersions containing M0, MG or MR, isolated or combined with benzophenone-3 or octyl methoxycinnamate, suggested that the microspheres, at a 5.0% w/w, had no additional chemical or physical photoprotective effect in vitro. Crosslinking with RUT had occurred, but in a lower degree than GTA. Microspheres had not improved sun protection parameters, although, non-treated gelatin interfered positively with the SPF for both UV filters. The in vivo studies demonstrated that these materials had very good skin compatibility.

  3. Ozonation of the oxybenzone, octinoxate, and octocrylene UV-filters: Reaction kinetics, absorbance characteristics, and transformation products.

    Science.gov (United States)

    Hopkins, Zachary R; Snowberger, Sebastian; Blaney, Lee

    2017-09-15

    UV-filters (UVFs) are active ingredients in personal care products that protect skin from exposure to UV light. Environmentally-relevant concentrations of UVFs have recently been linked to toxicity in aquatic organisms, necessitating research into improved UVF removal in water/wastewater treatment. Here, we investigated ozonation of the three most commonly employed UVFs: octinoxate (OMC), octocrylene (OC), and oxybenzone (OXY). Specific second-order rate constants for UVF reaction with ozone were identified as follows: OMC, 5.25×10 4 M -1 s -1 ; OC, 1.58M -1 s -1 ; OXY (neutral), 3.80×10 2 M -1 s -1 ; and, OXY (anion), 1.51×10 6 M -1 s -1 . These kinetic parameters indicated that OMC and OXY undergo significant (2-log or greater) transformation for typical ozone exposures in disinfection processes; however, minimal oxidation is expected for OC. UV absorbance mapping was employed to characterize the loss of UVF activity (i.e., absorbance across the UV-A, UV-B, and UV-C ranges) during ozonation. These 4-dimensional maps also confirmed ozone attack mechanisms, namely reaction at phenolate (OXY) and olefin (OMC, OC) groups. Primary transformation products from these reactions were identified for all three UVFs of concern. For OC and OXY, the benzophenone structure is conserved, suggesting that transformation products retain toxicity concerns. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Photostability of cosmetic UV filters on mammalian skin under UV exposure.

    Science.gov (United States)

    Stiefel, Constanze; Schwack, Wolfgang; Nguyen, Yen-Thi Hai

    2015-01-01

    Previous studies showed that the common UV filter substances benzophenone-3 (BP-3), butyl methoxydibenzoylmethane (BM-DBM), octocrylene (OCR), ethylhexyl methoxycinnamate (EHMC), ethylhexyl salicylate (EHS) and ethylhexyl triazone (EHT) were able to react with amino side chains of different proteins in vitro. To transfer the results to mammalian skin conditions, sunscreen products were applied on both prepared fresh porcine skin and glass plates, followed by UV irradiation and the determination of depletion of the respective UV filters. Significantly lower recoveries of the UV filters extracted from skin samples than from glass plates indicated the additional reaction of the UV filters with skin constituents, when proteins will be the most important reactants. Among the products tested, BP-3 showed the greatest differences in recoveries between glass and skin samples of about 13% and 24% after 2 and 4 h of irradiation, respectively, followed by EHS > BM-DBM > OCR > EHMC > EHT. The obtained results raise the question, whether the common in vitro evaluations of sunscreens, using inert substrate materials like roughened quartz or polymethyl methacrylate (PMMA) plates are really suitable to fully replace in vivo methods, as they cannot include skin-typical reactions. © 2014 The American Society of Photobiology.

  5. Occurrence of eight UV filters in beaches of Gran Canaria (Canary Islands). An approach to environmental risk assessment.

    Science.gov (United States)

    Sánchez Rodríguez, A; Rodrigo Sanz, M; Betancort Rodríguez, J R

    2015-07-01

    Due to the growing concern about human health effects of ultraviolet (UV) radiation, the use of UV filters has increased in recent decades. Unfortunately, some common UV filters are bioaccumulated in aquatic organisms and show a potential for estrogenic activity. The aim of the present study is to determine the presence of some UV filters in the coastal waters of six beaches around Gran Canaria Island as consequence of recreational seaside activities. Eight commonly used UV filters: benzophenone-3 (BP-3), octocrylene (OC), octyl-dimethyl-PABA (OD-PABA), ethylhexyl methoxy cinnamate (EHMC), homosalate (HMS), butyl methoxydibenzoyl methane (BMDBM), 4-methylbenzylidene camphor (4-MBC) and diethylamino hydroxybenzoyl hexyl benzoate (DHHB), were monitored and, with the exception of OD-PABA, all were detected in the samples collected. 99% of the samples showed some UV filters and concentration levels reached up to 3316.7 ng/L for BP-3. Environmental risk assessment (ERA) approach showed risk quotients (RQ) higher than 10, which means that there is a significant potential for adverse effects, for 4-MBC and EHMC for those samples with highest levels of UV filters. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Sediments as a sink for UV filters and benzotriazoles: the case study of Upper Iguaçu watershed, Curitiba (Brazil).

    Science.gov (United States)

    Mizukawa, Alinne; Molins-Delgado, Daniel; de Azevedo, Júlio César Rodrigues; Fernandes, Cristóvão Vicente Scapulatempo; Díaz-Cruz, Silvia; Barceló, Damià

    2017-08-01

    Ingredients in home and personal care products, including UV filters and benzotriazoles, are high production volume chemicals extensively used in our daily life, despite several studies revealed their potential eco-toxicity and endocrine-disrupting capacity. Due to some features, such as high lipophilicity, low degradability, and persistence of many of these compounds, sediments can be considered a sink for them in the aquatic environment. In the present study, nine organic UV filters and three benzotriazoles were investigated for the first time in sediments from four urban rivers in Brazil. The contaminants were analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The results revealed that octocrylene (OC), etylhexyl-methoxycinnamate (EHMC), benzophenone-3 (oxybenzone, BP3), and benzotriazole (BZT) were the predominant compounds adsorbed on the sediments, with concentrations ranging from 5.6 to 322.2 ng g -1 dry weight. The results reported in this work constitute the first data on the accumulation of polar benzotriazoles and lipophilic organic UV filters in sediments from Brazil.

  7. Occurrence, Distribution, and Fate of Organic UV Filters in Coral Communities.

    Science.gov (United States)

    Tsui, Mirabelle M P; Lam, James C W; Ng, T Y; Ang, P O; Murphy, Margaret B; Lam, Paul K S

    2017-04-18

    Organic ultraviolet (UV) filters are widely used in personal care products and occur ubiquitously in the aquatic environment. In this study, concentrations of seven commonly used organic UV filters were determined in seawater, sediment and five coral species collected from the eastern Pearl River Estuary of South China Sea. Five compounds, benzophenone-1, -3, and -8 (BP-1, -3, and -8), octocrylene (OC) and octyl dimethyl-p-aminobenzoic acid (ODPABA), were detected in the coral tissues with the highest detection frequencies (>65%) and concentrations (31.8 ± 8.6 and 24.7 ± 10.6 ng/g ww, respectively) found for BP-3 and BP-8. Significantly higher concentrations of BP-3 were observed in coral tissues in the wet season, indicating that higher inputs of sunscreen agents could be attributed to the increased coastal recreational activities. Accumulation of UV filters was only observed in soft coral tissues with bioaccumulation factors (log 10 -values) ranging from 2.21 to 3.01. The results of a preliminary risk assessment indicated that over 20% of coral samples from the study sites contained BP-3 concentrations exceeding the threshold values for causing larval deformities and mortality in the worst-case scenario. Higher probabilities of negative impacts of BP-3 on coral communities are predicted to occur in wet season.

  8. Novel poly (arylene-ether-ether-ketone)s containing preformed imide unit and pendant long chain alkyl group

    International Nuclear Information System (INIS)

    Sayyed, Maheboob M.; Maldar, Noormahmad N.

    2010-01-01

    The studies were carried out to get preformed imide unit containing PEEKs and Co-PEEKs with pendant long chain alkyl group. Thus two new bisphenols; N,N'-bis (4-hydroxy 2-pentadecyl phenyl) pyromellitimide (HPI) (I) and N,N'-bis (4-hydroxy 2-pentadecyl phenyl 3,3',4,4'-benzophenone tetracarboxylic imide (HBI) (II) containing imide unit, pendant C-15 alkyl substituents were synthesized, characterized by spectral data and polycondensed with 4,4'-difluorobenzophenone (DFB) to yield several PEEK and Co-PEEKs. The polymers were characterized by FTIR, inherent viscosity, solubility, and XRD. The polymers were obtained in good yields and had inherent viscosities up to 0.65 dL/g in NMP. Polymerization of mixture of two bisphenols; [(I) and BPA]; and [(II) and BPA] in various mol%, with DFB gave number of the copolymers viz. Co-PEEK-BPAPI and Co-PEEK-BPABI. Many of the Co-PEEKs had good solubility in polar solvents. The solubility of PEEK containing bulky pendant alkyl substituents did not much improve probably due to simultaneous presence of rigid imide structures. XRD analysis indicated that PEEK and Co-PEEKs were partially crystalline or amorphous depending on the nature and % content of imide-bisphenol. These new PEEK materials can be used as high performance films, coatings, gas separation membranes, in aerospace and nuclear industries.

  9. Preparation of Mach-Zehnder interferometric photonic biosensors by inkjet printing technology

    Science.gov (United States)

    Strasser, Florian; Melnik, Eva; Muellner, Paul; Jiménez-Meneses, Pilar; Nechvile, Magdalena; Koppitsch, Guenther; Lieberzeit, Peter; Laemmerhofer, Michael; Heer, Rudolf; Hainberger, Rainer

    2017-05-01

    Inkjet printing is a versatile method to apply surface modification procedures in a spatially controlled, cost-effective and mass-fabrication compatible manner. Utilizing this technology, we investigate two different approaches for functionalizing label-free optical waveguide based biosensors: a) surface modification with amine-based functional polymers (biotin-modified polyethylenimine (PEI-B)) employing active ester chemistry and b) modification with dextran based hydrogel thin films employing photoactive benzophenone crosslinker moieties. Whereas the modification with PEI-B ensures high receptor density at the surface, the hydrogel films can serve both as a voluminous matrix binding matrix and as a semipermeable separation layer between the sensor surface and the sample. We use the two surface modification strategies both individually and in combination for binding studies towards the detection of the protein inflammation biomarker, C-reactive protein (CRP). For the specific detection of CRP, we compare two kinds of capture molecules, namely biotinylated antibodies and biotinylated CRP-specific DNA based aptamers. Both kinds of capture molecules were immobilized on the PEI-B by means of streptavidin-biotin affinity binding. As transducer, we use an integrated four-channel silicon nitride (Si3N4) waveguide based Mach-Zehnder interferometric (MZI) photonic sensing platform operating at a wavelength of 850nm (TM-mode).

  10. Photocatalytic degradation of sunscreen active ingredients mediated by nanostructured materials

    Science.gov (United States)

    Soto-Vazquez, Loraine

    Water scarcity and pollution are environmental issues with terrible consequences. In recent years several pharmaceutical and personal care products, such as sunscreen active ingredients, have been detected in different water matrices. Its recalcitrant behavior in the environment has caused controversies and generated countless questions about its safety. During this research, we employed an advanced oxidation process (photocatalysis) to degrade sunscreen active ingredients. For this study, we used a 3x3 system, evaluating three photocatalysts and three different contaminants. From the three catalysts employed, two of them were synthesized. ZnO nanoparticles were obtained using zinc acetate dihydrated as the precursor, and TiO2 nanowires were synthesized from titanium tetrachloride precursor. The third catalyst employed (namely, P25) was obtained commercially. The synthesized photocatalysts were characterized in terms of the morphology, elemental composition, crystalline structure, elemental oxidation states, vibrational modes and surface area, using SEM-EDS, XRD, XPS, Raman spectroscopy and BET measurements, respectively. The photocatalysts were employed during the study of the degradation of p-aminobenzoic acid, phenylbenzimidazole sulfonic acid, and benzophenone-4. In all the cases, at least 50% degradation was achieved. P25 showed degradation efficiencies above 90%, and from the nine systems, 7 of them degraded at least 86%.

  11. Maternal exposure to UV filters and associations to maternal thyroid hormones and IGF-I/IGFBP3 and birth outcomes

    DEFF Research Database (Denmark)

    Krause, Marianna; Frederiksen, Hanne; Sundberg, Karin

    2018-01-01

    BACKGROUND: Several chemical UV filters/absorbers (in the following called UV filters) have endocrine disrupting properties in vitro and in vivo. Exposure to these chemicals, especially during prenatal development, is of concern. OBJECTIVES: To examine maternal exposure to UV filters and associat......BACKGROUND: Several chemical UV filters/absorbers (in the following called UV filters) have endocrine disrupting properties in vitro and in vivo. Exposure to these chemicals, especially during prenatal development, is of concern. OBJECTIVES: To examine maternal exposure to UV filters......) in urine and 4-hydroxy-benzophenone (4-HBP) in serum were measured by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The relationships between 2nd trimester maternal concentrations of the three chemical UV filters and maternal serum concentrations of thyroid hormones and growth factors, as well...... and the possible impact on maternal thyroid hormones and growth factors, and on fetal growth, calls for further studies on possible long term consequences of the exposure to UV filters on fetal development and children's health....

  12. Effect of the calcination temperature on the photocatalytic efficiency of acidic sol-gel synthesized TiO2nanoparticles in the degradation of alprazolam.

    Science.gov (United States)

    Romeiro, Andreia; Freitas, Diana; Emília Azenha, M; Canle, Moisés; Burrows, Hugh D

    2017-06-14

    We report a comparative study on the photodegradation of the widely used benzodiazepine psychoactive drug alprazolam (8-chloro-1-methyl-6-phenyl-4H-[1,2,4]triazolo[4,3-a][1,4]benzodiazepine, ALP) using direct photolysis, and titanium dioxide photocatalyzed reaction. Titanium dioxide photocatalysts were prepared as nanoparticles by acidic sol-gel methods, calcined at two different temperatures, and their behavior compared with P25 (Degussa type) TiO 2 . Efficient photodegradation was observed in the photocatalytic process, with over 90% degradation after 90 minutes under optimized conditions. Triazolaminoquinoline, 5-chloro-(5-methyl-4H-1,2,4-triazol-4-yl)benzophenone, triazolbenzophenone, and α-hydroxyalprazolam were identified as the degradation products by fluorescence spectroscopy and HPLC-MS. A comparison with the literature suggests that 8H-alprazolam may also be formed. Good mineralization was observed with TiO 2 photocatalysts. ALP photodegradation with TiO 2 follows pseudo-first order kinetics, with rates depending on the photocatalyst used. The effects of the quantity of the photocatalyst and concentration of alprazolam were studied.

  13. Nanostructured polymer and lipid carriers for sunscreen. Biological effects and skin permeation.

    Science.gov (United States)

    Marcato, P D; Caverzan, J; Rossi-Bergmann, B; Pinto, E F; Machado, D; Silva, R A; Justo, G Z; Ferreira, C V; Durán, N

    2011-03-01

    The interest in developing new sunscreens is increasing due to the harmful effects of UV radiation on the skin, such as erythema, accelerated skin ageing (photoageing) and the induction of skin cancer. However, many molecular sunscreens penetrate into the skin causing photoallergies, phototoxic reactions and skin irritation. Thus, the aim of this work was the preparation and characterization of polymeric and solid lipid nanoparticles to act carriers of benzophenone-3 (BZ3), aiming to improve the safety of sunscreen products by increasing the sun protection factor (SPF), decreasing BZ3 skin penetration and decreasing BZ3 concentration in sunscreen formulation. BZ3 was encapsulated in poly(epsilon-caprolactone) (PCL) nanoparticles by the nanoprecipitation method and in solid lipid nanoparticles (SLN) by the hot high pressure homogenization method. The particles were stable for 40 days. The BZ3 encapsulated in PCL nanoparticles was released faster than BZ3 encapsulated in SLN. The sun protection factor increased when BZ3 was encapsulated in both nanostructures. However, BZ3 encapsulated in PCL nanoparticles decreased its skin permeation more than SLN-BZ3. Furthermore, BZ3 encapsulated in SLN did not exhibit cytotoxic or phototoxic effects in human keratinocytes (HaCaT cells) and BABL/c 3T3 fibroblasts, whereas PCL nanoparticles with BZ3 showed phototoxic potential in HaCaT cells. Nevertheless, BZ3 free and encapsulated in PCL nanoparticles or in SLN did not show allergic reactions in mice. Our results suggest that these nanostructures are interesting carriers for sunscreen.

  14. Estrogenic potential of the Venice, Italy, lagoon waters.

    Science.gov (United States)

    Pojana, Giulio; Bonfà, Angela; Busetti, Francesco; Collarin, Anna; Marcomini, Antonio

    2004-08-01

    The exposure of the Venice lagoon (Italy) to endocrine-disrupting compounds (EDCs) from different sources was investigated. Spatial and time distribution of EDC concentrations were determined in four sampling sessions (December 2001-May 2002) by solid phase extraction followed by high-performance liquid chromatography separation coupled with mass spectrometry detection via electrospray interface (SPE-HPLC-ESI-MS), which allowed identification of natural (estradiol, estrone) and synthetic estrogenic compounds, both steroidal (ethinylestradiol, mestranol) and nonsteroidal (benzophenone, bisphenol-A, nonylphenol, nonylphenol monoethoxylate carboxylate). No significant differences in the EDC distribution were observed between stations located near selected sources (raw sewage from the historical center of Venice, treated municipal and industrial effluents from sewage treatment plants, and areas undergoing the inflow of rivers). While synthetic nonsteroidal analytes were recorded in the 1 to 1040 ng/L range (average concentration: 34 ng/L), steroidal EDC (estradiol, ethinylestradiol) concentrations were lower (1-125 ng/L; average concentration: 8 ng/L). The estrogenic activity of lagoon waters was estimated in terms of estradiol equivalent concentration (EEQ) by applying the estradiol equivalency factors (EEFs). Steroidal EDCs (estradiol, ethinylestradiol) contributed >97% to the total potential estrogenicity of the waters, which accounted for 4 to 172 ng/L (average: 25 ng/L), as total EEQs. These levels are likely to pose adverse effects on the Venice lagoon aquatic organisms.

  15. Monitoring pharmaceuticals and personal care products in reservoir water used for drinking water supply.

    Science.gov (United States)

    Aristizabal-Ciro, Carolina; Botero-Coy, Ana María; López, Francisco J; Peñuela, Gustavo A

    2017-03-01

    In this work, the presence of selected emerging contaminants has been investigated in two reservoirs, La Fe (LF) and Rio Grande (RG), which supply water to two drinking water treatment plants (DWTPs) of Medellin, one of the most populated cities of Colombia. An analytical method based on solid-phase extraction (SPE) of the sample followed by measurement by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was developed and validated for this purpose. Five monitoring campaigns were performed in each reservoir, collecting samples from 7 sites (LF) and 10 sites (RG) at 3 different depths of the water column. In addition, water samples entering in the DWTPs and treated water samples from these plans were also analysed for the selected compounds. Data from this work showed that parabens, UV filters and the pharmaceutical ibuprofen were commonly present in most of the reservoir samples. Thus, methyl paraben was detected in around 90% of the samples collected, while ibuprofen was found in around 60% of the samples. Water samples feeding the DWTPs also contained these two compounds, as well as benzophenone at low concentrations, which was in general agreement with the results from the reservoir samples. After treatment in the DWTPs, these three compounds were still present in the samples although at low concentrations (water are still unknown. Further research is needed to evaluate the effect of chronic exposure to these compounds via consumption of drinking water.

  16. Evaluation of the QuEChERS method for the extraction of pharmaceuticals and personal care products from drinking-water treatment sludge with determination by UPLC-ESI-MS/MS.

    Science.gov (United States)

    Cerqueira, Maristela B R; Guilherme, Juliana R; Caldas, Sergiane S; Martins, Manoel L; Zanella, Renato; Primel, Ednei G

    2014-07-01

    A modified version of the QuEChERS method has been evaluated for the determination of 21 pharmaceuticals and 6 personal care products (PPCPs) in drinking-water sludge samples by employing ultra high liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The performance of the method was evaluated through linearity, recovery, precision (intra-day), method detection and quantification limits (MDL and MQL) and matrix effect. The calibration curves prepared in acetonitrile and in the matrix extract showed a correlation coefficient ranging from 0.98 to 0.99. MQLs values were on the ng g(-1) order of magnitude for most compounds. Recoveries between 50% and 93% were reached with RSDs lower than 10% for most compounds. Matrix effect was almost absent with values lower than 16% for 93% of the compounds. By coupling a quick and simple extraction called QuEChERS with the UPLC-MS/MS analysis, a method that is both selective and sensitive was obtained. This methodology was successfully applied to real samples and caffeine and benzophenone-3 were detected in ng g(-1) levels. Copyright © 2014 Elsevier Ltd. All rights reserved.

  17. Effect of 2,4-dihydroxybenzophenone (BP1) on early life-stage development of the marine copepod Acartia tonsa at different temperatures and salinities

    DEFF Research Database (Denmark)

    Kusk, Kresten Ole; Avdolli, Manola; Wollenberger, Leah

    2011-01-01

    Benzophenone (BP)-type ultraviolet (UV) filters are widely used in cosmetic and sunscreen products and can enter the aquatic environment. Therefore, we investigated the subchronic toxicity of 2,4-dihydroxybenzophenone (BP1) on the marine calanoid copepod Acartia tonsa in an early life-stage...... was found acutely toxic at 2.6 mg/L (48-h median lethal concentration [LC50]). The toxicity of BP1 on early life-stage development was studied in combinations of three temperatures (15, 20, 25°C) and three salinities (15, 20, 25‰) using five toxicant concentrations between 0.051 and 2 mg/L in each scenario...... a copepodite stage (DT(½) ) at the different conditions were calculated. The DT(½) values decreased from 296 h at 15°C to 89 h at 25°C and were also affected by salinity (126 h at 15‰ and 167 h at 30‰), whereas the light:dark regime and culture density influenced development only to a minor extent. BP1...

  18. Influence of particle size on appearance and in vitro efficacy of sunscreens

    Directory of Open Access Journals (Sweden)

    Débora Granemann e Silva

    2013-06-01

    Full Text Available Nanotechnology applies to diverse sectors of science. In cosmetic area, investments have strengthened the idea that nanoproducts provide innumerable benefits to consumers. Extreme exposition to solar light can cause undesirable effects, thus, adding UV filters in cosmetic products are often used as prevention. Ethylhexyl methoxycinnamate and benzophenone-3 are UV filters widely used in sunscreen formulations, this UV filters absorb UVB and UVA radiation, respectively. In this study, sunscreen formulations were developed as nano and macroemulsion, but composed by the same raw material. Nanoemulsion was obtained by phase inversion temperature method (PIT. Physical and functional properties were evaluated by visual analysis, particle size distribution and by diffuse reflectance spectrophotometry. Achieved nanoemulsion showed bluish brightness aspect, less apparent consistency than macroemulsion, stability longer than 48 hours (22.0 ± 2.0 °C and bimodal particle size distribution with average (mean sizes around 10 nm (61% and 4.5 µm (39%. Macroemulsion showed milky aspect, higher consistency than nanoemulsion, instability after 48 hours (22.0 ± 2.0 °C and bimodal particle size distribution with average (mean size around 202 nm (9% and 10.4 µm (91%. Effectiveness profile of sunscreen formulations remained apparently similar, based on achieved results of in vitro SPF, UVA/UVB ratio and critical wavelength assays.

  19. Cosmetics as a potential source of environmental contamination in the UK.

    Science.gov (United States)

    Dhanirama, Danelle; Gronow, Jan; Voulvoulis, Nikolaos

    2012-01-01

    Chemicals of emerging concern (CECs) are frequently used in cosmetic formulations and can potentially reach the environment at concentrations that may cause harm. A methodology was developed to assess over 120 chemicals assembled from product ingredient listings to identify and validate potential CECs in cosmetics, based on Annex XIII of REACH legislation. Ten potential CECs were identified: polydimethylsiloxane, butylated hydroxylanisole (BHA), butylated hydroxytoluene, triclosan, nano titanium dioxide, nano zinc oxide, butylparaben, diethyl phthalate, octinoxate methoxycinnamate and benzophenone. These chemicals were quantified based on their consumption and concentrations in cosmetics and percentage market penetration. The initial predicted environmental concentrations (PEC initial) were estimated to determine their exposure to the environment. With the exception of BHA, the PEC initial highlighted levels of exposure to the environment that triggered the need for further investigation of the chemicals. These chemicals were linked to cosmetics to highlight products with the potential to cause environmental harm. Skin care products had the highest quantities of CECs, with titanium dioxide and zinc oxide nanomaterials being dominant potential contaminants. Further research is required to assess the exposure pathways and fate of these chemicals to determine environmental risks associated with their use and disposal.

  20. A lateral electrophoretic flow diagnostic assay.

    Science.gov (United States)

    Lin, Robert; Skandarajah, Arunan; Gerver, Rachel E; Neira, Hector D; Fletcher, Daniel A; Herr, Amy E

    2015-03-21

    Immunochromatographic assays are a cornerstone tool in disease screening. To complement existing lateral flow assays (based on wicking flow) we introduce a lateral flow format that employs directed electrophoretic transport. The format is termed a "lateral e-flow assay" and is designed to support multiplexed detection using immobilized reaction volumes of capture antigen. To fabricate the lateral e-flow device, we employ mask-based UV photopatterning to selectively immobilize unmodified capture antigen along the microchannel in a barcode-like pattern. The channel-filling polyacrylamide hydrogel incorporates a photoactive moiety (benzophenone) to immobilize capture antigen to the hydrogel without a priori antigen modification. We report a heterogeneous sandwich assay using low-power electrophoresis to drive biospecimen through the capture antigen barcode. Fluorescence barcode readout is collected via a low-resource appropriate imaging system (CellScope). We characterize lateral e-flow assay performance and demonstrate a serum assay for antibodies to the hepatitis C virus (HCV). In a pilot study, the lateral e-flow assay positively identifies HCV+ human sera in 60 min. The lateral e-flow assay provides a flexible format for conducting multiplexed immunoassays relevant to confirmatory diagnosis in near-patient settings.

  1. Development of an analytical method for the determination of photoinitiators used for food packaging materials with potential to migrate into milk.

    Science.gov (United States)

    Sanches-Silva, A; Pastorelli, S; Cruz, J M; Simoneau, C; Castanheira, I; Paseiro-Losada, P

    2008-03-01

    Photoinitiators are used in the curing process during UV printing of food carton labels. The alarm concerning the detection of a photoinitiator, 2-isopropyl thioxanthone (ITX), in food samples packed with cartons printed with UV-cured inks has focused the attention of legislative authorities on the potential migrants from packaging inks into foods. For this reason it is very important to carry out analytical methods for the detection of those compounds in food as potential migrants from packaging. The aim of the present work was to develop a multimethod for the analysis of 6 photoinitiators in milk. The selected photoinitiators were Irgacure 184, benzophenone, Irgacure 651, Irgacure 907, Quantacure ITX, and Quantacure EHA (2-ethylhexyl-4-dimethylaminobenzoate). Milk (10 mL) extraction was carried out by using ammoniac and hexane. The supernatant was evaporated and the residue was redissolved with acetonitrile. Then, the extract was analyzed by HPLC-UV. Calibration lines were carried out over the concentration range of 0.1 to 10 mg/L. The calibration data presented high correlation coefficients (>0.9999). Mean recoveries (n = 6) of the 6 photoinitiators were 83.4% (residual standard deviation = 2.3%) at 0.5 mg/kg and 81.0% (residual standard deviation = 4.6%) at 1 mg/kg. Several milk samples and their respective packaging cartons were analyzed. Results were confirmed by HPLC-mass spectrometry.

  2. Three Novel Lanthanide Metal-Organic Frameworks (Ln-MOFs Constructed by Unsymmetrical Aromatic Dicarboxylatic Tectonics: Synthesis, Crystal Structures and Luminescent Properties

    Directory of Open Access Journals (Sweden)

    Ya-Pan Wu

    2014-09-01

    Full Text Available Three novel Ln(III-based coordination polymers, {[Ln2 (2,4-bpda3 (H2Ox]·yH2O}n (Ln = La (III (1, x = 2, y = 0, Ce (III (2, Pr (III (3, x = 4, y = 1 (2,4-H2bpda = benzophenone-2,4-dicarboxylic acid have been prepared via a solvothermal method and characterized by elemental analysis, IR, and single-crystal X-ray diffraction techniques. Complex 1 exhibits a 3D complicated framework with a new 2-nodal (3,7-connected (42·5 (44·51·66·8 topology. Complexes 2 and 3 are isomorphous, and feature a 3D 4-connected (65·8-CdSO4 network. Moreover, solid-state properties such as thermal stabilities and luminescent properties of 1 and 2 were also investigated. Complex 1 crystallized in a monoclinic space group P21/c with a = 14.800 (3, b = 14.500 (3, c = 18.800 (4 Å, β = 91.00 (3, V = 4033.9 (14 Å3 and Z = 4. Complex 2 crystallized in a monoclinic space group Cc with a = 13.5432 (4, b = 12.9981 (4, c = 25.7567 (11 Å, β = 104.028 (4, V = 1374.16 (7 Å3 and Z = 4.

  3. Inhibitors of testosterone biosynthetic and metabolic activation enzymes.

    Science.gov (United States)

    Ye, Leping; Su, Zhi-Jian; Ge, Ren-Shan

    2011-12-02

    The Leydig cells of the testis have the capacity to biosynthesize testosterone from cholesterol. Testosterone and its metabolically activated product dihydrotestosterone are critical for the development of male reproductive system and spermatogenesis. At least four steroidogenic enzymes are involved in testosterone biosynthesis: Cholesterol side chain cleavage enzyme (CYP11A1) for the conversion of cholesterol into pregnenolone within the mitochondria, 3β-hydroxysteroid dehydrogenase (HSD3B), for the conversion of pregnenolone into progesterone, 17α-hydroxylase/17,20-lyase (CYP17A1) for the conversion of progesterone into androstenedione and 17β-hydroxysteroid dehydrogenase (HSD17B3) for the formation of testosterone from androstenedione. Testosterone is also metabolically activated into more potent androgen dihydrotestosterone by two isoforms 5α-reductase 1 (SRD5A1) and 2 (SRD5A2) in Leydig cells and peripheral tissues. Many endocrine disruptors act as antiandrogens via directly inhibiting one or more enzymes for testosterone biosynthesis and metabolic activation. These chemicals include industrial materials (perfluoroalkyl compounds, phthalates, bisphenol A and benzophenone) and pesticides/biocides (methoxychlor, organotins, 1,2-dibromo-3-chloropropane and prochloraz) and plant constituents (genistein and gossypol). This paper reviews these endocrine disruptors targeting steroidogenic enzymes.

  4. Improvement of the polymer stability by radiation grafting

    International Nuclear Information System (INIS)

    Ranogajec, F.; Mlinac-Misak, M.

    2004-01-01

    Losses of the stabilizer due to extractability or volatility immediately affect the ultimate performance of polymer products. A new approach to increase the persistence of the stabilizer in the final product is to chemically bind it to the polymer backbone. Radiation grafting or crosslinking could be an efficient method for this, when the stabilizer is polymerizable. By a mutual gamma irradiation method photoprotector 2-hydroxy-4-(3-methacryloxy-2-hydroxy-propoxy) benzophenone has been readily grafted to low-density polyethylene in benzene, tetrahydrofuran and methanol solution, respectively. Surface grafting occurs in a methanol solution of stabilizer, while in benzene and tetrahydrofuran solutions of the stabilizer, grafting proceeds more or less in the inner parts of the polymeric film as well. UV stability tests and changes in the mechanical properties of artificially and naturally aged films indicate pronounced protective effect achieved by the grafted stabilizer. Surface grafting is an efficient photostabilization method since the grafted stabilizer is chemically bound to a polymeric surface and in this way the problem of evaporation of blended stabilizers during the prolonged use of polymeric materials is eliminated

  5. Design and implementation of two-dimensional polymer adsorption models: evaluating the stability of Candida antarctica lipase B/solid-support interfaces by QCM-D.

    Science.gov (United States)

    Orski, Sara V; Kundu, Santanu; Gross, Richard; Beers, Kathryn L

    2013-02-11

    A two-dimensional model of a solid-supported enzyme catalyst bead is fabricated on a quartz crystal microbalance with dissipation monitoring (QCM-D) sensor to measure in situ interfacial stability and mechanical properties of Candida antarctica Lipase B (CAL B) under varied conditions relating to ring-opening polymerization. The model was fabricated using a dual photochemical approach, where poly(methyl methacrylate) (PMMA) thin films were cross-linked by a photoactive benzophenone monolayer and blended cross-linking agent. This process produces two-dimensional, homogeneous, rigid PMMA layers, which mimic commercial acrylic resins in a QCM-D experiment. Adsorption of CAL B to PMMA in QCM-D under varied buffer ionic strengths produces a viscoelastic enzyme surface that becomes more rigid as ionic strength increases. The rigid CAL B/PMMA interface demonstrates up to 20% desorption of enzyme with increasing trace water content. Increased polycaprolactone (PCL) binding at the enzyme surface was also observed, indicating greater PCL affinity for a more hydrated enzyme surface. The enzyme layer destabilized with increasing temperature, yielding near complete reversible catalyst desorption in the model.

  6. Novel poly (arylene-ether-ether-ketone)s containing preformed imide unit and pendant long chain alkyl group

    Energy Technology Data Exchange (ETDEWEB)

    Sayyed, Maheboob M. [Department of Chemistry, Solapur University, Pune-Solapur High Way, Kegaon, Solapur 413 255, Maharashtra (India); Maldar, Noormahmad N., E-mail: maldar_nn@rediffmail.co [Department of Chemistry, Solapur University, Pune-Solapur High Way, Kegaon, Solapur 413 255, Maharashtra (India)

    2010-04-15

    The studies were carried out to get preformed imide unit containing PEEKs and Co-PEEKs with pendant long chain alkyl group. Thus two new bisphenols; N,N'-bis (4-hydroxy 2-pentadecyl phenyl) pyromellitimide (HPI) (I) and N,N'-bis (4-hydroxy 2-pentadecyl phenyl 3,3',4,4'-benzophenone tetracarboxylic imide (HBI) (II) containing imide unit, pendant C-15 alkyl substituents were synthesized, characterized by spectral data and polycondensed with 4,4'-difluorobenzophenone (DFB) to yield several PEEK and Co-PEEKs. The polymers were characterized by FTIR, inherent viscosity, solubility, and XRD. The polymers were obtained in good yields and had inherent viscosities up to 0.65 dL/g in NMP. Polymerization of mixture of two bisphenols; [(I) and BPA]; and [(II) and BPA] in various mol%, with DFB gave number of the copolymers viz. Co-PEEK-BPAPI and Co-PEEK-BPABI. Many of the Co-PEEKs had good solubility in polar solvents. The solubility of PEEK containing bulky pendant alkyl substituents did not much improve probably due to simultaneous presence of rigid imide structures. XRD analysis indicated that PEEK and Co-PEEKs were partially crystalline or amorphous depending on the nature and % content of imide-bisphenol. These new PEEK materials can be used as high performance films, coatings, gas separation membranes, in aerospace and nuclear industries.

  7. Novel modification method to prepare crosslinked sulfonated poly(ether ether ketone)/silica hybrid membranes for fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Feng, Shaoguang; Shang, Yuming; Liu, Guoshun; Dong, Wenqi; Xie, Xiaofeng; Xu, Jingming [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Mathur, V.K. [Department of Chemical Engineering, University of New Hampshire, NH 03824 (United States)

    2010-10-01

    Crosslinked organic-inorganic hybrid membranes are prepared from hydroxyl-functionalized sulfonated poly(ether ether ketone) (SPEEK) and various amounts of silica with the aims to improve dimensional stability and methanol resistance. The partially hydroxyl-functionalized SPEEK is prepared by the reduction of some benzophenone moieties of SPEEK into the corresponding benzhydrol moieties which is then reacted with (3-isocyanatopropyl)triethoxysilane (ICPTES) to get a side chained polymer bearing triethoxysilyl groups. These groups are subsequently co-hydrolyzed with tetraethoxysilane (TEOS) and allow the membrane to form a crosslinked network via a sol-gel process. The obtained hybrid membranes with covalent bonds between organic and inorganic phases exhibit much lower methanol swelling ratio and water uptake. With the increase of silica content, the methanol permeability coefficient of the hybrid membranes decreases at first and then increased. At silica content of about 6 wt.%, the methanol permeability coefficient reaches a minimum of 7.15 x 10{sup -7} cm{sup 2} s{sup -1}, a 5-fold decrease compared with that of the pristine SPEEK. Despite the fact that the proton conductivity is decreased to some extent as a result of introduction of the silica, the hybrid membranes with silica content of 4-8 wt.% shows higher selectivity than Nafion117. (author)

  8. Luminescent single-ion magnets from Lanthanoid(III) complexes with monodentate ketone ligands

    Energy Technology Data Exchange (ETDEWEB)

    Kanetomo, Takuya; Ishida, Takayuki, E-mail: takayuki.ishida@uec.ac.jp [Department of Engineering Science, The University of Electro-Communications, Tokyo (Japan)

    2016-02-01

    We synthesized [Ln{sup III}(hfac){sub 3}(H{sub 2}O)(L)] (abbreviated as Ln-L; Ln = Gd, Tb, Eu; L = DTBK (di-t-butyl ketone), BP (benzophenone)), in which the carbonyl oxygen atom was coordinated to the Ln ion center, despite of such bulky substituents. Their crystal structures were determined by means of X-ray diffraction study. Gd-DTBK is completely isomorphous to the di-t-butyl nitroxide derivative and accordingly can be regarded as a model with the ligand spin masked. The ac magnetic susceptibility measurements on Tb-DTBK and -BP showed frequency dependence, characteristic of single-ion magnets. They also displayed photoluminescence in the solid state at room temperature. The quantum yields of the luminescence of Tb-DTBK and -BP (λ{sub ex} = 360 nm) were improved to 57 and 35%, respectively, from that of the starting material [TbI{sup III}(hfac){sub 3}(H{sub 2}O){sub 2}] (28% at λ{sub ex} = 370 nm). Similarly, the quantum yields for Eu-DTBK and -BP were 8 and 15%, respectively, with λ{sub ex} = 400 nm, while that of the starting material [EuI{sup III}(hfac){sub 3}(H{sub 2}O){sub 2}] was 4% at λ{sub ex}=400 nm.

  9. Periodic Trends in the Binding of a Phosphine-Tethered Ketone Ligand to Fe, Co, Ni, and Cu.

    Science.gov (United States)

    Verhoeven, Dide G A; van Wiggen, Maxime A C; Kwakernaak, Joost; Lutz, Martin; Klein Gebbink, Robertus J M; Moret, Marc-Etienne

    2018-04-06

    π-Coordinating ligands are commonly found in intermediate structures in homogeneous catalysis, and are gaining interest as supporting ligands for the development of cooperative catalysts. Herein, we systematically investigate the binding of the ketone group, a strongly accepting π ligand, to mid-to-late metals of the first transition series. To this end, the coordination of 2,2'-bis(diphenylphosphino)benzophenone ( Ph dpbp), which features a ketone moiety flanked by two strongly binding P-donor groups, to Fe, Co, Ni, and Cu was explored. The ketone moiety does not bind to the metal in M II complexes, whereas M I complexes (Fe, Co, Ni) adopt an η 2 (C,O) coordination. A structural and computational investigation of periodic trends in this series was performed. These data suggest that the coordination of the ketone to M I can mostly be described by the resonance extremes of the Dewar-Chatt-Duncanson model, that is, the π complex and the metallaoxacycle extreme, with a possible minor contribution from a ketyl radical resonance structure in the case of the iron complex. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Luminescent single-ion magnets from Lanthanoid(III) complexes with monodentate ketone ligands

    Science.gov (United States)

    Kanetomo, Takuya; Ishida, Takayuki

    2016-02-01

    We synthesized [LnIII(hfac)3(H2O)(L)] (abbreviated as Ln-L; Ln = Gd, Tb, Eu; L = DTBK (di-t-butyl ketone), BP (benzophenone)), in which the carbonyl oxygen atom was coordinated to the Ln ion center, despite of such bulky substituents. Their crystal structures were determined by means of X-ray diffraction study. Gd-DTBK is completely isomorphous to the di-t-butyl nitroxide derivative and accordingly can be regarded as a model with the ligand spin masked. The ac magnetic susceptibility measurements on Tb-DTBK and -BP showed frequency dependence, characteristic of single-ion magnets. They also displayed photoluminescence in the solid state at room temperature. The quantum yields of the luminescence of Tb-DTBK and -BP (λex = 360 nm) were improved to 57 and 35%, respectively, from that of the starting material [TbIIII(hfac)3(H2O)2] (28% at λex = 370 nm). Similarly, the quantum yields for Eu-DTBK and -BP were 8 and 15%, respectively, with λex = 400 nm, while that of the starting material [EuIIII(hfac)3(H2O)2] was 4% at λex=400 nm.

  11. Functionalizing carbon nitride with heavy atom-free spin converters for enhanced 1 O 2 generation

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Wenting; Han, Congcong; Zhang, Qinhua; Zhang, Qinggang; Li, Zhongtao; Gosztola, David J.; Wiederrecht, Gary P.; Wu, Mingbo

    2018-05-01

    advanced photosensitizers for singlet oxygen (1O2) generation. However, the intersystem crossing (ISC) process is quite insufficient in carbon nitride, limiting the 1O2 generation. Here, we report a facile and general strategy to confined benzophenone as a heavy atom-free spin converter dopant in carbon nitride via the facile copolymerization. With proper energy level matching between the heavy atom-free spin converter and various ligands based on carbon nitride precursors, the proper combination can decrease the singlet-triplet energy gap (DEST) and hence generate 1O2 effectively. Due to its significant and selectivity for 1O2 generation, the as-prepared carbon nitride-based photosensitizer shows a high selective photooxidation activity for 1,5-dihydroxy-naphthalene (1,5-DHN). The product yield reached 71.8% after irradiation for 60 min, which was higher than that of cyclometalated PtII complexes (53.6%) in homogeneous photooxidation. This study can broaden the application of carbon nitride in the field of selective heterogeneous photooxidation due to simple operation, low cost, and high efficiency, making it a strong candidate for future industrialization.

  12. UV filters are an environmental threat in the Gulf of Mexico: a case study of Texas coastal zones

    Directory of Open Access Journals (Sweden)

    Hamidreza Sharifan

    2016-10-01

    Full Text Available UV filters are the main ingredients in many cosmetics and personal care products. A significant amount of lipophilic UV filters annually enters the surface water due to large numbers of swimmers and sunbathers. The nature of these compounds cause bioaccumulation in commercial fish, particularly in estuarine areas. Consequently, biomagnification in the food chain will occur. This study estimated the amount of four common UV filters (ethylhexyl methoxycinnamate, EHMC; octocrylene, OC; butyl methoxydibenzoylmethane, BM-DBM; and benzophenone-3, BP3, which may enter surface water in the Gulf of Mexico. Our data analysis was based on the available research data and EPA standards (age classification/human body parts. The results indicated that among the 14 counties in Texas coastal zones, Nueces, with 43 beaches, has a high potential of water contamination through UV filters; EHMC: 477 kg year−1; OC: 318 kg year−1; BM-DBM: 258 kg year−1; and BP by 159 kg year−1. Refugio County, with a minimum number of beaches, indicated the lowest potential of UV filter contamination. The sensitive estuarine areas of Galveston receive a significant amount of UV filters. This article suggests action for protecting Texas estuarine areas and controlling the number of tourists and ecotourism that occurs in sensitive areas of the Gulf of Mexico.

  13. Determination of personal care products and hormones in leachate and groundwater from Polish MSW landfills by ultrasound-assisted emulsification microextraction and GC-MS.

    Science.gov (United States)

    Kapelewska, Justyna; Kotowska, Urszula; Wiśniewska, Katarzyna

    2016-01-01

    Determination of the endocrine disrupting compounds (EDCs) in leachate and groundwater samples from the landfill sites is very important because of the proven harmful effects of these compounds on human and animal organisms. A method combining ultrasound-assisted emulsification microextraction (USAEME) and gas chromatography-mass spectrometry (GC-MS) was developed for simultaneous determination of seven personal care products (PCPs): methylparaben (MP), ethylparaben (EP), propylparaben (PP), buthylparaben (BP), benzophenone (BPh), 3-(4-methylbenzylidene)camphor (4-MBC), N,N-diethyltoluamide (DEET), and two hormones: estrone (E1) and β-estradiol (E2) in landfill leachate and groundwater samples. The limit of detection (LOD)/limit of quantification (LOQ) values in landfill leachate and groundwater samples were in the range of 0.003-0.083/0.009-0.277 μg L(-1) and 0.001-0.015/0.002-0.049 μg L(-1), respectively. Quantitative recoveries and satisfactory precision were obtained. All studied compounds were found in the landfill leachates from Polish municipal solid waste (MSW) landfills; the concentrations were between 0.66 and 202.42 μg L(-1). The concentration of pollutants in groundwater samples was generally below 0.1 μg L(-1).

  14. Reduced Reactivity of Amines against Nucleophilic Substitution via Reversible Reaction with Carbon Dioxide.

    Science.gov (United States)

    Mohammed, Fiaz S; Kitchens, Christopher L

    2015-12-23

    The reversible reaction of carbon dioxide (CO₂) with primary amines to form alkyl-ammonium carbamates is demonstrated in this work to reduce amine reactivity against nucleophilic substitution reactions with benzophenone and phenyl isocyanate. The reversible formation of carbamates has been recently exploited for a number of unique applications including the formation of reversible ionic liquids and surfactants. For these applications, reduced reactivity of the carbamate is imperative, particularly for applications in reactions and separations. In this work, carbamate formation resulted in a 67% reduction in yield for urea synthesis and 55% reduction for imine synthesis. Furthermore, the amine reactivity can be recovered upon reversal of the carbamate reaction, demonstrating reversibility. The strong nucleophilic properties of amines often require protection/de-protection schemes during bi-functional coupling reactions. This typically requires three separate reaction steps to achieve a single transformation, which is the motivation behind Green Chemistry Principle #8: Reduce Derivatives. Based upon the reduced reactivity, there is potential to employ the reversible carbamate reaction as an alternative method for amine protection in the presence of competing reactions. For the context of this work, CO₂ is envisioned as a green protecting agent to suppress formation of n-phenyl benzophenoneimine and various n-phenyl-n-alky ureas.

  15. Nuclear Energy Gradients for Internally Contracted Complete Active Space Second-Order Perturbation Theory: Multistate Extensions.

    Science.gov (United States)

    Vlaisavljevich, Bess; Shiozaki, Toru

    2016-08-09

    We report the development of the theory and computer program for analytical nuclear energy gradients for (extended) multistate complete active space perturbation theory (CASPT2) with full internal contraction. The vertical shifts are also considered in this work. This is an extension of the fully internally contracted CASPT2 nuclear gradient program recently developed for a state-specific variant by us [MacLeod and Shiozaki, J. Chem. Phys. 2015, 142, 051103]; in this extension, the so-called λ equation is solved to account for the variation of the multistate CASPT2 energies with respect to the change in the amplitudes obtained in the preceding state-specific CASPT2 calculations, and the Z vector equations are modified accordingly. The program is parallelized using the MPI3 remote memory access protocol that allows us to perform efficient one-sided communication. The optimized geometries of the ground and excited states of a copper corrole and benzophenone are presented as numerical examples. The code is publicly available under the GNU General Public License.

  16. Benzoylphenyl thiocyanates are new, effective inhibitors of the mycobacterial resuscitation promoting factor B protein

    Directory of Open Access Journals (Sweden)

    Galina R. Demina

    2017-11-01

    Full Text Available Abstract Background Resuscitation promoting factors (Rpfs are the proteins involved in the process of reactivation of the dormant cells of mycobacteria. Recently a new class of nitrophenylthiocyanates (NPTs, capable of inhibiting the biological and enzymatic activities of Rpfs has been discovered. In the current study the inhibitory properties of the compounds containing both nitro and thiocyanate groups alongside with the compounds with the modified number and different spatial location of the substituents are compared. Methods New benzoylphenyl thiocyanates alongside with nitrophenylthiocyanates were tested in the enzymatic assay of bacterial peptidoglycan hydrolysis as well as against strains of several actinobacteria (Mycobacterium smegmatis, Mycobacterium tuberculosis on in-lab developed models of resuscitation of the dormant forms. Results Introduction of the additional nitro and thiocyanate groups to the benzophenone scaffold did not influence the inhibitory activity of the compounds. Removal of the nitro groups analogously did not impair the functional properties of the molecules. Among the tested compounds two molecules without nitro group: 3-benzoylphenyl thiocyanate and 4-benzoylphenyl thiocyanate demonstrated the maximum activity in both enzymatic assay (inhibition of the Rpf-mediated peptidoglycan hydrolysis and in the resuscitation assay of the dormant M. tuberculosis cells. Conclusions The current study demonstrates dispensability of the nitro group in the NPT’s structure for inhibition of the enzymatic and biological activities of the Rpf protein molecules. These findings provide new prospects in anti-TB drug discovery especially in finding of molecular scaffolds effective for the latent infection treatment.

  17. Photochemical reaction of 2-(3-benzoylphenyl)propionic acid (ketoprofen) with basic amino acids and dipeptides.

    Science.gov (United States)

    Suzuki, Tadashi; Shinoda, Mio; Osanai, Yohei; Isozaki, Tasuku

    2013-08-22

    Photoreaction of 2-(3-benzoylphenyl)propionic acid (ketoprofen, KP) with basic amino acids (histidine, lysine, and arginine) and dipeptides (carnosine and anserine) including a histidine moiety in phosphate buffer solution (pH 7.4) has been investigated with transient absorption spectroscopy. With UV irradiation KP(-) gave rise to a carbanion through a decarboxylation reaction, and the carbanion easily abstracted a proton from the surrounding molecule to yield a 3-ethylbenzophenone ketyl biradical (EBPH). The dipeptides as well as the basic amino acids were found to accelerate the proton transfer reaction whereas alanine and glycine had no effect on the reaction, revealing that these amino acids having a protonated side chain act as a proton donor. The formation quantum yield of EBPH was estimated to be fairly large by means of an actinometrical method with benzophenone, and the bimolecular reaction rate constant for the proton transfer between the carbanion and the protonated basic amino acids or the protonated dipeptides was successfully determined. It has become apparent that the bimolecular reaction rate constant for the proton transfer depended on the acid dissociation constant for the side chain of the amino acids for the first time. This reaction mechanism was interpreted by difference of the heat of reaction for each basic amino acid based on the thermodynamical consideration. These results strongly suggest that the side chain of the basic amino acid residue in protein should play an important role for photochemistry of KP in vivo.

  18. Associations between maternal phenol and paraben urinary biomarkers and maternal hormones during pregnancy: A repeated measures study.

    Science.gov (United States)

    Aker, Amira M; Johns, Lauren; McElrath, Thomas F; Cantonwine, David E; Mukherjee, Bhramar; Meeker, John D

    2018-01-20

    A number of phenols and parabens are added to consumer products for a variety of functions, and have been found at detectable levels in the majority of the U.S. Among other functions, thyroid hormones are essential in fetal neurodevelopment, and could be impacted by the endocrine disrupting effects of phenols and parabens. The present study investigated the association between ten maternal urinary phenol and paraben biomarkers (bisphenol S, triclosan, triclocarban, benzophenone-3, 2,4-dichlorophenol, 2,5-dichlorophenol, and ethyl, butyl, methyl and propyl paraben) and four plasma thyroid hormones in 439 pregnant women in a case-control sample nested within a cohort study based in Boston, MA. Urine and blood samples were collected from up to four visits during pregnancy (median weeks of gestation at each visit: Visit 1: 9.64, Visit 2: 17.9, Visit 3: 26.0, Visit 4: 35.1). Linear mixed models were constructed to take into account the repeated measures jointly, followed by multivariate linear regression models stratified by gestational age to explore potential windows of susceptibility. We observed decreased total triiodothyronine (T3) in relation to an IQR increase in benzophenone-3 (percent change [%Δ] = -2.07; 95% confidence interval [CI] = -4.16, 0.01), butyl paraben (%Δ = -2.76; 95% CI = -5.25, -0.26) and triclosan (%Δ = -2.53; 95% CI = -4.75, -0.30), and triclocarban at levels above the LOD (%Δ = -5.71; 95% CI = -10.45, -0.97). A 2.41% increase in T3 was associated with an IQR increase in methyl paraben (95% CI = 0.58, 4.24). We also detected a negative association between free thyroxine (FT4) and propyl paraben (%Δ = -3.14; 95% CI = -6.12, -0.06), and a suggestive positive association between total thyroxine (T4) and methyl paraben (%Δ = 1.19; 95% CI = -0.10, 2.47). Gestational age-specific multivariate regression analyses showed that the magnitude and direction of some of the observed associations were

  19. Coordination and reductive chemistry of tetraphenylborate complexes of trivalent rare earth metallocene cations, [(C5Me5)2Ln][(μ-Ph)2BPh2].

    Science.gov (United States)

    MacDonald, Matthew R; Ziller, Joseph W; Evans, William J

    2011-05-02

    The reactivity of the tetraphenylborate salts of the rare earth metallocene cations [(C(5)Me(5))(2)Ln][(μ-Ph)(2)BPh(2)] (Ln = Y, 1; Sm, 2) has been investigated with substrates that undergo reduction with f element complexes to probe metal-substrate interactions prior to reduction. Results with NaN(3), 1-adamantyl azide, acetone, benzophenone, phenanthroline, pyridine, azobenzene, and phenazine are described. Not only were coordination complexes isolated, but substrate reduction by (BPh(4))(-) was also observed. Complex 1 reacts with NaN(3) to form the azide [(C(5)Me(5))(2)YN(3)](x), 3, which crystallizes as [(C(5)Me(5))(2)Y(μ-N(3))](3), 4, when obtained from 1 and 1-adamantyl azide. The samarium analogue [(C(5)Me(5))(2)SmN(3)](x), 5, can be produced similarly from 2 and NaN(3) and crystallized from MeCN as [(C(5)Me(5))(2)Sm(NCMe)(μ-N(3))](3), 6, and {[(C(5)Me(5))(2)Sm(μ-N(3))][(C(5)Me(5))(2)Sm(NCMe)(μ-N(3))]}(n), 7. Complexes 1 and 2 react with stoichiometric amounts of acetone and benzophenone to form the ketone adducts [(C(5)Me(5))(2)Ln(OCMe(2))(2)][BPh(4)] (Ln = Y, 8; Sm, 9) and [(C(5)Me(5))(2)Ln(OCPh(2))(2)][BPh(4)] (Ln = Y, 10; Sm, 11), respectively. Phenanthroline (phen) coordinates to 1 to form [(C(5)Me(5))(2)Y(phen)][BPh(4)], 12. Complexes 1 and 2 react with pyridine (py) to form [(C(5)Me(5))(2)Ln(py)(2)][BPh(4)], (Ln = Y, 13; Sm, 14). Complexes 3, 8, 10, and 12 can also be made from the solvated cation [(C(5)Me(5))(2)Y(THF)(2)][BPh(4)]. The reaction of 1 with PhNNPh yields the diamagnetic adduct [(C(5)Me(5))(2)Y(PhNNPh)][BPh(4)], 15, which transforms in benzene to the radical anion complex (C(5)Me(5))(2)Y(PhNNPh), 16, via a one electron reduction by (BPh(4))(-). Complex 1 similarly reacts with phenazine (phz) to produce the first rare earth phenazine radical anion complex {[(C(5)Me(5))(2)Y](2)(phz)}{BPh(4)}, 17. Further reduction of phenazine by (BPh(4))(-) in 17 yields [(C(5)Me(5))(2)Y](2)(phz), 18, which contains the common (phz)(2-) dianion. The

  20. A multi-defense strategy: Enhancing bactericidal activity of a medical grade polymer with a nitric oxide donor and surface-immobilized quaternary ammonium compound.

    Science.gov (United States)

    Pant, Jitendra; Gao, Jing; Goudie, Marcus J; Hopkins, Sean P; Locklin, Jason; Handa, Hitesh

    2017-08-01

    Although the use of biomedical devices in hospital-based care is inevitable, unfortunately, it is also one of the leading causes of the nosocomial infections, and thus demands development of novel antimicrobial materials for medical device fabrication. In the current study, a multi-defense mechanism against Gram-positive and Gram-negative bacteria is demonstrated by combining a nitric oxide (NO) releasing agent with a quaternary ammonium antimicrobial that can be covalently grafted to medical devices. Antibacterial polymeric composites were fabricated by incorporating an NO donor, S-nitroso-N-acetyl-penicillamine (SNAP) in CarboSil® polymer and top coated with surface immobilized benzophenone based quaternary ammonium antimicrobial (BPAM) small molecule. The results suggest that SNAP and BPAM individually have a different degree of toxicity towards Gram-positive and Gram-negative bacteria, while the SNAP-BPAM combination is effective in reducing both types of adhered viable bacteria equally well. SNAP-BPAM combinations reduced the adhered viable Pseudomonas aeruginosa by 99.0% and Staphylococcus aureus by 99.98% as compared to the control CarboSil films. Agar diffusion tests demonstrate that the diffusive nature of NO kills bacteria beyond the direct point of contact which the non-leaching BPAM cannot achieve alone. This is important for potential application in biofilm eradication. The live-dead bacteria staining shows that the SNAP-BPAM combination has more attached dead bacteria (than live) as compared to the controls. The SNAP-BPAM films have increased hydrophilicity and higher NO flux as compared to the SNAP films useful for preventing blood protein and bacterial adhesion. Overall the combination of SNAP and BPAM imparts different attributes to the polymeric composite that can be used in the fabrication of antimicrobial surfaces for various medical device applications. A significant increase in the biomedical device related infections (BDRIs), inability of

  1. Inhibition of Saccharomyces cerevisiae Pdr5p by a natural compound extracted from Brazilian Red Propolis

    Directory of Open Access Journals (Sweden)

    Cinzia Lotti

    2011-08-01

    Full Text Available Multidrug resistance of cancer cells and pathogenic microorganisms leading to the treatment failure of some forms of cancer or life-threatening bacterial or fungal infections is often caused by the overexpression of multidrug efflux pumps belonging to the ATP-binding cassette transporters superfamily. The multidrug resistance of fungal cells often involves the overexpression of efflux pumps belonging to the pleiotropic drug resistance (PDR family of ABC transporters. Possibly the best-studied fungal PDR transporter is the multidrug resistance transporter Pdr5p of Saccharomyces cerevisiae. Some research groups have been searching for new inhibitors of these efflux pumps in order to alleviate resistance. Natural products are a great source for the discovery of new compounds with biological activity. Propolis is a complex resinous material collected by honeybees from exudates and buds of certain plant sources and this material is thought to serve as a defense substance for bee hives. Propolis is widely used in traditional medicine and is reported to have a broad spectrum of pharmacological properties. Literature reported some biological functionalities of propolis, such as antibacterial, antiviral, fungicidal, anti-inflammatory and anti-carcinogenic activities. The chemical composition of propolis is qualitatively and quantitatively variable. Components isolated from methanolic extract of red Brazilian propolis (Alagoas, Northeast of Brazil are isoflavonoids (including pterocarpans, isoflavans, isoflavones, flavanones and polyprenylated benzophenones. In this work we demonstrated the effects of five different isolated compounds on the ATPase activity of Pdr5p. Out of all five substances tested, only BRP-1 was able to completely abolish the enzymatic activity while others worked as positive modulators of the enzyme activity. BRP-1also inhibited the efflux of Rhodamine 6G from yeast cells overexpressing Pdr5p. Taken together, these results

  2. Conformational Change in the Mechanism of Inclusion of Ketoprofen in β-Cyclodextrin: NMR Spectroscopy, Ab Initio Calculations, Molecular Dynamics Simulations, and Photoreactivity.

    Science.gov (United States)

    Guzzo, T; Mandaliti, W; Nepravishta, R; Aramini, A; Bodo, E; Daidone, I; Allegretti, M; Topai, A; Paci, M

    2016-10-11

    Inclusion of drugs in cyclodextrins (CDs) is a recognized tool for modifying several properties such as solubility, stability, bioavailability, and so on. The photoreactive behavior of the β-CD/ketoprofen (KP) complex upon UV exposure showed a significant increase in photodecarboxylation, whereas the secondary degradation products by hydroxylation of the benzophenone moiety were inhibited. The results may account for an improvement of KP photophysical properties upon inclusion, thus better fostering its topical use. To correlate the structural details of the inclusion with these results, an NMR spectroscopic study of KP upon inclusion in β-CD was performed. Effects of the magnetically anisotropic centers of KP, changing their orientations upon inclusion and giving chemical shift variations, were specifically correlated with the results of the molecular dynamic simulations and ab initio calculations. In the large variety of papers focusing on the structural analysis of β-CD complexes, this work represents one of the few examples in which a detailed analysis of these simultaneous upfield-downfield NMR shifts of the same aromatic molecule upon inclusion is reported. Interestingly, the results demonstrate that the observed upfield and downfield shifts upon inclusion are not related to any direct magnetic role of β-CD. The conformational change of KP upon the inclusion process consists of a slight reduction in the angle between the two phenyl rings and in a remarkable reduction in the mobility of the carboxyl group, the latter being one of the main contributions to the NMR resonance shifts. These structural details help in understanding the features of the inclusion complex and, eventually, the driving force for its formation.

  3. Development of palm oil-based UV-curable epoxy acrylate and urethane acrylate resins for wood coating application

    Science.gov (United States)

    Tajau, Rida; Ibrahim, Mohammad Izzat; Yunus, Nurulhuda Mohd; Mahmood, Mohd Hilmi; Salleh, Mek Zah; Salleh, Nik Ghazali Nik

    2014-02-01

    The trend of using renewable sources such as palm oil as raw material in radiation curing is growing due to the demand from the market to produce a more environmental friendly product. In this study, the radiation curable process was done using epoxy acrylate and urethane acrylate resins which are known as epoxidised palm olein acrylate (EPOLA) and palm oil based urethane acrylate (POBUA), respectively. The purpose of the study was to investigate curing properties and the application of this UV-curable palm oil resins for wood coating. Furthermore, the properties of palm oil based coatings are compared with the petrochemical-based compound such as ebecryl (EB) i.e. EB264 and EB830. From the experiment done, the resins from petrochemical-based compounds resulted higher degree of crosslinking (up to 80%) than the palm oil based compounds (up to 70%), where the different is around 10-15%. The hardness property from this two type coatings can reached until 50% at the lower percentage of the oligomer. However, the coatings from petrochemical-based have a high scratch resistance as it can withstand at least up to 3.0 Newtons (N) compared to the palm oil-based compounds which are difficult to withstand the load up to 1.0 N. Finally, the test on the rubber wood substrate showed that the coatings containing benzophenone photoinitiator give higher adhesion property and their also showed a higher glosiness property on the glass substrate compared to the coatings containing irgacure-819 photoinitiator. This study showed that the palm oil coatings can be a suitable for the replacement of petrochemicals compound for wood coating. The palm oil coatings can be more competitive in the market if the problems of using high percentage palm oil oligomer can be overcome as the palm oil price is cheap enough.

  4. Divide and Conquer May Not Be the Optimal Approach to Retain the Desirable Estrogenic Attributes of the Cyclopia Nutraceutical Extract, SM6Met.

    Directory of Open Access Journals (Sweden)

    M Mortimer

    Full Text Available The genus Cyclopia, an indigenous South African fynbos plant used to prepare honeybush tea, contains phytoestrogenic compounds. An extract from C. subternata, SM6Met, displays three desirable estrogenic attributes for future development of a phytoestrogenic nutraceutical, namely, ERα antagonism, ERβ agonism, and also antagonism of E2-induced breast cancer cell proliferation. Activity-guided fractionation of SM6Met was used in an attempt to isolate and identify compounds conferring the desirable estrogenic profile to SM6Met. Initial liquid-liquid fractionation of SM6Met yielded a polar fraction (PF and a non-polar fraction (NPF, with the desirable estrogenic attributes retained in the NPF. Subsequent high performance counter-current chromatography (HPCCC fractionation of the NPF yielded three fractions (F1-F3. Interestingly, the fractions revealed separation of the previously demonstrated positive estrogenic attributes of the NPF into separate fractions, with F1 and F2 acting as ERα antagonists, only F2 inducing antagonism of E2-induced breast cancer cell proliferation and only F3 retaining robust ERβ agonist activity. In terms of major polyphenols, quantitative HPLC and liquid chromatography tandem mass spectrometry (LC-MS/MS indicated that HPCCC fractionation resulted in a divergence of polyphenolic classes, with F1 emerging as the dihydrochalcone-rich fraction and F2 as the flavanone- and benzophenone-rich fraction, while the xanthones, flavones and phenolic acids were retained in F3. F3 was re-engineered into F3R by reassembling the major polyphenols identified in the fraction. F3R could, however, not replicate the effect of F3. In conclusion, although activity-guided fractionation results suggest that retention of all the desirable estrogenic attributes of the original SM6Met in one fraction is not an attainable goal, fractionation is a useful tool to enhance specific desirable estrogenic attributes.

  5. Fate of the sunscreen compound oxybenzone in Cyperus alternifolius based hydroponic culture: Uptake, biotransformation and phytotoxicity.

    Science.gov (United States)

    Chen, Feiran; Huber, Christian; Schröder, Peter

    2017-09-01

    Oxybenzone (OBZ), a common ingredient in sunscreens and personal care products, has been frequently detected in effluents from municipal wastewater treatment plants and also in surface waters. OBZ is an emerging contaminant due to its adverse impacts on marine/aquatic ecosystems. To investigate the removal and degradation capacity of phytotreatment for OBZ, the common wetland plant species Cyperus alternifolius L. was exposed to this compound at 5, 25 and 50 μM for 120 h, respectively. Continuous uptake by roots and accumulation in plant tissues was observed over the exposure time, and depletion of spiked OBZ from the aqueous medium exceeded 73.9 ± 9.1% after 120 h. Similar to its fate in mammalian cells, OBZ is activated in a phase I reaction resulting in the hydroxylated metabolite 2,4-dihydroxybenzophenone (DHB). Independently, two phase II metabolites were identified as oxybenzone-glucoside (OBZ-Glu) and oxybenzone-(6-O-malonyl)-glucoside (OBZ-Mal-Glu) by LC-MS/MS. Formation of these metabolites increased over the experimental period. To our knowledge this is the first time that DHB, OBZ-Glu and OBZ-Mal-Glu are shown to be formed in higher plant tissues. Furthermore, plant defense systems-antioxidative enzymes (SOD, CAT, APOX and POX) were found to be elevated to counteract stress caused by exposure to OBZ. This study presents the huge potential of aquatic plants to cope with benzophenone type UV filters in contaminated water bodies. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Development of palm oil-based UV-curable epoxy acrylate and urethane acrylate resins for wood coating application

    International Nuclear Information System (INIS)

    Rida Tajau; Nurulhuda Mohd Yunus; Mohd Hilmi Mahmood; Mek Zah Salleh; Nik Ghazali Nik Salleh

    2013-01-01

    Full-text: The trend of using renewable sources such as palm oil as raw material in radiation curing is growing due to the demand from the market to produce a more environmental friendly product. In this study, the radiation curable process was done using epoxy acrylate and urethane acrylate resins which are known as epoxidized palm olein acrylate (EPOLA) and palm oil based urethane acrylate (POBUA), respectively. The purpose of the study was to investigate curing properties and the application of this UV-curable palm oil resins for wood coating. Furthermore, the properties of palm oil based coatings are compared with the petrochemical-based compound such as ebecryl (EB) for example EB264 and EB830. From the experiment done, the resins from petrochemical-based compounds resulted higher degree of crosslinking (up to 80 %) than the palm oil based compounds (up to 70 %), where the different is around 10-15 %. The hardness property from this two type coatings can reached until 50 % at the lower percentage of the oligomer. However, the coatings from petrochemical-based have a high scratch resistance as it can withstand at least up to 3.0 Newton's (N) compared to the palm oil-based compounds which are difficult to withstand the load up to 1.0 N. Finally, the test on the rubber wood substrate showed that the coatings containing benzophenone photo initiator give higher adhesion property and their also showed a higher glossiness property on the glass substrate compared to the coatings containing irgacure-819 photo initiator. This study showed that the palm oil coatings can be a suitable for the replacement of petrochemicals compound for wood coating. The palm oil coatings can be more competitive in the market if the problems of using high percentage palm oil oligomer can be overcome as the palm oil price is cheap enough. (author)

  7. Development of palm oil-based UV-curable epoxy acrylate and urethane acrylate resins for wood coating application

    International Nuclear Information System (INIS)

    Tajau, Rida; Mahmood, Mohd Hilmi; Salleh, Mek Zah; Salleh, Nik Ghazali Nik; Ibrahim, Mohammad Izzat; Yunus, Nurulhuda Mohd

    2014-01-01

    The trend of using renewable sources such as palm oil as raw material in radiation curing is growing due to the demand from the market to produce a more environmental friendly product. In this study, the radiation curable process was done using epoxy acrylate and urethane acrylate resins which are known as epoxidised palm olein acrylate (EPOLA) and palm oil based urethane acrylate (POBUA), respectively. The purpose of the study was to investigate curing properties and the application of this UV-curable palm oil resins for wood coating. Furthermore, the properties of palm oil based coatings are compared with the petrochemical-based compound such as ebecryl (EB) i.e. EB264 and EB830. From the experiment done, the resins from petrochemical-based compounds resulted higher degree of crosslinking (up to 80%) than the palm oil based compounds (up to 70%), where the different is around 10-15%. The hardness property from this two type coatings can reached until 50% at the lower percentage of the oligomer. However, the coatings from petrochemical-based have a high scratch resistance as it can withstand at least up to 3.0 Newtons (N) compared to the palm oil-based compounds which are difficult to withstand the load up to 1.0 N. Finally, the test on the rubber wood substrate showed that the coatings containing benzophenone photoinitiator give higher adhesion property and their also showed a higher glosiness property on the glass substrate compared to the coatings containing irgacure-819 photoinitiator. This study showed that the palm oil coatings can be a suitable for the replacement of petrochemicals compound for wood coating. The palm oil coatings can be more competitive in the market if the problems of using high percentage palm oil oligomer can be overcome as the palm oil price is cheap enough

  8. Associations between urinary phenol and paraben concentrations and markers of oxidative stress and inflammation among pregnant women in Puerto Rico.

    Science.gov (United States)

    Watkins, Deborah J; Ferguson, Kelly K; Anzalota Del Toro, Liza V; Alshawabkeh, Akram N; Cordero, José F; Meeker, John D

    2015-03-01

    Phenols and parabens are used in a multitude of consumer products resulting in ubiquitous human exposure. Animal and in vitro studies suggest that exposure to these compounds may be related to a number of adverse health outcomes, as well as potential mediators such as oxidative stress and inflammation. We examined urinary phenol (bisphenol A (BPA), triclosan (TCS), benzophenone-3 (BP-3), 2,4-dichlorophenol (24-DCP), 2,5-dichlorophenol (25-DCP)) and paraben (butyl paraben (B-PB), methyl paraben (M-PB), propyl paraben (P-PB)) concentrations measured three times during pregnancy in relation to markers of oxidative stress and inflammation among participants in the Puerto Rico Testsite for Exploring Contamination Threats (PROTECT) project. Serum markers of inflammation (c-reactive protein (CRP), IL-1β, IL-6, IL-10, and tumor necrosis factor-α (TNF-α)) were measured twice during pregnancy (n=105 subjects, 187 measurements) and urinary markers of oxidative stress (8-hydroxydeoxyguanosine (OHdG) and isoprostane) were measured three times during pregnancy (n=54 subjects, 146 measurements). We used linear mixed models to assess relationships between natural log-transformed exposure and outcome biomarkers while accounting for within individual correlation across study visits. After adjustment for urinary specific gravity, study visit, maternal pre-pregnancy BMI, and maternal education, an interquartile range (IQR) increase in urinary BPA was associated with 21% higher OHdG (p=0.001) and 29% higher isoprostane (p=0.0002), indicating increased oxidative stress. The adjusted increase in isoprostane per IQR increase in marker of exposure was 17% for BP-3, 27% for B-PB, and 20% for P-PB (all pparabens, and TCS during pregnancy may be related to oxidative stress and inflammation, potential mechanisms by which exposure to these compounds may influence birth outcomes and other adverse health effects, but additional research is needed. Copyright © 2014 Elsevier GmbH. All rights

  9. Antimicrobial and antiproliferative activities of stingless bee Melipona scutellaris geopropolis

    Science.gov (United States)

    2013-01-01

    Background Geopropolis is a type of propolis containing resin, wax, and soil, collected by threatened stingless bee species native to tropical countries and used in folk medicine. However, studies concerning the biological activity and chemical composition of geopropolis are scarce. In this study, we evaluated the antimicrobial and antiproliferative activity of the ethanolic extract of geopropolis (EEGP) collected by Melipona scutellaris and its bioactive fraction against important clinical microorganisms as well as their in vitro cytotoxicity and chemical profile. Methods The antimicrobial activity of EEGP and fractions was examined by determining their minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) against six bacteria strains as well as their ability to inhibit Streptococcus mutans biofilm adherence. Total growth inhibition (TGI) was chosen to assay the antiproliferative activity of EEGP and its bioactive fraction against normal and cancer cell lines. The chemical composition of M. scutellaris geopropolis was identified by reversed-phase high-performance liquid chromatography and gas chromatography–mass spectrometry. Results EEGP significantly inhibited the growth of Staphylococcus aureus strains and S. mutans at low concentrations, and its hexane fraction (HF) presented the highest antibacterial activity. Also, both EEGP and HF inhibited S. mutans biofilm adherence (p HF demonstrated selectivity at low concentrations. The chemical analyses performed suggest the absence of flavonoids and the presence of benzophenones as geopropolis major compounds. Conclusions The empirical use of this unique type of geopropolis by folk medicine practitioners was confirmed in the present study, since it showed antimicrobial and antiproliferative potential against the cancer cell lines studied. It is possible that the major compounds found in this type of geopropolis are responsible for its properties. PMID:23356696

  10. Improvement of polymer stability by radiation grafting

    International Nuclear Information System (INIS)

    Ranogajec, F.; Mlinac-Misak, M.

    1999-01-01

    Losses of the stabilizer due to extractability or volatility immediately affect ultimate performance of polymer product. A new approach to increase the persistence of the stabilizer in the final product is to chemically bind it to the polymer backbone. Radiation grafting or crosslinking could be an efficient method for this, when the stabilizer is polymerizable. By a mutual gamma irradiation method, photoprotector 2-hydroxy-4-(3-methacryloxy-2- hydroxy-propoxy) benzophenone (HMB) has been readily grafted to low density polyethylene (LDPE) in benzene, tetrahydrofuran and methanol solution, respectively. Surface grafting occurs in a methanol solution of stabilizer, while in benzene and tetrahydrofuran solutions of stabilizer, grafting proceeds more or less in the inner parts of the polymeric film as well. The grafted LDPE film in methanol and tetrahydrofuran (containing 1 w/w % of grafted HMB), 1 w/w % blended HMB with LDPE and nongrafted LDPE film, were all exposed to accelerated aging and natural weathering and their spectral changes, expressed by the carbonyl index, were then compared. The change of elongation at break and tensile strength were measured in the course of aging. UV stability tests on aged films and change in mechanical properties indicate a pronounced protective effect achieved by grafted stabilizer. Grafting in methanol solution appears to be an efficient photostabilization treatment and the most economical with respect to the consumption of monomer, the grafting yield being less than 0.5%. Surface grafting is an efficient photostabilization method since grafted stabilizer is chemically bound to a polymeric surface and in this way the problem of evaporation of blended stabilizers during the prolonged use of polymeric materials is eliminated. (author)

  11. Ecotoxicological risk assessment and seasonal variation of some pharmaceuticals and personal care products in the sewage treatment plant and surface water bodies (lakes).

    Science.gov (United States)

    Archana, G; Dhodapkar, Rita; Kumar, Anupama

    2017-08-10

    This paper reports the seasonal variation and environmental quality control data for five fingerprint pharmaceuticals and personal care products (PPCPs) (acetaminophen ciprofloxacin, caffeine, irgasan and benzophenone) in the influent and the effluent of the sewage treatment plant (STP) and surface water bodies (six major lakes) in and around Nagpur, one of the "A class city" in the central India over a period of 1 year. The target compounds were analysed using developed offline solid-phase extraction (SPE) coupled with reversed phase high-performance liquid chromatography (RP-HPLC-PDA) method. All the five PPCPs were found in the influent, whereas four were found in the effluent of the STP. However, in the surface water bodies, three PPCPs were detected in all the seasons. Above PPCPs were present in the concentration range of 1-174 μg L -1 in the surface water bodies, 12-373 μg L -1 in the influent and 11-233 μg L -1 in the effluent of the STP. Amongst the five PPCPs, caffeine was found to be in higher concentration as compared to others. The seasonal trends indicate higher concentrations of PPCPs in summer season and lowest in the rainy season. Additionally, physico-chemical characterisations (inorganic and organic parameters) of the collected samples were performed to access the anthropogenic pollution. Ecotoxicological risk assessment was done to appraise the degree of toxicity of the targeted compounds. Hazard quotient (HQ) values were found to be < 1 indicating no adverse effect on the targeted organism.

  12. Endocrine disruptors in food contact materials; is there a health threat?

    Science.gov (United States)

    Cwiek-Ludwicka, Kazimiera; Ludwicki, Jan K

    2014-01-01

    Food Contact Materials (FCMs) are a major source of endocrine disrupting chemical substances (EDCs), thus forming an important part of human exposure to these compounds, to which this article is addressed. The potential impact of such exposures on endocrine function, and thereby health outcomes, requires scientifically valid evidence so that appropriate risk management decisions can be taken to diminish human exposure, particularly in vulnerable population groups like infants and small children. Relevant aspects of exposure assessment are discussed based on testing migration of EDCs from FCMs, together with the different approaches so used. The specific migration testing determines whether limits for defined substances are met. However not all EDCs present in the leachate may be found by these means. In fact, the chances of detecting EDCs in the food simulant (leachate) are improved when it is subjected the relevant biological testing, thus helping to provide improved protection against these chemical substances. Nevertheless, official controls and risk management decisions do not necessarily take such testing into account, as the relevant legislation is based on specific migration limits that may be easily quantified and addressed in the risk management process. Elucidating the link between observed endocrine activity and any toxic effects so arising, is complicated by the complexity of endocrine interrelationships coupled with relatively limited sensitivity of toxicological tests. Any risk assessment implies a rather high uncertainty and should include also any cumulative effects. This review discusses the effects of the EDCs like bisphenol A, phthalates and benzophenone found in FCMs. In addition, the approaches from the USA and EU for systematically evaluating man-made EDCs in the environment are also considered, including appropriate prioritisation criteria.

  13. A comprehensive scientific overview of Garcinia cambogia.

    Science.gov (United States)

    Semwal, Ruchi Badoni; Semwal, Deepak Kumar; Vermaak, Ilze; Viljoen, Alvaro

    2015-04-01

    The fruit rind of Garcinia gummi-gutta, commonly known as Garcinia cambogia (syn.), is extensively used traditionally as a flavourant in fish curries due to its sharp sour taste. Additional ethnobotanical uses include its use as a digestive and a traditional remedy to treat bowel complaints, intestinal parasites and rheumatism. This small fruit, reminiscent of a pumpkin in appearance, is currently most popularly used and widely advertised as a weight-loss supplement. Studies have shown that the extracts as well as (-)-hydroxycitric acid (HCA), a main organic acid component of the fruit rind, exhibited anti-obesity activity including reduced food intake and body fat gain by regulating the serotonin levels related to satiety, increased fat oxidation and decreased de novo lipogenesis. HCA is a potent inhibitor of adenosine triphosphate-citrate lyase, a catalyst for the conversion process of citrate to acetyl-coenzyme A, which plays a key role in fatty acid, cholesterol and triglycerides syntheses. The crude extract or constituents from the plant also exerted hypolipidaemic, antidiabetic, anti-inflammatory, anticancer, anthelmintic, anticholinesterase and hepatoprotective activities in in vitro and in vivo models. Phytochemical studies of various plant parts revealed the presence of mainly xanthones (e.g. carbogiol) and benzophenones (e.g. garcinol) together with organic acids (e.g. HCA) and amino acids (e.g. gamma aminobutyric acid). Currently, a large number of G. cambogia/HCA dietary supplements for weight management are being sold although the possible toxicity associated with the regular use of these supplements has raised concerns. In most cases, complaints have been related to multicomponent formulations and at this stage G. cambogia has not been confirmed as the potentially toxic culprit. This review presents a scientific overview of G. cambogia with reference to relevant botanical aspects, ethnobotanical uses, phytochemistry and biological activity as well as

  14. People with diabetes, respiratory, liver or mental disorders, higher urinary antimony, bisphenol A, or pesticides had higher food insecurity: USA NHANES, 2005-2006.

    Science.gov (United States)

    Shiue, Ivy

    2016-01-01

    This study was aimed to examine the prevalence of food insecurity and what social, health, and environmental characteristics could constitute such situation in a national and population-based setting. Data was retrieved from the National Health and Nutrition Examination Survey, 2005-2006. Information on demographics, lifestyle factors, self-reported ever medical conditions in the past and self-reported food security conditions in the last 12 months calculated on the household level was obtained by household interview. Bloods and urines (subsample) were collected at the interview as well. Only adults aged 20 years and above (n = 4979) were included for statistical analysis in the present study. Chi-square test, t test, and survey-weighted logistic regression modeling were performed. Three thousand eight hundred thirty-four (77.9%) people were with full food security, 466 (9.5%) people were with marginal food security and 624 (12.7%) people were with low or very low food security. Being younger, having higher ratios of family income to poverty thresholds (due to low level of education or lack of financial support), having prior asthma, arthritis, chronic bronchitis, depression, diabetes, eczema, emphysema or liver problems, having higher levels of serum cotinine, urinary antimony, bisphenol A, pesticides, or having lower levels of urinary Benzophenone-3 were associated with food insecurity. In addition to socioeconomic and smoking conditions, evidence on people with several prior health conditions and being exposed to environmental chemicals and food insecurity is further provided. Future social, health and environmental policy, and programs protecting people from food insecurity by considering both health and environmental factors mentioned above would be suggested.

  15. Deep eutectic solvent-based ultrasound-assisted dispersive liquid-liquid microextraction coupled with high-performance liquid chromatography for the determination of ultraviolet filters in water samples.

    Science.gov (United States)

    Wang, Huazi; Hu, Lu; Liu, Xinya; Yin, Shujun; Lu, Runhua; Zhang, Sanbing; Zhou, Wenfeng; Gao, Haixiang

    2017-09-22

    In the present study, a simple and rapid sample preparation method designated ultrasound-assisted dispersive liquid-liquid microextraction based on a deep eutectic solvent (DES) followed by high-performance liquid chromatography with ultraviolet (UV) detection (HPLC-UVD) was developed for the extraction and determination of UV filters from water samples. The model analytes were 2,4-dihydroxybenzophenone (BP-1), benzophenone (BP) and 2-hydroxy-4-methoxybenzophenone (BP-3). The hydrophobic DES was prepared by mixing trioctylmethylammonium chloride (TAC) and decanoic acid (DecA). Various influencing factors (selection of the extractant, amount of DES, ultrasound duration, salt addition, sample volume, sample pH, centrifuge rate and duration) on UV filter recovery were systematically investigated. Under optimal conditions, the proposed method provided good recoveries in the range of 90.2-103.5% and relative standard deviations (inter-day and intra-day precision, n=5) below 5.9%. The enrichment factors for the analytes ranged from 67 to 76. The limits of detection varied from 0.15 to 0.30ngmL -1 , depending on the analytes. The linearities were between 0.5 and 500ngmL -1 for BP-1 and BP and between 1 and 500ngmL -1 for BP-3, with coefficients of determination greater than 0.99. Finally, the proposed method was applied to the determination of UV filters in swimming pool and river water samples, and acceptable relative recoveries ranging from 82.1 to 106.5% were obtained. Copyright © 2017. Published by Elsevier B.V.

  16. Oxidation by-products and ecotoxicity assessment during the photodegradation of fenofibric acid in aqueous solution with UV and UV/H{sub 2}O{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Santiago, Javier [Department of Chemical Engineering, University of Alcala, E-28771 Alcala de Henares (Spain); Agueera, Ana; Mar Gomez-Ramos, Maria del [Department of Analytical Chemistry, University of Almeria, E-04010 Almeria (Spain); Fernandez Alba, Amadeo R. [Department of Analytical Chemistry, University of Almeria, E-04010 Almeria (Spain); Advanced Study Institute of Madrid, IMDEA-Agua, Parque Cientifico Tecnologico, E-28805 Alcala de Henares, Madrid (Spain); Garcia-Calvo, Eloy [Department of Chemical Engineering, University of Alcala, E-28771 Alcala de Henares (Spain); Advanced Study Institute of Madrid, IMDEA-Agua, Parque Cientifico Tecnologico, E-28805 Alcala de Henares, Madrid (Spain); Rosal, Roberto, E-mail: roberto.rosal@uah.es [Department of Chemical Engineering, University of Alcala, E-28771 Alcala de Henares (Spain); Advanced Study Institute of Madrid, IMDEA-Agua, Parque Cientifico Tecnologico, E-28805 Alcala de Henares, Madrid (Spain)

    2011-10-30

    Highlights: {yields} UV and UV/H{sub 2}O{sub 2} photolysis of fenofibric acid. {yields} Identification of reaction intermediates using exact mass measurements. {yields} UV/H{sub 2}O{sub 2} removed toxicity towards Pseudokirchneriella subcapitata. {yields} Irradiated samples contain a number of chlorinated products. - Abstract: The degradation of an aqueous solution of fenofibric acid was investigated using ultraviolet (UV) photolysis and UV/H{sub 2}O{sub 2} with a low-pressure mercury lamp. We obtained quantum yields at different temperatures and the rate constant for the reaction of fenofibric acid with hydroxyl radicals. The maximum radical exposure per fluence ratio obtained was 1.4 x 10{sup -10} M L{sup -1} mW{sup -1}. Several reaction intermediates were detected by means of exact mass measurements performed by liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry (LC-ESI-QTOF-MS). UV and UV/H{sub 2}O{sub 2} pathways involve the decarboxylation of fenofibric acid to 4-chloro-4'-(1-hydroxy-1-methylethyl)benzophenone and other minor products, predominantly chlorinated aromatics. We detected several intermediates from reactions with hydroxyl radicals and some lower molecular weight products from the scission of the carbonyl carbon-to-aromatic-carbon bond. We recorded high toxicity in UV irradiated samples for the growth of Pseudokirchneriella subcapitata even after the total depletion of fenofibric acid; this was probably due to the presence of chlorinated aromatics. A degree of toxicity reappeared in highly irradiated UV/H{sub 2}O{sub 2} samples, probably because of the formation of ring-opening products. The degree of mineralization was closely related to that of dechlorination and reached values of over 50% after 3-4 min before stabilizing thereafter.

  17. Simultaneous determination of UV-filters and estrogens in aquatic invertebrates by modified quick, easy, cheap, effective, rugged, and safe extraction and liquid chromatography tandem mass spectrometry.

    Science.gov (United States)

    He, Ke; Timm, Anne; Blaney, Lee

    2017-08-04

    Ultraviolet-filters (UV-filters) and estrogens have attracted increased attention as contaminants of emerging concern (CECs) due to their widespread occurrence in the environment. Most of these CECs are hydrophobic and have the potential to accumulate in aquatic organisms. To date, co-analysis of UV-filters and estrogens has not been reported due, in part, to the complex environmental matrices. Here, a multi-residue method has been developed for simultaneous determination of five UV-filters and three estrogens in tissue from aquatic and marine organisms. The procedure involved a modified Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) extraction with a novel reverse-solid-phase extraction (reverse-SPE) cleanup in place of dispersive-SPE, followed by liquid chromatography tandem mass spectrometry (LC-MS/MS) analysis. The tissue mass, acetonitrile content, and salt conditions for QuEChERS extraction, along with the reverse-SPE cartridge material and elution conditions, were thoroughly investigated and optimized. Five UV-filters (i.e., 3-(4-methylbenzylidene) camphor, benzophenone-3, ethylhexylmethoxycinnamate, homosalate, and octocrylene) and three estrogens (i.e., estrone, 17β-estradiol, and 17α-ethinylestradiol) were simultaneously analyzed by taking advantage of wrong-way-round ionization in LC-MS/MS. The optimized analytical protocol exhibited good recoveries (>80%) for target compounds and enabled their detection at concentrations as low as 0.2ng/g in 50mg tissue samples. The method was applied to determine concentrations of target analytes in four invertebrates (i.e., Orconectes virilis, Procambarus clarkii, Crassostrea virginica, and Ischadium recurvum). All eight target analytes were detected at least once in the tissue samples, with the highest concentration being 399ng/g of homosalate in O. virilis. These results highlight the ubiquitous bioaccumulation of CECs in aquatic and marine invertebrates. Copyright © 2017 Elsevier B.V. All rights

  18. Contaminants of emerging concern in fresh leachate from landfills in the conterminous United States

    Science.gov (United States)

    Masoner, Jason R.; Kolpin, Dana W.; Furlong, Edward T.; Cozzarelli, Isabelle M.; Gray, James L.; Schwab, Eric A.

    2014-01-01

    To better understand the composition of contaminants of emerging concern (CECs) in landfill leachate, fresh leachate from 19 landfills was sampled across the United States during 2011. The sampled network included 12 municipal and 7 private landfills with varying landfill waste compositions, geographic and climatic settings, ages of waste, waste loads, and leachate production. A total of 129 out of 202 CECs were detected during this study, including 62 prescription pharmaceuticals, 23 industrial chemicals, 18 nonprescription pharmaceuticals, 16 household chemicals, 6 steroid hormones, and 4 plant/animal sterols. CECs were detected in every leachate sample, with the total number of detected CECs in samples ranging from 6 to 82 (median = 31). Bisphenol A (BPA), cotinine, and N,N-diethyltoluamide (DEET) were the most frequently detected CECs, being found in 95% of the leachate samples, followed by lidocaine (89%) and camphor (84%). Other frequently detected CECs included benzophenone, naphthalene, and amphetamine, each detected in 79% of the leachate samples. CEC concentrations spanned six orders of magnitude, ranging from ng L−1 to mg L−1. Industrial and household chemicals were measured in the greatest concentrations, composing more than 82% of the total measured CEC concentrations. Maximum concentrations for three household and industrial chemicals, para-cresol (7020000 ng L−1), BPA (6380000 ng L−1), and phenol (1550000 ng L−1), were the largest measured, with these CECs composing 70% of the total measured CEC concentrations. Nonprescription pharmaceuticals represented 12%, plant/animal sterols 4%, prescription pharmaceuticals 1%, and steroid hormones amounts of precipitation had greater frequencies of CEC detections and concentrations in leachate than landfills receiving less precipitation.

  19. Anti-inflammatory activity of Vismia guianensis (Aubl.) Pers. extracts and antifungal activity against Sporothrix schenckii.

    Science.gov (United States)

    Oliveira, A H; de Oliveira, G G; Carnevale Neto, F; Portuondo, D F; Batista-Duharte, A; Carlos, I Z

    2017-01-04

    Vismia guianensis (Aubl.) Pers. is traditionally used in North and Northeast of Brazil for the treatment of dermatomycoses. Since the strategy associating immunomodulators with antifungal drugs seems to be promissory to improve the treatment efficacy in fungal infections, we aimed to investigate the antifungal activity of V. guianensis ethanolic extract of leaves (VGL) and bark (VGB) against Sporothrix schenckii ATCC 16345 and their antinflammatory activities. The extracts were analyzed by HPLC-DAD-IT MS/MS for in situ identification of major compounds. Antifungal activity was evaluated in vitro (microdilution test) and in vivo using a murine model of S. schenckii infection. The production of TNF-α, IFN-γ, IL-4, IL-10 and IL-12 by measured by ELISA, as well as measured the production and inhibition of the NO after treatment with the plant extracts or itraconazole (ITR). Two O-glucosyl-flavonoids and 16 prenylated benzophenone derivatives already described for Vismia were detected. Both VGL and VGB showed significant antifungal activity either in in vitro assay of microdilution (MIC=3.9µg/mL) and in vivo model of infection with reduction of S. schenckii load in spleen. It was also observed a predominance of reduction in the production of NO and the proinflammatory cytokines evaluated except TNFα, but with stimulation of IL-10, as evidence of a potential anti-inflammatory effect associated. The results showed that both VGL and VGB have a significant antifungal against S. schenckii and an anti-inflammatory activity. These results can support the use of these extracts for alternative treatment of sporotrichosis. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Bio-based coatings as potential barriers to chemical contaminants from recycled paper and board for food packaging.

    Science.gov (United States)

    Guazzotti, V; Marti, A; Piergiovanni, L; Limbo, S

    2014-01-01

    Partition and diffusion experiments were carried out with paper and board samples coated with different biopolymers. The aim was to evaluate the physicochemical behaviour and barrier properties of bio-coatings against migration of typical contaminants from recycled paper packaging. Focus was directed towards water-based, renewable biopolymers, such as modified starches (cationic starch and cationic waxy starch), plant and animal proteins (gluten and gelatine), poured onto paper with an automatic applicator. Additionally, a comparison with polyethylene-laminated paper was performed. Microstructural observations of the bio-coated paper allowed the characterisation of samples. From the partitioning studies, considerable differences in the adsorption behaviour of the selected contaminants between bio-coated or uncoated paper and air were highlighted. For both the polar and non-polar compounds considered (benzophenone and diisobutyl phthalate, respectively), the lowest values of partition coefficients were found when paper was bio-coated, making it evident that biopolymers acted as chemical/physical barriers towards these contaminants. These findings are discussed considering the characteristics of the tested biopolymers. Diffusion studies into the solid food simulant poly 2,6-diphenyl-p-phenylene oxide, also known as Tenax(®), confirmed that all the tested biopolymers slowed down migration. The Weibull kinetic model was fitted to the experimental data to compare migration from paper and bio-coated paper. Values found for β, an index determining the pattern of curvature, ranged from 1.1 to 1.7 for uncoated and polyethylene paper, whereas for bio-coated papers they ranged from 2.2 to 4.9, corresponding to the presence of an evident lag phase due to barrier properties of the tested bio-coatings.

  1. The Paleobiosphere: a novel device for the in vivo testing of hydrocarbon producing-utilizing microorganisms.

    Science.gov (United States)

    Strobel, Gary; Booth, Eric; Schaible, George; Mends, Morgan Tess; Sears, Joe; Geary, Brad

    2013-04-01

    The construction and testing of a unique instrument, the Paleobiosphere, which mimics some of the conditions of the ancient earth, is described. The instrument provides an experimental testing system for determining if certain microbes, when provided an adequate environment, can degrade biological materials to produce fuel-like hydrocarbons in a relatively short time frame that become trapped by the shale. The conditions selected for testing included a particulate Montana shale (serving as the "Trap Shale"), plant materials (leaves and stems of three extant species whose origins are in the late Cretaceous), a water-circulating system, sterile air, and a specially designed Carbotrap through which all air was passed as exhaust and volatile were hydrocarbons trapped. The fungus for initial testing was Annulohypoxylon sp., isolated as an endophyte of Citrus aurantifolia. It produces, in solid and liquid media, a series of hydrocarbon-like molecules. Some of these including 1,8-cineole, 2-butanone, propanoic acid, 2-methyl-, methyl ester, benzene (1-methylethyl)-, phenylethyl alcohol, benzophenone and azulene, 1,2,3,5,6,7,8,8a-octahydro-1,4-dimethyl-7-(1-methylethenyl), [1S-(1α,7α,8aβ)]. These were the key signature compounds used in an initial Paleobiosphere test. After 3 weeks, incubation, the volatiles associated with the harvested "Trap Shale" included each of the signature substances as well as other fungal-associated products: some indanes, benzene derivatives, some cyclohexanes, 3-octanone, naphthalenes and others. The fungus thus produced a series of "Trap Shale" products that were representative of each of the major classes of hydrocarbons in diesel fuel (Mycodiesel). Initial tests with the Paleobiosphere offer some evidence for a possible origin of hydrocarbons trapped in bentonite shale. Thus, with modifications, numerous other tests can also be designed for utilization in the Paleobiosphere.

  2. UV filters induce transcriptional changes of different hormonal receptors in Chironomus riparius embryos and larvae.

    Science.gov (United States)

    Ozáez, Irene; Aquilino, Mónica; Morcillo, Gloria; Martínez-Guitarte, José-Luis

    2016-07-01

    Organic ultraviolet (UV) filters are emerging contaminants that are ubiquitous in fresh and marine aquatic systems due to their extensive use in cosmetics, plastics, paints, textiles, and many other industrial products. The estrogenic effects of organic UV filters have been long demonstrated in vertebrates, and other hormonal activities may be altered, according to more recent reports. The impact of UV filters on the endocrine system of invertebrates is largely unknown. We have previously reported that some UV filters may affect ecdysone-related genes in the aquatic insect Chironomus riparius, an ecotoxicologically important model organism. To further analyze other possible effects on endocrine pathways, we first characterized four pivotal genes related with hormonal pathways in insects; thereafter, these genes were assessed for alterations in transcriptional activity after exposure to 4-methylbenzylidene camphor (4MBC) or benzophenone-3 (BP-3), two extensively used sunscreens. We found that both chemicals disturbed the expression of all four genes analyzed: hormonal receptor 38 (HR38), methoprene-tolerant (Met), membrane-associate progesterone receptor (MAPR) and insulin-like receptor (INSR), measured by changes in mRNA levels by real-time PCR. An upregulatory effect at the genomic level was detected in different developmental stages. Interestingly, embryos appeared to be more sensitive to the action of the UV filters than larvae. Our results suggest that the risk of disruption through different endocrine routes is not negligible, considering the significant effects of UV filters on key hormonal receptor and regulatory genes. Further effort is needed to develop environmental risk assessment studies on these pollutants, particularly for aquatic invertebrate model organisms. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Reactive low temperature plasma ionization mass spectrometry for the determination of organic UV filters in personal care products.

    Science.gov (United States)

    Ding, Xuelu; Gerbig, Stefanie; Spengler, Bernhard; Schulz, Sabine

    2018-02-01

    Organic UV filters in personal care products (PCPs) have been persistently reported as a potential threat to human health. In order to guarantee consumers ' safety, the dose of these compounds in PCPs needs to be monitored. Here, a methodology based on reactive low temperature plasma ionization (LTP) mass spectrometry (MS) has been developed for the determination of common organic UV filters in PCPs including benzophenone-3, ethylhexyl dimethyl p-aminobenzoic acid, ethylhexyl methoxycinnamate, 4-methylbenzylidene camphor, octocrylene, and ethylhexyl salicylate. The experiments were carried out in transmission geometry where the LTP ion source, samples loaded on a stainless steel mesh, and the MS inlet were aligned coaxially. Four chemicals, ammonia, ammonium formate, aniline, and methylamine were considered as reactive additives allowing reactions with the UV filters through different mechanisms. Methylamine-induced reactive LTP-MS showed the most prominent improvement on the detection of UV filter compounds. Compared to direct LTP-MS, the developed method improved the detection limits of UV filters more than 10 fold. Moreover, the method enabled fast semi-quantitative screening of UV filters in authentic PCPs. Concentrations of active ingredients in eight authentic PCPs as determined with reactive LTP-MS were found comparable to values offered by the cosmetic companies and corresponding HPLC data. The methodology provides high throughput analysis (70s per sample) and sensitive identification of organic UV filters. Lowest detectable concentrations ranged from 0.13µg/g for 4-methylbenzylidene camphor to 7.67µg/g for octocrylene in spiked cream. In addition, it shows the potential to be used as a screening tool for legal authentications of these chemicals in the future due to its semi-quantitative determination of UV filters in PCPs without tedious sample preparation and time-consuming chromatographic separation. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Inhibition of Saccharomyces cerevisiae Pdr5p by a natural compound extracted from Brazilian Red Propolis

    Directory of Open Access Journals (Sweden)

    Cinzia Lotti

    2011-10-01

    Full Text Available Multidrug resistance of cancer cells and pathogenic microorganisms leading to the treatment failure of some forms of cancer or life-threatening bacterial or fungal infections is often caused by the overexpression of multidrug efflux pumps belonging to the ATP-binding cassette transporters superfamily. The multidrug resistance of fungal cells often involves the overexpression of efflux pumps belonging to the pleiotropic drug resistance (PDR family of ABC transporters. Possibly the best-studied fungal PDR transporter is the multidrug resistance transporter Pdr5p of Saccharomyces cerevisiae. Some research groups have been searching for new inhibitors of these efflux pumps in order to alleviate resistance. Natural products are a great source for the discovery of new compounds with biological activity. Propolis is a complex resinous material collected by honeybees from exudates and buds of certain plant sources and this material is thought to serve as a defense substance for bee hives. Propolis is widely used in traditional medicine and is reported to have a broad spectrum of pharmacological properties. Literature reported some biological functionalities of propolis, such as antibacterial, antiviral, fungicidal, anti-inflammatory and anti-carcinogenic activities. The chemical composition of propolis is qualitatively and quantitatively variable. Components isolated from methanolic extract of red Brazilian propolis (Alagoas, Northeast of Brazil are isoflavonoids (including pterocarpans, isoflavans, isoflavones, flavanones and polyprenylated benzophenones. In this work we demonstrated the effects of five different isolated compounds on the ATPase activity of Pdr5p. Out of all five substances tested, only BRP-1 was able to completely abolish the enzymatic activity while others worked as positive modulators of the enzyme activity. BRP-1also inhibited the efflux of Rhodamine 6G from yeast cells overexpressing Pdr5p. Taken together, these results

  5. The production of reactive oxygen species by irradiated camphorquinone-related photosensitizers and their effect on cytotoxicity.

    Science.gov (United States)

    Atsumi, T; Iwakura, I; Fujisawa, S; Ueha, T

    2001-05-01

    Camphorquinone (CQ) is widely used as an initiator in modern light-cured resin systems but there are few reports about its effects on living cells. To clarify the mechanism of photosensitizer-induced cytotoxicity, the production of initiator radicals and subsequent reactive oxygen species (ROS) by CQ, benzil (BZ), benzophenone (BP), 9-fluorenone (9-F) in the presence of the reducing agent (2-dimethylaminoethyl methacrylate or N,N-dimethyl-p-toluidine, DMT) with visible-light irradiation was examined in a cell or cell-free system. Initiator radical production was estimated by the reduction rate of 1,1-diphenyl-2-picrylhydrazyl and by the conversion of poly-triethyleneglycol dimethacrylate; the results indicated that CQ/DMT had the highest activity among them. The cytotoxic effects of the photosensitizers on both human submandibular gland (HSG) adenocarcinoma cell line and primary human gingival fibroblast (HGF) showed that the 50% toxic concentration (TC(50)) declined in the order: CQ>BP>9-F>BZ. ROS produced in HSG or HGF cells by elicited, irradiated photosensitizers were evaluated in two different assays, one using adherent cell analysis and sorting cytometry against adherent cells and the other, flow cytometry against floating cells, with fluorescent probes. ROS production was dose- and time- dependent, and declined in the order: BZ>9-F>BP>CQ. Cytotoxic activity was correlated with the amount of ROS. Cytotoxicity and ROS generation in HGF cells was significantly lower than in HSG cells. ROS induced by aliphatic ketones (CQ) were efficiently scavenged by hydroquinone and vitamin E, whereas those by aromatic ketones (9-F) were diminished by mannitol and catalase, suggesting that OH radicals were involved in ROS derived from 9-F. A possible link between the cytotoxic activity and ROS is suggested.

  6. Universal and non-universal features of the dynamic susceptibility of supercooled liquids

    Energy Technology Data Exchange (ETDEWEB)

    Brodin, Alexander; Roessler, Ernst A [Experimentalphysik II, Universitaet Bayreuth, D-95440 Bayreuth (Germany)

    2006-09-20

    We discuss the dynamics of the glass-forming liquids glycerol, propylene carbonate, and benzophenone, as revealed in their dielectric behaviour and in depolarized light scattering (DLS) data. Above the melting point, the liquids exhibit two-step stretched relaxation behaviour typical of 'glassy dynamics' at all attainable temperatures {>=}2T{sub g}. There is no sign of a transition to exponential relaxation; rather, the stretching depends only weakly on the temperature. The spectral change, in first approximation, amounts to shifting the {alpha}-relaxation peak with the temperature. This behaviour is in contrast with the temperature-dependent spectral shapes observed in the low-temperature state close to T{sub g}. Analysing corresponding dielectric spectroscopic (DS) data for comparisons, similar tendencies are observed, except that the stretching parameters are different. Below a certain temperature in glycerol, the tail of the excess wing, which is clearly pronounced in the DS data, appears also in the DLS spectra, with the same ratio of the wing exponents in DLS versus DS as of the stretching exponents at higher T. In propylene carbonate, the presence of a wing in the DLS data is not immediately obvious. However, its low-temperature DLS spectra are fully compatible with an empirical model for the temperature-dependent spectral shape that adequately describes the DS data of both materials and includes the wing. We were however unable to reconcile the DLS results of glycerol with this model. This, together with the pronounced difference in DLS and DS spectral widths of glycerol, cast doubts over the general validity of universal scaling procedures for different techniques.

  7. Novel approach to high-throughput determination of endocrine disruptors using recycled diatomaceous earth as a green sorbent phase for thin-film solid-phase microextraction combined with 96-well plate system.

    Science.gov (United States)

    Kirschner, Nicolas; Dias, Adriana Neves; Budziak, Dilma; da Silveira, Cristian Berto; Merib, Josias; Carasek, Eduardo

    2017-12-15

    A sustainable approach to TF-SPME is presented using recycled diatomaceous earth, obtained from a beer purification process, as a green sorbent phase for the determination of bisphenol A (BPA), benzophenone (BzP), triclocarban (TCC), 4-methylbenzylidene camphor (4-MBC) and 2-ethylhexyl-p-methoxycinnamate (EHMC) in environmental water samples. TF-SPME was combined with a 96-well plate system allowing for high-throughput analysis due to the simultaneous extraction/desorption up to 96 samples. The proposed sorbent phase exhibited good stability in organic solvents, as well as satisfactory analytical performance. The optimized method consisted of 240 min of extraction at pH 6 with the addition of NaCl (15% w/v). A mixture of MeOH:ACN (50:50 v/v) was used for the desorption the analytes, using a time of 30 min. Limits of detection varied from 1 μg L -1 for BzP and TCC to 8 μg L -1 for the other analytes, and R 2 ranged from 0.9926 for 4-MBC to 0.9988 for BPA. This novel and straightforward approach offers an environmentally-friendly and very promising alternative for routine analysis. . The total sample preparation time per sample was approximately 2.8 min, which is a significant advantage when a large number of analytical run is required. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Low-cost approach to increase the analysis throughput of bar adsorptive microextraction (BAµE) combined with environmentally-friendly renewable sorbent phase of recycled diatomaceous earth.

    Science.gov (United States)

    Mafra, Gabriela; Oenning, Anderson Luiz; Dias, Adriana Neves; Merib, Josias; Budziak, Dilma; Silveira, Cristian Berto da; Carasek, Eduardo

    2018-02-01

    In this study, a novel apparatus for bar adsorptive microextraction (BAµE) using a voltage regulator was proposed as an alternative tool to improve the analysis throughput. In addition, recycled diatomaceous earth obtained as a brewery residue was employed as a biosorbent coating for the determination of methyl paraben, ethyl paraben, benzophenone and triclocarban in water samples by high-performance liquid chromatography-diode array detection (HPLC-DAD). The use of the extraction devices, comprised of floating adsorptive bars of 7.5mm length, in the extractions with magnetic stirrers linked to a voltage regulator enabled the analysis of multiple samples, simultaneously. The method optimization was carried out by univariate and multivariate analyses. The optimal conditions for the method were sample solution at pH 5, extraction time of 90min and liquid desorption in 100µL of acetonitrile:methanol (50:50, v/v) for 15min. The total sample preparation time was 17.5min per sample for a simultaneous batch of six extractions. The R 2 values for the calibration curves obtained were higher than 0.9985. The limits of detection (LODs) varied from 0.19 to 2μgL -1 and the limits of quantification (LOQs) ranged from 0.63 to 6.9μgL -1 . The method was applied to freshwater samples collected from Peri Lagoon (Florianópolis, SC, Brazil) and the relative recoveries ranged from 63% to 124% with relative standard deviations (RSDs) of < 20% (n = 2). The RSD values for the reproducibility of the performance of the magnetic stirrers and inter-device extraction efficiency were lower than 14% (n = 3) and 11% (n = 3), respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Borata-Wittig olefination reactions of ketones, carboxylic esters and amides with bis(pentafluorophenyl)borata-alkene reagents.

    Science.gov (United States)

    Wang, Tongdao; Kohrt, Sonja; Daniliuc, Constantin G; Kehr, Gerald; Erker, Gerhard

    2017-08-07

    The strongly electrophilic borane derivative amino-CH 2 CH 2 CH 2 -B(C 6 F 5 ) 2 6 was α-CH deprotonated with LiTMP to give the borata-alkene {[amino-(CH 2 ) 2 -CH[double bond, length as m-dash]B(C 6 F 5 ) 2 - ][Li + ]} 2 9 which underwent facile [2 + 2] cycloaddition reactions with benzophenone or fluorenone to yield the respective 1,2-oxaboretanides 11a,b. Compounds 9 and 11 were characterized by the X-ray diffraction. Thermolysis or hydrolysis of compounds 11a,b gave the corresponding borata-Wittig olefination products 12a,b. A variety of R-CH 2 -CH 2 -B(C 6 F 5 ) 2 boranes (conveniently generated by hydroboration of terminal alkenes R-CH[double bond, length as m-dash]CH 2 with Piers' borane [HB(C 6 F 5 ) 2 ]) were analogously deprotonated to give the respective borata-alkenes 16a-e (R: Ph-CH 2 -, n C 4 H 9 , t Bu, Cy, PhCH 2 CH 2 -). They underwent "non-classical" borata-Wittig olefination reactions with ethylformate to give the respective enolether carbonylation products, or their C 1 -elongated aldehydes (after hydrolysis). The borata-alkene [Ph-(CH 2 ) 2 -CH[double bond, length as m-dash]B(C 6 F 5 ) 2 - ] [Li + HTMP] (16a) gave the respective "non-classical" borata-Wittig olefination products, the enolethers 25a,b and 27, respectively, upon treatment with methyl- or ethyl acetate or γ-butyrolactone.

  10. Bespoke contrast-matched diblock copolymer nanoparticles enable the rational design of highly transparent Pickering double emulsions† †Electronic supplementary information (ESI) available: GPC chromatograms, additional transmission electron micrographs, digital photographs, visible absorption spectra and laser diffraction data, further optical and fluorescence micrographs. See DOI: 10.1039/c6nr03856e Click here for additional data file.

    Science.gov (United States)

    Thompson, Kate L.; Derry, Matthew J.; Warren, Nicholas J.; Ratcliffe, Liam P. D.; Williams, Clive N.; Brown, Steven L.

    2016-01-01

    We report the preparation of highly transparent oil-in-water Pickering emulsions using contrast-matched organic nanoparticles. This is achieved via addition of judicious amounts of either sucrose or glycerol to an aqueous dispersion of poly(glycerol monomethacrylate)56–poly(2,2,2-trifluoroethyl methacrylate)500 [PGMA–PTFEMA] diblock copolymer nanoparticles prior to high shear homogenization with an equal volume of n-dodecane. The resulting Pickering emulsions comprise polydisperse n-dodecane droplets of 20–100 μm diameter and exhibit up to 96% transmittance across the visible spectrum. In contrast, control experiments using non-contrast-matched poly(glycerol monomethacrylate)56–poly(benzyl methacrylate)300 [PGMA56–PBzMA300] diblock copolymer nanoparticles as a Pickering emulsifier only produced conventional highly turbid emulsions. Thus contrast-matching of the two immiscible phases is a necessary but not sufficient condition for the preparation of highly transparent Pickering emulsions: it is essential to use isorefractive nanoparticles in order to minimize light scattering. Furthermore, highly transparent oil-in-water-in-oil Pickering double emulsions can be obtained by homogenizing the contrast-matched oil-in-water Pickering emulsion prepared using the PGMA56–PTFEMA500 nanoparticles with a contrast-matched dispersion of hydrophobic poly(lauryl methacrylate)39–poly(2,2,2-trifluoroethyl methacrylate)800 [PLMA39–PTFEMA800] diblock copolymer nanoparticles in n-dodecane. Finally, we show that an isorefractive oil-in-water Pickering emulsion enables fluorescence spectroscopy to be used to monitor the transport of water-insoluble small molecules (pyrene and benzophenone) between n-dodecane droplets. Such transport is significantly less efficient than that observed for the equivalent isorefractive surfactant-stabilized emulsion. Conventional turbid emulsions do not enable such a comparison to be made because the intense light scattering leads to

  11. Environmental occurrence and risk of organic UV filters and stabilizers in multiple matrices in Norway.

    Science.gov (United States)

    Langford, Katherine H; Reid, Malcolm J; Fjeld, Eirik; Øxnevad, Sigurd; Thomas, Kevin V

    2015-07-01

    Eight organic UV filters and stabilizers were quantitatively determined in wastewater sludge and effluent, landfill leachate, sediments, and marine and freshwater biota. Crab, prawn and cod from Oslofjord, and perch, whitefish and burbot from Lake Mjøsa were selected in order to evaluate the potential for trophic accumulation. All of the cod livers analysed were contaminated with at least 1 UV filter, and a maximum concentration of almost 12 μg/g wet weight for octocrylene (OC) was measured in one individual. 80% of the cod livers contained OC, and approximately 50% of cod liver and prawn samples contained benzophenone (BP3). Lower concentrations and detection frequencies were observed in freshwater species and the data of most interest is the 4 individual whitefish that contained both BP3 and ethylhexylmethoxycinnamate (EHMC) with maximum concentrations of almost 200 ng/g wet weight. The data shows a difference in the loads of UV filters entering receiving water dependent on the extent of wastewater treatment. Primary screening alone is insufficient for the removal of selected UV filters (BP3, Padimate, EHMC, OC, UV-234, UV-327, UV-328, UV-329). Likely due in part to the hydrophobic nature of the majority of the UV filters studied, particulate loading and organic carbon content appear to be related to concentrations of UV filters in landfill leachate and an order of magnitude difference in these parameters correlates with an order of magnitude difference in the effluent concentrations of selected UV filters (Fig. 2). From the data, it is possible that under certain low flow conditions selected organic UV filters may pose a risk to surface waters but under the present conditions the risk is low, but some UV filters will potentially accumulate through the trophic food chain. Copyright © 2015. Published by Elsevier Ltd.

  12. Organic UV filters inhibit multixenobiotic resistance (MXR) activity in Tetrahymena thermophila: investigations by the Rhodamine 123 accumulation assay and molecular docking.

    Science.gov (United States)

    Gao, Li; Yuan, Tao; Cheng, Peng; Zhou, Chuanqi; Ao, Junjie; Wang, Wenhua; Zhang, Haimou

    2016-09-01

    Multixenobiotic resistance (MXR) transporters, which belong to ATP-binding cassette (ABC) family proteins, are present in living organisms as a first line of defense system against xenobiotics and environmental contaminants. The effects of six organic UV filters (4-methyl -benzylidene camphor, 4-MBC; benzophenone-3, BP-3; butyl methoxydibenzoyl-methane, BM-DBM; ethylhexyl methoxy cinnamate, EHMC; octocrylene, OC and homosalate, HMS) on multixenobiotic resistance (MXR) in Tetrahymena thermophila were investigated in this study. It was found that 4-MBC, BP-3 and BM-DBM could significantly inhibit activity of the MXR system, causing concentration dependent accumulation of rhodamine 123; while EHMC, OC and HMS had weak MXR inhibition. The IC50 (50 % inhibition concentration) values of 4-MBC, BP-3 and BM-DBM were 23.54, 40.59 and 26.37 μM, respectively, with inhibitory potentials of 23.1, 13.4 and 20.6 % relative to verapamil (VER, a model inhibitor of P-glycoprotein). Our results firstly provide the evidence for UV filters inhibition effect on MXR in aquatic organisms. In addition, it was revealed by molecular docking analysis that the selected six UV filters can occupy the same binding site on T. thermophila P-gp as VER does; and form H-bonds with residues Ser 328 and/or Asn 281. This study raises the awareness of aquatic ecological risk from the organic UV filters exposure, as they would be involved in potentiating toxic effects by chemosensitizing.

  13. A new carbon-based magnetic material for the dispersive solid-phase extraction of UV filters from water samples before liquid chromatography-tandem mass spectrometry analysis.

    Science.gov (United States)

    Piovesana, Susy; Capriotti, Anna Laura; Cavaliere, Chiara; La Barbera, Giorgia; Samperi, Roberto; Zenezini Chiozzi, Riccardo; Laganà, Aldo

    2017-07-01

    Magnetic solid-phase extraction is one of the most promising new extraction methods for liquid samples before ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) analysis. Several types of materials, including carbonaceous ones, have been prepared for this purpose. In this paper, for the first time, the preparation, characterization, and sorption capability of Fe 3 O 4 -graphitized carbon black (mGCB) composite toward some compounds of environmental interest were investigated. The synthesized mGCB consisted of micrometric GCB particles with 55 m 2  g -1 surface area bearing some carbonyl and hydroxyl functionalities and the surface partially decorated by Fe 3 O 4 microparticles. The prepared mGCB was firstly tested as an adsorbent for the extraction from surface water of 50 pollutants, including estrogens, perfluoroalkyl compounds, UV filters, and quinolones. The material showed good affinity to many of the tested compounds, except carboxylates and glucoronates; however, some compounds were difficult to desorb. Ten UV filters belonging to the chemical classes of benzophenones and p-aminobenzoates were selected, and parameters were optimized for the extraction of these compounds from surface water before UHPLC-MS/MS determination. Then, the method was validated in terms of linearity, trueness, intra-laboratory precision, and detection and quantification limits. In summary, the method performance (trueness, expressed as analytical recovery, 85-114%; RSD 5-15%) appears suitable for the determination of the selected compounds at the level of 10-100 ng L -1 , with detection limits in the range of 1-5 ng L -1 . Finally, the new method was compared with a published one, based on conventional solid-phase extraction with GCB, showing similar performance in real sample analysis. Graphical Abstract Workflow of the analytical method based on magnetic solid-phase extraction followed by LC-MS/MS determination.

  14. UV filters bioaccumulation in fish from Iberian river basins.

    Science.gov (United States)

    Gago-Ferrero, Pablo; Díaz-Cruz, M Silvia; Barceló, Damià

    2015-06-15

    The occurrence of eight organic UV filters (UV-Fs) was assessed in fish from four Iberian river basins. This group of compounds is extensively used in cosmetic products and other industrial goods to avoid the damaging effects of UV radiation, and has been found to be ubiquitous contaminants in the aquatic ecosystem. In particular, fish are considered by the scientific community to be the most feasible organism for contamination monitoring in aquatic ecosystems. Despite that, studies on the bioaccumulation of UV-F are scarce. In this study fish samples from four Iberian river basins under high anthropogenic pressure were analysed by liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Benzophenone-3 (BP3), ethylhexyl methoxycinnamate (EHMC), 4-methylbenzylidene camphor (4MBC) and octocrylene (OC) were the predominant pollutants in the fish samples, with concentrations in the range of ng/g dry weight (d.w.). The results indicated that most polluted area corresponded to Guadalquivir River basin, where maximum concentrations were found for EHMC (241.7 ng/gd.w.). Sediments from this river basin were also analysed. Lower values were observed in relation to fish for OC and EHMC, ranging from below the limits of detection to 23 ng/gd.w. Accumulation levels of UV-F in the fish were used to calculate biota-sediment accumulation factors (BSAFs). These values were always below 1, in the range of 0.04-0.3, indicating that the target UV-Fs are excreted by fish only to some extent. The fact that the highest concentrations were determined in predators suggests that biomagnification of UV-F may take place along the freshwater food web. Copyright © 2015. Published by Elsevier B.V.

  15. The occurrence of UV filters in natural and drinking water in São Paulo State (Brazil).

    Science.gov (United States)

    da Silva, Claudia Pereira; Emídio, Elissandro Soares; de Marchi, Mary Rosa Rodrigues

    2015-12-01

    Ultraviolet (UV) filters are widely used in the formulation of personal care products (PCPs) to prevent damage to the skin, lips, and hair caused by excessive UV radiation. Therefore, large amounts of these substances are released daily into the aquatic environment through either recreational activities or the release of domestic sewage. The concern regarding the presence of such substances in the environment and the exposure of aquatic organisms is based on their potential for bioaccumulation and their potential as endocrine disruptors. Although there are several reports regarding the occurrence and fate of UV filters in the aquatic environment, these compounds are still overlooked in tropical areas. In this study, we investigated the occurrence of the organic UV filters benzophenone-3 (BP-3), ethylhexyl salicylate (ES), ethylhexyl methoxycinnamate (EHMC), and octocrylene (OC) in six water treatment plants in various cities in Southeast Brazil over a period of 6 months to 1 year. All of the UV filters studied were detected at some time during the sampling period; however, only EHMC and BP-3 were found in quantifiable concentrations, ranging from 55 to 101 and 18 to 115 ng L(-1), respectively. Seasonal variation of BP-3 was most clearly noticed in the water treatment plant in Araraquara, São Paulo, where sampling was performed for 12 months. BP-3 was not quantifiable in winter but was quantifiable in summer. The levels of BP-3 were in the same range in raw, treated and chlorinated water, indicating that the compound was not removed by the water treatment process.

  16. Transcriptional activity of detoxification genes is altered by ultraviolet filters in Chironomus riparius.

    Science.gov (United States)

    Martínez-Guitarte, José-Luis

    2018-03-01

    Ultraviolet (UV) filters are compounds used to prevent the damage produced by UV radiation in personal care products, plastics, etc. They have been associated with endocrine disruption, showing anti-estrogen activity in vertebrates and altering the ecdysone pathway in invertebrates. Although they have attracted the attention of multiple research teams there is a lack of data about how animals activate detoxification systems, especially in invertebrates. Here, analysis of the effects of two UV filters, benzophenone-3 (BP3) and 4-methylbenzylidene camphor (4MBC), on the transcriptional activity of nine genes covering the three steps of the detoxification process has been performed. Four cytochrome P450 genes belonging to different members of this family, five GST genes, and the multidrug resistance protein 1 (MRP1) gene were studied by RT-PCR to analyze their transcriptional activity in fourth instar larvae exposed to the UV filters for 8 and 24h. The obtained results show a differential response with downregulation of the different Cyp450s tested by 4MBC while BP3 seems not to modify their expression. On the other hand, some of the GST genes were affected by one or other of the filters, showing a less homogenous response. Finally, MRP1 was activated by both filters but at different times. These results demonstrate for first time that UV filters alter the expression of genes involved in the different steps of the detoxification process and that they can be processed by phase I enzymes other than Cyp450s. They also suggest that UV filters affect biotransformation processes, compromising the ability of the individual to respond to chemical stress, so further research is needed to know the extent of the damage that they can produce in the resistance of the cell to chemicals. Copyright © 2017 Elsevier Inc. All rights reserved.

  17. Ecotoxicity of two organic UV-filters to the freshwater caddisfly Sericostoma vittatum.

    Science.gov (United States)

    Campos, Diana; Gravato, Carlos; Fedorova, Ganna; Burkina, Viktoriia; Soares, Amadeu M V M; Pestana, João L T

    2017-09-01

    Organic ultraviolet filters (UV-filters) used for protection against radiation in personal care products and other materials (e.g. textiles, plastic products) are considered emerging contaminants of aquatic ecosystem. Benzophenone-3 (BP3) and 3-(4-methylbenzylidene)camphor (4-MBC) are the most commonly used organic UV-filters and have been reported in freshwater environments due to contamination through discharges from wastewater treatment plants and swimming pools or by direct contamination from recreational activities. Our aim was to evaluate the ecotoxicological effects of these UV-filters using the freshwater caddisfly Sericostoma vittatum' biochemical biomarkers and energy processing related endpoints (feeding behaviour, energy reserves and cellular metabolism). In laboratory trials, both compounds induced feeding inhibition of S. vittatum at 3.55 mg/kg of BP3 and at concentrations ≥2.57 mg/kg of 4-MBC, decreased carbohydrates content at 3.55 and 6.95 mg/kg of BP3 and 4-MBC respectively, and increased total glutathione levels at concentrations ≥1.45 and 1.35 mg/kg of BP3 and 4-MBC respectively. No significant effects were observed on endpoints associated with oxidative stress, antioxidant defences, phase II biotransformation or neurotoxicity after exposure to the two UV-filters. Our results show that environmental relevant concentrations of BP3 and 4-MBC, can negatively impact freshwater insects and demonstrate the importance of monitoring the ecological effects of organic UV-filters using non-model invertebrate species. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Sunscreens: are they beneficial for health? An overview of endocrine disrupting properties of UV-filters.

    Science.gov (United States)

    Krause, M; Klit, A; Blomberg Jensen, M; Søeborg, T; Frederiksen, H; Schlumpf, M; Lichtensteiger, W; Skakkebaek, N E; Drzewiecki, K T

    2012-06-01

    Today, topical application of sunscreens, containing ultraviolet-filters (UV-filters), is preferred protection against adverse effects of ultraviolet radiation. Evidently, use of sunscreens is effective in prevention of sunburns in various models. However, evidence for their protective effects against melanoma skin cancer is less conclusive. Three important observations prompted us to review the animal data and human studies on possible side effects of selected chemical UV-filters in cosmetics. (1) the utilization of sunscreens with UV-filters is increasing worldwide; (2) the incidence of the malignant disorder for which sunscreens should protect, malignant melanoma, is rapidly increasing and (3) an increasing number of experimental studies indicating that several UV-filters might have endocrine disruptive effects. The selected UV-filters we review in this article are benzophenone-3 (BP-3), 3-benzylidene camphor (3-BC), 3-(4-methyl-benzylidene) camphor (4-MBC), 2-ethylhexyl 4-methoxy cinnamate (OMC), Homosalate (HMS), 2-ethylhexyl 4-dimethylaminobenzoate (OD-PABA) and 4-aminobenzoic acid (PABA). The potential adverse effects induced by UV-filters in experimental animals include reproductive/developmental toxicity and disturbance of hypothalamic-pituitary-thyroid axis (HPT). Few human studies have investigated potential side effects of UV-filters, although human exposure is high as UV-filters in sunscreens are rapidly absorbed from the skin. One of the UV-filters, BP-3, has been found in 96% of urine samples in the US and several UV-filters in 85% of Swiss breast milk samples. It seems pertinent to evaluate whether exposure to UV-filters contribute to possible adverse effects on the developing organs of foetuses and children. © 2012 The Authors. International Journal of Andrology © 2012 European Academy of Andrology.

  19. Toxicity of organic UV-filters to the aquatic midge Chironomus riparius.

    Science.gov (United States)

    Campos, Diana; Gravato, Carlos; Quintaneiro, Carla; Golovko, Oksana; Žlábek, Vladimír; Soares, Amadeu M V M; Pestana, João L T

    2017-09-01

    Despite the frequent detection of organic ultraviolet-filters (UV-filters) in freshwater sediments, there is a lack of ecotoxicological data undermining a correct risk assessment for these emerging contaminants. The present study assessed the effects of three of the most commonly used UV-filters (benzophenone-3 - BP3; 3-(4-methylbenzylidene)camphor - 4-MBC and octocrylene - OC) on Chironomus riparius life history and biochemical responses. Standard ecotoxicological assays confirmed that all compounds impaired growth of C. riparius larvae and induced developmental effects such as delayed emergence and a reduction of imagoes weight. Concerning the biochemical responses analysed no evidences of oxidative damage in lipids or neurotoxicity (tested assessing acetylcholinesterase activity) were observed for any of the tested compounds. However, 4-MBC exposure induced a decrease in catalase activity and an increase in glutathione-S-transferase activity at 14.13mg/Kg while OC exposure caused an increase in total glutathione levels at 0.23 and 18.23mg/Kg. Exposure to all UV-filters tested, increased energy consumption on C. riparius with significant differences above 1.00mg/Kg for BP3, 0.09mg/Kg for 4-MBC and 2.13mg/Kg for OC. These results suggest that environmental relevant concentrations of UV-filters can cause deleterious effects to aquatic benthic species, such as C. riparius, and call for further research concerning effects of organic UV-filters on natural invertebrate communities and ecosystem functioning. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. UV filters bioaccumulation in fish from Iberian river basins

    Energy Technology Data Exchange (ETDEWEB)

    Gago-Ferrero, Pablo [Dept. of Environmental Chemistry, Institute of Environmental Assessment and Water Research (IDAEA), Spanish Council for Scientific Research (CSIC), Jordi Girona 18-26, E-08034 Barcelona (Spain); Laboratory of Analytical Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis, 15771 Athens (Greece); Díaz-Cruz, M. Silvia, E-mail: sdcqam@cid.csic.es [Dept. of Environmental Chemistry, Institute of Environmental Assessment and Water Research (IDAEA), Spanish Council for Scientific Research (CSIC), Jordi Girona 18-26, E-08034 Barcelona (Spain); Barceló, Damià [Dept. of Environmental Chemistry, Institute of Environmental Assessment and Water Research (IDAEA), Spanish Council for Scientific Research (CSIC), Jordi Girona 18-26, E-08034 Barcelona (Spain); Catalan Institute for Water Research (ICRA), Parc Científic i Tecnològic de la Universitat de Girona, C/ Emili Grahit, 101 Edifici H2O, E-17003 Girona (Spain)

    2015-06-15

    The occurrence of eight organic UV filters (UV-Fs) was assessed in fish from four Iberian river basins. This group of compounds is extensively used in cosmetic products and other industrial goods to avoid the damaging effects of UV radiation, and has been found to be ubiquitous contaminants in the aquatic ecosystem. In particular, fish are considered by the scientific community to be the most feasible organism for contamination monitoring in aquatic ecosystems. Despite that, studies on the bioaccumulation of UV-F are scarce. In this study fish samples from four Iberian river basins under high anthropogenic pressure were analysed by liquid chromatography–tandem mass spectrometry (HPLC–MS/MS). Benzophenone-3 (BP3), ethylhexyl methoxycinnamate (EHMC), 4-methylbenzylidene camphor (4MBC) and octocrylene (OC) were the predominant pollutants in the fish samples, with concentrations in the range of ng/g dry weight (d.w.). The results indicated that most polluted area corresponded to Guadalquivir River basin, where maximum concentrations were found for EHMC (241.7 ng/g d.w.). Sediments from this river basin were also analysed. Lower values were observed in relation to fish for OC and EHMC, ranging from below the limits of detection to 23 ng/g d.w. Accumulation levels of UV-F in the fish were used to calculate biota-sediment accumulation factors (BSAFs). These values were always below 1, in the range of 0.04–0.3, indicating that the target UV-Fs are excreted by fish only to some extent. The fact that the highest concentrations were determined in predators suggests that biomagnification of UV-F may take place along the freshwater food web. - Highlights: • First evidence of UV filters in fish from Iberian rivers • Biota-sediment accumulation factors (BSAFs) were always below 1. • Predator species presented higher UV-F concentrations suggesting trophic magnification.

  1. Deep Soil Carbon: The Insight into Global Carbon Estimation and Deforestation Impacts

    Science.gov (United States)

    Sangmanee, Podjanee; Dell, Bernard; Harper, Richard; Henry, David

    2015-04-01

    World carbon stocks have been dramatically changed by deforestation. The current estimation of carbon loss is based on allometric techniques assisted with satellite imagery and the assumption that, 20% of the total biomass carbon stock is below ground. However, the monitoring of soil carbon is limited to 0.3 m despite many soils being much deeper than this. For example, direct measurement of soil carbon demonstrated the occurrence of two to five times more carbon stored in deep soils of south Western Australia (SWA) compared to what would normally be reported, although the land had been deforested for 80 years. This raises important questions about the dynamics of this deeper carbon and whether it will contribute to global climate change. This paper reports the form and variation of carbon in soil at three adjacent areas at three different depths (0-1, 11-12 and 18-19 m). Techniques were developed to quantitatively and qualitatively determine small concentrations of carbon in deep soils. There were marked differences in carbon compounds with depth. Near the surface these were macromolecular organic compounds derived from lignin, polysaccharides, proteins, terpenes, whereas at depth they were low molecular weight compounds, 13-docosenamide, 13-docosenoate, xanthone, benzophenone. The deeper compounds are likely derived from the roots of the previous forest whereas the surface soils are affected by current land use. The in situ decomposition of deep roots was revealed by the pyridine compound. The variation of compounds and location of carbon in clay could imply the state of decomposition. The result demonstrated that carbon is contained in deep soils and should be considered in global carbon accounting, particularly given ongoing deforestation on deep soils.

  2. Development of palm oil-based UV-curable epoxy acrylate and urethane acrylate resins for wood coating application

    Energy Technology Data Exchange (ETDEWEB)

    Tajau, Rida; Mahmood, Mohd Hilmi; Salleh, Mek Zah; Salleh, Nik Ghazali Nik [Radiation Processing Technology Division, Malaysian Nuclear Agency (Nuclear Malaysia), Bangi, 43000 Kajang, Selangor (Malaysia); Ibrahim, Mohammad Izzat [Faculty of Science, University of Malaya (UM), 50603 Kuala Lumpur (Malaysia); Yunus, Nurulhuda Mohd [Faculty of Science and Technology, National University Malaysia (UKM), 43600 Bangi, Selangor (Malaysia)

    2014-02-12

    The trend of using renewable sources such as palm oil as raw material in radiation curing is growing due to the demand from the market to produce a more environmental friendly product. In this study, the radiation curable process was done using epoxy acrylate and urethane acrylate resins which are known as epoxidised palm olein acrylate (EPOLA) and palm oil based urethane acrylate (POBUA), respectively. The purpose of the study was to investigate curing properties and the application of this UV-curable palm oil resins for wood coating. Furthermore, the properties of palm oil based coatings are compared with the petrochemical-based compound such as ebecryl (EB) i.e. EB264 and EB830. From the experiment done, the resins from petrochemical-based compounds resulted higher degree of crosslinking (up to 80%) than the palm oil based compounds (up to 70%), where the different is around 10-15%. The hardness property from this two type coatings can reached until 50% at the lower percentage of the oligomer. However, the coatings from petrochemical-based have a high scratch resistance as it can withstand at least up to 3.0 Newtons (N) compared to the palm oil-based compounds which are difficult to withstand the load up to 1.0 N. Finally, the test on the rubber wood substrate showed that the coatings containing benzophenone photoinitiator give higher adhesion property and their also showed a higher glosiness property on the glass substrate compared to the coatings containing irgacure-819 photoinitiator. This study showed that the palm oil coatings can be a suitable for the replacement of petrochemicals compound for wood coating. The palm oil coatings can be more competitive in the market if the problems of using high percentage palm oil oligomer can be overcome as the palm oil price is cheap enough.

  3. Stability-Indicating UPLC and TLC-Densitometric Methods for Determination of Benztropine Mesylate and Its Carcinogenic Degradation Product.

    Science.gov (United States)

    Fares, Michel Y; Abdelwahab, Nada S; Abdelrahman, Maha M; Abdel-Rahman, Hamdy M

    2017-10-01

    Two accurate, precise and highly selective stability-indicating methods were adopted for simultaneous determination of benztropine mesylate (BNZ) in presence of its hepatotoxic and carcinogenic degradation product, benzophenone (BPH) either in pure form or in the pharmaceutical formulation without any preliminary separation steps. The first method is a thin layer chromatography (TLC)-densitometric method that depended on separation of BNZ from its degradate on TLC aluminum plates precoated with silica gel 60 F254 as the stationary phase using a developing system consisted of hexane:methylene chloride:triethylamine (5:5:0.6, by volume) and scanning the separated bands at 235 nm. Linear regression analysis data for the calibration plots of BNZ and BPH showed perfect linear relationships over the concentration range of 1.5-10 and 1-10 μg band-1, respectively. The second method is (UPLC) method, at which the mixture was separated on a reversed phase C8 analytical column (1.9 μm ps, 50 mm × 2.1 i.d.) using a mobile phase of acetonitrile: aqueous sodium dodecyl sulfate (50:50, v/v) Adjusted to pH = 3 with phosphoric acid, at a flow rate of 0.5 mL min-1. Quantification was achieved at 210 nm based on peak area and linear calibration curves over the concentration ranges of (20-200 μg mL-1) and (5-50 μg mL-1) for BNZ and BPH, respectively, were obtained. The investigated methods were successfully applied to available dosage form and method validation has been carried out. The results obtained by applying the proposed methods were statistically analyzed and compared with those obtained by reported one and no significant differences were obtained regarding both accuracy and precision. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  4. Vasorelaxant and cardiovascular properties of the essential oil of Pogostemon elsholtzioides.

    Science.gov (United States)

    Shiva Kumar, Arumugasamy; Jeyaprakash, Karnan; Chellappan, David Raj; Murugan, Ramar

    2017-03-06

    Pogostemon elsholtzioides Benth. (Lamiaceae) is an aromatic shrub, endemic to eastern Himalaya region. The leaves are used for treating goiter and high blood pressure (BP) by indigenous people in Arunachal Pradesh, India. Young leaves are used as vegetable and leaf decoction is also used for cough, cold and headache by some indigenous communities in Northeast India. This species is used for treating hypertension and the genus Pogostemon is rich in essential oil. Therefore, the present study was aimed at investigation of the chemical constituents, vasorelaxant and cardiovascular effects of the essential oil of P. elsholtzioides. P. elsholtzioides was collected from Pasighat, Arunachal Pradesh, India and essential oil was extracted from shade dried leaves. Essential oil was analyzed by GC-FID and GC-MS and the volatile constituents were identified. Vasorelaxant and cardiovascular properties of the essential oil were studied against phenylephrine induced contraction in isolated endothelium intact aortic preparations and by measuring systolic and diastolic BP, mean arterial pressure (MAP) and heart rate (HR) after carotid artery cannulation in Wistar rats. The essential oil was rich in sesquiterpenes and curzerene, benzophenone, α-cadinol and germacrone were major constituents. The essential oil exhibited significant vasodilation effect in phenylephrine induced contracted aortic rings. Vasorelaxant effect of the essential oil was also observed both in the presence and absence of Nitro-L-arginine methyl ester against phenylephrine-contracted aortic rings. It also induced reduction of systolic and diastolic BP, MAP and HR. Essential oil of P. elsholtzioides exhibited significant vasorelaxant effect against endothelium intact aortic preparation mediated through nitric oxide dependent pathway and also reduced BP. However, further study is needed to screen the role of calcium ions in both intracellular and extracellular pathway. Copyright © 2017 Elsevier Ireland Ltd. All

  5. Associations between urinary phenol and paraben concentrations and markers of oxidative stress and inflammation among pregnant women in Puerto Rico

    Science.gov (United States)

    Watkins, Deborah J.; Ferguson, Kelly K.; Toro, Liza V. Anzalota Del; Alshawabkeh, Akram N.; Cordero, José F.; Meeker, John D.

    2014-01-01

    Phenols and parabens are used in a multitude of consumer products resulting in ubiquitous human exposure. Animal and in vitro studies suggest that exposure to these compounds may be related to a number of adverse health outcomes, as well as potential mediators such as oxidative stress and inflammation. We examined urinary phenol (bisphenol A (BPA), triclosan (TCS), benzophenone-3 (BP-3), 2,4-dichlorophenol (24-DCP), 2,5-dichlorophenol (25-DCP)) and paraben (butyl paraben (B-PB), methyl paraben (M-PB), propyl paraben (P-PB)) concentrations measured three times during pregnancy in relation to markers of oxidative stress and inflammation among participants in the Puerto Rico Testsite for Exploring Contamination Threats (PROTECT) project. Serum markers of inflammation (c-reactive protein (CRP), IL-1β, IL-6, IL-10, and tumor necrosis factor-α (TNF-α)) were measured twice during pregnancy (n=105 subjects, 187 measurements) and urinary markers of oxidative stress (8-hydroxydeoxyguanosine (OHdG) and isoprostane) were measured three times during pregnancy (n=54 subjects, 146 measurements). We used linear mixed models to assess relationships between natural log-transformed exposure and outcome biomarkers while accounting for within individual correlation across study visits. After adjustment for urinary specific gravity, study visit, maternal pre-pregnancy BMI, and maternal education, an interquartile range (IQR) increase in urinary BPA was associated with 21% higher OHdG (p=0.001) and 29% higher isoprostane (p=0.0002), indicating increased oxidative stress. The adjusted increase in isoprostane per IQR increase in marker of exposure was 17% for BP-3, 27% for B-PB, and 20% for P-PB (all pparabens, and TCS during pregnancy may be related to oxidative stress and inflammation, potential mechanisms by which exposure to these compounds may influence birth outcomes and other adverse health effects, but additional research is needed. PMID:25435060

  6. Urinary heavy metals, phthalates, phenols, thiocyanate, parabens, pesticides, polyaromatic hydrocarbons but not arsenic or polyfluorinated compounds are associated with adult oral health: USA NHANES, 2011-2012.

    Science.gov (United States)

    Shiue, Ivy

    2015-10-01

    Links between environmental chemicals and human health have emerged over the last few decades, but the effects on oral health have been less studied. Therefore, it was aimed to study the relationships of different sets of urinary chemical concentrations and adult oral health conditions in a national and population-based setting. Data was retrieved from the United States National Health and Nutrition Examination Surveys, 2011-2012 including demographics, self-reported oral health conditions and urinary environmental chemical concentrations (one third representative sample of the study population). Chi-square test, t test, and survey-weighted logistic and multi-nominal regression modeling were performed. Of 4566 American adults aged 30-80, 541 adults (11.9 %) reported poor teeth health while 1020 adults (22.4 %) reported fair teeth. Eight hundred fifty-five people (19.1 %) claimed to have gum disease, presented with higher levels of urinary cadmium, cobalt and polyaromatic hydrocarbons. Six hundred three adults (13.3 %) had bone loss around the mouth, presented with higher levels of cadmium, nitrate, thiocyanate, propyl paraben and polyaromatic hydrocarbons. Eight hundred forty-five adults (18.5 %) had tooth loose not due to injury, presented with higher level of cadmium, thiocyanate and polyaromatic hydrocarbons. Eight hundred forty-five adults (18.5 %) with higher levels of lead, uranium, polyaromatic hydrocarbons but lower level of triclosan noticed their teeth did not look right. Three hundred fifty-one adults (7.7 %) often had aching in the mouth and 650 (14.3 %) had it occasionally, presented with higher levels of phthalates, pesticides and polyaromatic hydrocarbons. Benzophenone-3 and triclosan elicited protective effects. Regulation of environmental chemicals in prevention of adult oral health might need to be considered in future health and environmental policies.

  7. Photochemical generation of antimicrobial Ag-nanoparticles in intraocular lenses

    Science.gov (United States)

    Badur, Thorben; Kim, Hee-Cheol; Hampp, Norbert

    2017-02-01

    The antimicrobial properties of silver (Ag) nanoparticles (NP) have been investigated in depth during the last decades.[1] For cataract treatment minimal invasive surgery has become state-of-the-art. The physicians are still fighting against postoperative inflammations, such as endophthalmitis.[2] We present a novel approach to reduce these postoperative complications by equipping the hydrophilic intraocular lenses (IOL) with a Ag NP depot. As the Ag NP are completely entrapped inside the polymeric IOL no direct contact of the nanoparticles with epithelial cells may occur. Using 1-hydroxybenzotriazole (HOBt) or 7-hydroxycumarine (7HOCum) as photo reduction mediators (PRM) the formation of the Ag NP is accomplished in situ. PRM and Ag nitrate are diffused into the ready made IOL. By means of two-photon-absorption (TPA) photochemistry at λTPA = 532 nm the Ag NP generation is precisely controlled to occur inside the IOL only. At no point NP are directly exposed to the surface.[3] Interesting dependencies between the used PRM and the resulting particle size distribution or the effectiveness of the silver ion reduction inside the polymer matrix are reported. The Ag NP were prepared in the outer area of the IOL not to affect the optical properties of the ophthalmic implant. The amount of Ag ions released was determined and found to be sufficient to effectively reduce the counts of airborne germs. Besides HOBt and 7HOCum we also investigated the photo reductive properties of several other organic reagents, such as benzophenone (BP) and 4-hydroxybenzophenone (4HOBP) for the ability to produce even three-dimensional nanoparticle structures inside a polymer matrix.

  8. Collective epithelial cell sheet adhesion and migration on polyelectrolyte multilayers with uniform and gradients of compliance

    International Nuclear Information System (INIS)

    Martinez, Jessica S.; Schlenoff, Joseph B.; Keller, Thomas C.S.

    2016-01-01

    Polyelectrolyte multilayers (PEMUs) are tunable thin films that could serve as coatings for biomedical implants. PEMUs built layer by layer with the polyanion poly(acrylic acid) (PAA) modified with a photosensitive 4-(2-hydroxyethoxy) benzophenone (PAABp) group and the polycation poly(allylamine hydrochloride) (PAH) are mechanically tunable by UV irradiation, which forms covalent bonds between the layers and increases PEMU stiffness. PAH-terminated PEMUs (PAH-PEMUs) that were uncrosslinked, UV-crosslinked to a uniform stiffness, or UV-crosslinked with an edge mask or through a neutral density optical gradient filter to form continuous compliance gradients were used to investigate how differences in PEMU stiffness affect the adhesion and migration of epithelial cell sheets from scales of the fish Poecilia sphenops (Black Molly) and Carassius auratus (Comet Goldfish). During the progressive collective cell migration, the edge cells (also known as ‘leader’ cells) in the sheets on softer uncrosslinked PEMUs and less crosslinked regions of the gradient formed more actin filaments and vinculin-containing adherens junctions and focal adhesions than formed in the sheet cells on stiffer PEMUs or glass. During sheet migration, the ratio of edge cell to internal cell (also known as ‘follower’ cells) motilities were greater on the softer PEMUs than on the stiffer PEMUs or glass, causing tension to develop across the sheet and periods of retraction, during which the edge cells lost adhesion to the substrate and regions of the sheet retracted toward the more adherent internal cell region. These retraction events were inhibited by the myosin II inhibitor Blebbistatin, which reduced the motility velocity ratios to those for sheets on the stiffer PEMUs. Blebbistatin also caused disassembly of actin filaments, reorganization of focal adhesions, increased cell spreading at the leading edge, as well as loss of edge cell-cell connections in epithelial cell sheets on all

  9. Collective epithelial cell sheet adhesion and migration on polyelectrolyte multilayers with uniform and gradients of compliance

    Energy Technology Data Exchange (ETDEWEB)

    Martinez, Jessica S. [Department of Biological Science, Florida State University, Tallahassee, FL 32306 (United States); Schlenoff, Joseph B. [Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306 (United States); Keller, Thomas C.S., E-mail: tkeller@bio.fsu.edu [Department of Biological Science, Florida State University, Tallahassee, FL 32306 (United States)

    2016-08-01

    Polyelectrolyte multilayers (PEMUs) are tunable thin films that could serve as coatings for biomedical implants. PEMUs built layer by layer with the polyanion poly(acrylic acid) (PAA) modified with a photosensitive 4-(2-hydroxyethoxy) benzophenone (PAABp) group and the polycation poly(allylamine hydrochloride) (PAH) are mechanically tunable by UV irradiation, which forms covalent bonds between the layers and increases PEMU stiffness. PAH-terminated PEMUs (PAH-PEMUs) that were uncrosslinked, UV-crosslinked to a uniform stiffness, or UV-crosslinked with an edge mask or through a neutral density optical gradient filter to form continuous compliance gradients were used to investigate how differences in PEMU stiffness affect the adhesion and migration of epithelial cell sheets from scales of the fish Poecilia sphenops (Black Molly) and Carassius auratus (Comet Goldfish). During the progressive collective cell migration, the edge cells (also known as ‘leader’ cells) in the sheets on softer uncrosslinked PEMUs and less crosslinked regions of the gradient formed more actin filaments and vinculin-containing adherens junctions and focal adhesions than formed in the sheet cells on stiffer PEMUs or glass. During sheet migration, the ratio of edge cell to internal cell (also known as ‘follower’ cells) motilities were greater on the softer PEMUs than on the stiffer PEMUs or glass, causing tension to develop across the sheet and periods of retraction, during which the edge cells lost adhesion to the substrate and regions of the sheet retracted toward the more adherent internal cell region. These retraction events were inhibited by the myosin II inhibitor Blebbistatin, which reduced the motility velocity ratios to those for sheets on the stiffer PEMUs. Blebbistatin also caused disassembly of actin filaments, reorganization of focal adhesions, increased cell spreading at the leading edge, as well as loss of edge cell-cell connections in epithelial cell sheets on all

  10. Occurrence of organic wastewater and other contaminants in cave streams in northeastern Oklahoma and northwestern Arkansas

    Science.gov (United States)

    Bidwell, Joseph R.; Becker, C.; Hensley, S.; Stark, R.; Meyer, M.T.

    2010-01-01

    The prevalence of organic wastewater compounds in surface waters of the United States has been reported in a number of recent studies. In karstic areas, surface contaminants might be transported to groundwater and, ultimately, cave ecosystems, where they might impact resident biota. In this study, polar organic chemical integrative samplers (POCISs) and semipermeable membrane devices (SPMDs) were deployed in six caves and two surface-water sites located within the Ozark Plateau of northeastern Oklahoma and northwestern Arkansas in order to detect potential chemical contaminants in these systems. All caves sampled were known to contain populations of the threatened Ozark cavefish (Amblyopsis rosae). The surface-water site in Oklahoma was downstream from the outfall of a municipal wastewater treatment plant and a previous study indicated a hydrologic link between this stream and one of the caves. A total of 83 chemicals were detected in the POCIS and SPMD extracts from the surface-water and cave sites. Of these, 55 chemicals were detected in the caves. Regardless of the sampler used, more compounds were detected in the Oklahoma surface-water site than in the Arkansas site or the caves. The organic wastewater chemicals with the greatest mass measured in the sampler extracts included sterols (cholesterol and ??-sitosterol), plasticizers [diethylhexylphthalate and tris (2-butoxyethyl) phosphate], the herbicide bromacil, and the fragrance indole. Sampler extracts from most of the cave sites did not contain many wastewater contaminants, although extracts from samplers in the Oklahoma surfacewater site and the cave hydrologically linked to it had similar levels of diethylhexyphthalate and common detections of carbamazapine, sulfamethoxazole, benzophenone, N-diethyl-3-methylbenzamide (DEET), and octophenol monoethoxylate. Further evaluation of this system is warranted due to potential ongoing transport of wastewaterassociated chemicals into the cave. Halogenated organics

  11. Predictors and Variability of Repeat Measurements of Urinary Phenols and Parabens in a Cohort of Shanghai Women and Men

    Science.gov (United States)

    Buckley, Jessie P.; Yang, Gong; Liao, Linda M.; Satagopan, Jaya; Calafat, Antonia M.; Matthews, Charles E.; Cai, Qiuyin; Ji, Bu-Tian; Cai, Hui; Wolff, Mary S.; Rothman, Nathaniel; Zheng, Wei; Xiang, Yong-Bing; Shu, Xiao-Ou; Gao, Yu-Tang; Chow, Wong-Ho

    2014-01-01

    Background: Exposure to certain phenols is ubiquitous because of their use in many consumer and personal care products. However, predictors of exposure have not been well characterized in most populations. Objectives: We sought to identify predictors of exposure and to assess the reproducibility of phenol concentrations across serial spot urine samples among Chinese adults. Methods: We measured 2,4-dichlorophenol, 2,5-dichlorophenol, butyl paraben, methyl paraben, propyl paraben, benzophenone-3, bisphenol A, and triclosan in urine collected during 1997–2006 from 50 participants of the Shanghai Women’s Health Study cohort and during 2002–2006 from 50 participants of the Shanghai Men’s Health Study cohort. We investigated predictors of concentrations using the Satterthwaite t-test, and assessed reproducibility among serial samples using intraclass correlation coefficients (ICCs) and Spearman correlation coefficients (SCCs). Results: Creatinine-corrected phenol concentrations were generally higher among women than men. Participants who had taken medicine within the previous 24 hr had higher concentrations of propyl paraben. Cigarette smoking was associated with lower concentrations of propyl and methyl parabens among men. Bottled water consumption was associated with higher bisphenol A, 2,4-dichlorophenol, and 2,5-dichlorophenol concentrations among women. Among men, reproducibility across serial samples was moderate for 2,4-dichlorophenol and 2,5-dichlorophenol (ICC = 0.54–0.60, SCC = 0.43–0.56), but lower for other analytes (ICC = 0.20–0.29). Reproducibility among women was low (ICC = 0.13–0.39), but increased when restricted to morning-only urine samples. Conclusions: Among these 100 Shanghai residents, urinary phenol concentrations varied by sex, smoking, and consumption of bottled water. Our results suggest that a single urine sample may be adequate for ranking exposure to the precursors of 2,4-dichlorophenol and 2,5-dichlorophenol among men and

  12. Phenols and parabens in relation to reproductive and thyroid hormones in pregnant women.

    Science.gov (United States)

    Aker, Amira M; Watkins, Deborah J; Johns, Lauren E; Ferguson, Kelly K; Soldin, Offie P; Anzalota Del Toro, Liza V; Alshawabkeh, Akram N; Cordero, José F; Meeker, John D

    2016-11-01

    Phenols and parabens are ubiquitous environmental contaminants. Evidence from animal studies and limited human data suggest they may be endocrine disruptors. In the current study, we examined associations of phenols and parabens with reproductive and thyroid hormones in 106 pregnant women recruited for the prospective cohort, "Puerto Rico Testsite for Exploring Contamination Threats (PROTECT)". Urinary exposure biomarkers (bisphenol A, triclosan, benzophenone-3, 2,4-dichlorophenol, 2,5-dichlorophenol, butyl, methyl and propyl paraben) and serum hormone levels (estradiol, progesterone, sex hormone-binding globulin (SHBG), free triiodothyronine (FT3), free thyroxine (FT4) and thyroid stimulating hormone) were measured at up to two time points during pregnancy (16-20 weeks and 24-28 weeks). We used linear mixed models to assess relationships between exposure biomarkers and hormone levels across pregnancy, controlling for urinary specific gravity, maternal age, BMI and education. In sensitivity analyses, we evaluated cross-sectional relationships between exposure and hormone levels stratified by study visit using linear regression. An IQR increase in methyl paraben was associated with a 7.70% increase (95% CI 1.50, 13.90) in SHBG. Furthermore, an IQR increase in butyl paraben as associated with an 8.46% decrease (95% CI 16.92, 0.00) in estradiol, as well as a 9.34% decrease (95% CI -18.31,-0.38) in estradiol/progesterone. Conversely, an IQR increase in butyl paraben was associated with a 5.64% increase (95% CI 1.26, 10.02) in FT4. Progesterone was consistently negatively associated with phenols, but none reached statistical significance. After stratification, methyl and propyl paraben were suggestively negatively associated with estradiol at the first time point (16-20 weeks), and suggestively positively associated with estradiol at the second time point (24-28 weeks). Within this ongoing birth cohort, certain phenols and parabens were associated with altered

  13. Removal of micro pollutants using activated biochars and powdered activated carbon in water

    Science.gov (United States)

    Kim, E.; Jung, C.; Han, J.; Son, A.; Yoon, Y.

    2015-12-01

    Recent studies have suggested that emerging micropollutants containing endocrine disrupting compounds (EDCs); bisphenol A, 17 α-ethinylestradiol, 17 β-estradiol and pharmaceuticals and personal care products (PPCPs); sulfamethoxazole, carbamazepine, ibuprofen, atenolol, benzophenone, benzotriazole, caffeine, gemfibrozil, primidone, triclocarban in water have been linked to ecological impacts, even at trace concentrations (sub ug/L). Adsorption with adsorbent such as activated carbon having a high-binding affinity has been widely used to eliminate various contaminants in the aqueous phase. Recently, an efficient treatment strategy for EDCs and PPCPs has been considered by using cost effective adsorption particularly with biochar in aqueous environmentIn this study, the objective of this study is to determine the removal of 13 target EDCs/PPCPs having different physicochemical properties by a biochar at various water quality conditions (pH (3.5, 7, and 10.5), background ions (NaCl, CaCl2, Na₂SO₄), ionic strength, natural organic matter (NOM)). The activated biochar produced in a laboratory was also characterized by using conventional analytical methods as well as advanced solid-state nuclear magnetic resonance (NMR) techniques, which answer how these properties determine the competitive adsorption characteristics and mechanisms of EDCs and PPCPs.The primary findings suggest that micropollutants can be removed more effectively by the biochar than the commercially available powdered activated carbon. At pH values below the pKa of each compound, the adsorption affinity toward adsorbents increased significantly with the pH, whereas the adsorption affinity decreased significantly at the pH above the pKa values. Na+ did not significantly impact adsorption, while increasing the concentration of Ca2+lead to increase in the adsorption of these micropollutants. NOM adsorption with humic acids on these adsorbents disturbed adsorption capacity of the target compounds as

  14. Tailor-making a protein a-derived domain for efficient site-specific photocoupling to Fc of mouse IgG₁.

    Directory of Open Access Journals (Sweden)

    Feifan Yu

    Full Text Available Affinity proteins binding to antibody constant regions have proved to be invaluable tools in biotechnology. Here, protein engineering was used to expand the repertoire of available immunoglobulin binding proteins via improvement of the binding strength between the widely used staphylococcal protein A-derived Z domain and the important immunoglobulin isotype mouse IgG₁ (mIgG₁. Addressing seven positions in the 58-residue three-helix bundle Z domain by single or double amino acid substitutions, a total of 170 variants were individually constructed, produced in E. coli and tested for binding to a set of mouse IgG₁ monoclonal antibodies (mAbs. The best variant, denoted Z(F5I corresponding to a Phe to Ile substitution at position 5, showed a typical ten-fold higher affinity than the wild-type as determined by biosensor technology. Eight amino acid positions in the Z(F5I variant were separately mutated to cysteine for incorporation of a photoactivable maleimide-benzophenone (MBP group as a probe for site-specific photoconjugation to Fc of mIgG₁, The best photocoupling efficiency to mIgG₁ Fc was seen when the MBP group was coupled to Cys at position 32, resulting in adduct formation to more than 60% of all heavy chains, with no observable non-selective conjugation to the light chains. A similar coupling yield was obtained for a panel of 19 different mIgG₁ mAbs, indicating a general characteristic. To exemplify functionalization of a mIgG₁ antibody via site-specific biotinylation, the Z(F5I-Q32C-MBP protein was first biotinylated using an amine reactive reagent and subsequently photoconjugated to an anti-human interferon-gamma mIgG₁ mAb. When comparing the specific antigen binding ability of the probe-biotinylated mAb to that of the directly biotinylated mAb, a significantly higher bioactivity was observed for the sample biotinylated using the Z(F5I-Q32C-MBP probe. This result indicates that the use of a site-specific and affinity probe

  15. Engineered Biosynthesis of Plant Polyketides: Structure-Based and Precursor-Directed Approach

    Science.gov (United States)

    Abe, Ikuro

    Pentaketide chromone synthase (PCS) and octaketide synthase (OKS) are novel plant-specific type III polyketide synthases (PKSs) obtained from Aloe arborescens. Recombinant PCS expressed in Escherichia coli catalyzes iterative condensations of five molecules of malonyl-CoA to produce a pentaketide 5,7-dihydroxy-2-methylchromone, while recombinant OKS carries out sequential condensations of eight molecules of malonyl-CoA to yield octaketides SEK4 and SEK4b, the longest polyketides produced by the structurally simple type III PKS. The amino acid sequences of PCS and OKS are 91% identical, sharing 50-60% identity with those of other chalcone synthase (CHS) superfamily type III PKSs of plant origin. One of the most characteristic features is that the conserved active-site Thr197 of CHS (numbering in Medicago sativa CHS) is uniquely replaced with Met207 in PCS and with Gly207 in OKS, respectively. Site-directed mutagenesis and X-ray crystallographic analyses demonstrated that the chemically inert single residue lining the active-site cavity controls the polyketide chain length and the product specificity depending on the steric bulk of the side chain. On the basis of the crystal structures, an F80A/Y82A/M207G triple mutant of the pentaketide-producing PCS was constructed and shown to catalyze condensations of nine molecules of malonyl-CoA to produce an unnatural novel nonaketide naphthopyrone, whereas an N222G mutant of the octaketides-producing OKS yielded a decaketide benzophenone SEK15 from ten molecules of malonyl-CoA. On the other hand, the type III PKSs exhibited broad substrate specificities and catalytic potential. OKS accepted p-coumaroyl-CoA as a starter substrate to produce an unnatural novel C19 hexaketide stilbene and a C21 heptaketide chalcone. Remarkably, the C21 chalcone-forming activity was dramatically increased in the structure-guided OKS N222G mutant. In addition, OKS N222G mutant also yielded unnatural novel polyketides from phenylacetyl-CoA and

  16. Removal of micropollutants from aerobically treated grey water via ozone and activated carbon.

    Science.gov (United States)

    Hernández-Leal, L; Temmink, H; Zeeman, G; Buisman, C J N

    2011-04-01

    Ozonation and adsorption onto activated carbon were tested for the removal micropollutants of personal care products from aerobically treated grey water. MilliQ water spiked with micropollutants (100-1600 μgL(-1)) was ozonated at a dosing rate of 1.22. In 45 min, this effectively removed (>99%): Four parabens, bisphenol-A, hexylcinnamic aldehyde, 4-methylbenzylidene-camphor (4MBC), benzophenone-3 (BP3), triclosan, galaxolide and ethylhexyl methoxycinnamate. After 60 min, the removal efficiency of benzalkonium chloride was 98%, tonalide and nonylphenol 95%, octocrylene 92% and 2-phenyl-5-benzimidazolesulfonic acid (PBSA) 84%. Ozonation of aerobically treated grey water at an applied ozone dose of 15 mgL(-1), reduced the concentrations of octocrylene, nonylphenol, triclosan, galaxolide, tonalide and 4-methylbenzylidene-camphor to below limits of quantification, with removal efficiencies of at least 79%. Complete adsorption of all studied micropollutants onto powdered activated carbon (PAC) was observed in batch tests with milliQ water spiked with 100-1600 μgL(-1) at a PAC dose of 1.25 gL(-1) and a contact time of 5 min. Three granular activated carbon (GAC) column experiments were operated to treat aerobically treated grey water. The operation of a GAC column with aerobically treated grey water spiked with micropollutants in the range of 0.1-10 μgL(-1) at a flow of 0.5 bed volumes (BV)h(-1) showed micropollutant removal efficiencies higher than 72%. During the operation time of 1728 BV, no breakthrough of TOC or micropollutants was observed. Removal of micropollutants from aerobically treated grey water was tested in a GAC column at a flow of 2 BVh(-1). Bisphenol-A, triclosan, tonalide, BP3, galaxolide, nonylphenol and PBSA were effectively removed even after a stable TOC breakthrough of 65% had been reached. After spiking the aerobically treated effluent with micropollutants to concentrations of 10-100 μgL(-1), efficient removal to below limits of quantification

  17. Ionic Liquids: Radiation Chemistry, Solvation Dynamics and Reactivity Patterns

    International Nuclear Information System (INIS)

    Wishart, J.F.

    2011-01-01

    , which need to be quantified for the successful use under radiolytic conditions. Electron solvation dynamics in ILs are measured directly when possible and estimated using proxies (e.g. coumarin-153 dynamic emission Stokes shifts or benzophenone anion solvation) in other cases. Electron reactivity is measured using ultrafast kinetics techniques for comparison with the solvation process.

  18. Potential of Central, Eastern and Western Africa Medicinal Plants for Cancer Therapy: Spotlight on Resistant Cells and Molecular Targets

    Directory of Open Access Journals (Sweden)

    Armelle T. Mbaveng

    2017-06-01

    , two benzophenones: guttiferone E (26 and isoxanthochymol (30, the isoflavonoid 6α-hydroxyphaseollidin (9, the naphthyl butenone guieranone A (25, two naphthoquinones: 2-acetylfuro-1,4-naphthoquinone (4 and plumbagin (37 and xanthone V1 (46. However, only few research activities in the African continent focus on cytotoxic drug discovery from botanicals. The present review is expected to stimulate further scientific efforts to better valorize the African flora.

  19. Geminate free radical processes and magnetic field effects

    International Nuclear Information System (INIS)

    Eveson, Robert W.

    2000-01-01

    introduction to the physical properties of simple micelles, the media for the all the magnetic field effect work. Low field effect measurements are then presented as function of micelle size for both anionic and non-ionic micelles, radical pair type and temperature for the benzophenone-surfactant derived radical pair. These are accounted for quantitatively by a simple model for the radical pair motion inside of the micelle. Completing the thesis is a brief comparison of the results with current theories of the low field effect and a discussion on their relevance to biological systems. (author)

  20. Reaction of diazepam and related benzodiazepines with chlorine. Kinetics, transformation products and in-silico toxicological assessment.

    Science.gov (United States)

    Carpinteiro, Inmaculada; Rodil, Rosario; Quintana, José Benito; Cela, Rafael

    2017-09-01

    In this work, the reaction of four benzodiazepines (diazepam, oxazepam, nordazepam and temazepam) during water chlorination was studied by means of liquid chromatography-quadrupole-time of flight-mass spectrometry (LC-QTOF-MS). For those compounds that showed a significant degradation, i.e. diazepam, oxazepam and nordazepam, parameters affecting to the reaction kinetics (pH, chlorine and bromide level) were studied in detail and transformation products were tentatively identified. The oxidation reactions followed pseudofirst-order kinetics with rate constants in the range of 1.8-42.5 M -1  s -1 , 0.13-1.16 M -1  s -1 and 0.04-20.4 M -1  s -1 corresponding to half-life values in the range of 1.9-146 min, 1.8-87 h and 2.5-637 h for oxazepam, nordazepam and diazepam, respectively, depending of the levels of studied parameters. Chlorine and pH affected significantly the reaction kinetics, where an increase of the pH resulted into a decrease of the reaction rate, whereas higher chlorine dosages led to faster kinetics, as expected in this case. The transformation of the studied benzodiazepines occurs mainly at the 1,4-diazepine 7-membered-ring, resulting in ring opening to form benzophenone derivatives or the formation of a 6-membered pyrimidine ring, leading to quinazoline derivatives. The formation of these by-products was also tested in real surface water samples observing kinetics of oxazepam degradation slower in river than in creek water, while the degradation of the two other benzodiazepines occurred only in the simpler sample (creek water). Finally, the acute and chronical toxicity and mutagenicity of precursors and transformation products were estimated using quantitative structure-activity relationship (QSAR) software tools: Ecological Structure Activity Relationships (ECOSAR) and Toxicity Estimation Software Tool (TEST), finding that some transformation products could be more toxic/mutagenic than the precursor drug, but additional test would be needed

  1. The effects of binary UV filter mixtures on the midge Chironomus riparius

    International Nuclear Information System (INIS)

    Ozáez, Irene; Morcillo, Gloria; Martínez-Guitarte, José-Luis

    2016-01-01

    Organic ultraviolet (UV) filters are used in a wide variety of products, including cosmetics, to prevent damage from UV light in tissues and industrial materials. Their extensive use has raised concerns about potential adverse effects in human health and aquatic ecosystems that accumulate these pollutants. To increase sun radiation protection, UV filters are commonly used in mixtures. Here, we studied the toxicity of binary mixtures of 4-methylbenzylidene camphor (4MBC), octyl-methoxycinnamate (OMC), and benzophenone-3 (BP-3), by evaluating the larval mortality of Chironomus riparius. Also molecular endpoints have been analyzed, including alterations in the expression levels of a gene related with the endocrine system (EcR, ecdysone receptor) and a gene related with the stress response (hsp70, heat shock protein 70). The results showed that the mortality caused by binary mixtures was similar to that observed for each compound alone; however, some differences in LC50 were observed between groups. Gene expression analysis showed that EcR mRNA levels increased in the presence of 0.1 mg/L 4MBC but returned to normal levels after exposure to mixtures of 4MBC with 0.1, 1, and 10 mg/L of BP-3 or OMC. In contrast, the hsp70 mRNA levels increased after exposure to the combinations tested of 4MBC and BP-3 or OMC mixtures. These data suggest that 4MBC, BP-3, and OMC may have antagonist effects on EcR gene transcription and a synergistic effect on hsp70 gene activation. This is the first experimental study to show the complex patterned effects of UV filter mixtures on invertebrates. The data suggest that the interactions within these chemicals mixtures are complex and show diverse effects on various endpoints. - Highlights: • Chironomus riparius is sensitive to UV filter binary mixtures. • UV filters binary mixtures show antagonism on survival of 4th instar larvae. • BP-3 and OMC antagonize the stimulatory effect of 4MBC on EcR gene. • 4MBC, OMC, and BP-3 induce hsp70

  2. Irradiated polymeric films and its possible application for radiation dosimetry

    International Nuclear Information System (INIS)

    Elkady, A.A.M.A.

    2002-01-01

    The aim of the present thesis is the development of a new polymeric films, laboratory prepared by sample uncouthly methods through dying them with different types of dyes. First unit containing three forms were prepared by casting polymeric solution of poly (vinyl chloride). First film was prepared by dying poly ( vinyl chloride ) film with eosin dye. This flexible plastic film dosimeter is bleached when exposed to gamma ray photons at low doses (2-7 kGy) indicating their suitability for eventual application in food irradiation processing. Also, another polyvinyl chloride film contain a Ph indicating dye namely methyl red undergo bleaching in the rang of (20-120 kGy) indicating their suitability for eventual application in sterilization. The third film was a Ph indicating dye cresol red dyed polyvinyl chloride in the presence of CI- containing substance (E.g.Chloralhydrate). This film have the advantage of clear visual in color at high dose gamma radiation. This film was developed using the phenomenon of HCl generation from the CI- containing substance upon irradiation. The produced HCl in turn changes the color of the indicator contained in the polymer. The Dosimetric parameters e.g. dose response, effect of relative humidity and temperature during irradiation on response as well as pre-and post-irradiation stability of all above films are discussed. In second unit, the film was prepared by sandwiching the radiochromic film (nylon 66) containing (Hexa-hydroxyethyl pararosaniline) by two layers of polyvinyl chloride containing UV absorption material namely (2-hydroxy-4n-octoxy-benzophenone) to improve the stability of this famous film towards UV-radiation. Finally, a mixed dyes of ph indicating dyes bromophenol red and cresol red dying a poly vinyl alcohol in the presence of chloral hydrate were prepared. This film exhibit color changes from original color (bagel), yellow to red. The useful dose range of this is (5-50 kGy) indicate its suitability for eventual

  3. The effects of binary UV filter mixtures on the midge Chironomus riparius

    Energy Technology Data Exchange (ETDEWEB)

    Ozáez, Irene; Morcillo, Gloria; Martínez-Guitarte, José-Luis, E-mail: jlmartinez@ccia.uned.es

    2016-06-15

    Organic ultraviolet (UV) filters are used in a wide variety of products, including cosmetics, to prevent damage from UV light in tissues and industrial materials. Their extensive use has raised concerns about potential adverse effects in human health and aquatic ecosystems that accumulate these pollutants. To increase sun radiation protection, UV filters are commonly used in mixtures. Here, we studied the toxicity of binary mixtures of 4-methylbenzylidene camphor (4MBC), octyl-methoxycinnamate (OMC), and benzophenone-3 (BP-3), by evaluating the larval mortality of Chironomus riparius. Also molecular endpoints have been analyzed, including alterations in the expression levels of a gene related with the endocrine system (EcR, ecdysone receptor) and a gene related with the stress response (hsp70, heat shock protein 70). The results showed that the mortality caused by binary mixtures was similar to that observed for each compound alone; however, some differences in LC50 were observed between groups. Gene expression analysis showed that EcR mRNA levels increased in the presence of 0.1 mg/L 4MBC but returned to normal levels after exposure to mixtures of 4MBC with 0.1, 1, and 10 mg/L of BP-3 or OMC. In contrast, the hsp70 mRNA levels increased after exposure to the combinations tested of 4MBC and BP-3 or OMC mixtures. These data suggest that 4MBC, BP-3, and OMC may have antagonist effects on EcR gene transcription and a synergistic effect on hsp70 gene activation. This is the first experimental study to show the complex patterned effects of UV filter mixtures on invertebrates. The data suggest that the interactions within these chemicals mixtures are complex and show diverse effects on various endpoints. - Highlights: • Chironomus riparius is sensitive to UV filter binary mixtures. • UV filters binary mixtures show antagonism on survival of 4th instar larvae. • BP-3 and OMC antagonize the stimulatory effect of 4MBC on EcR gene. • 4MBC, OMC, and BP-3 induce hsp70

  4. Migration of plasticizers from poly(vinyl chloride) and multilayer infusion bags using selective extraction and GC-MS.

    Science.gov (United States)

    Haned, Zohra; Moulay, Saad; Lacorte, Silvia

    2018-04-12

    Flexible poly(vinyl chloride) (PVC) is widely used in the pharmaceutical industry for the manufacture of medical devices (tubes, probes, bags, primary packaging, etc.). The objective of the present study was to develop a procedure to evaluate the migration potential of nine plastic additives in aqueous infusion bags (NaCl 0.9% and glucose 5%): five phthalates, one adipate, two alkylphenols, and benzophenone. Two types of materials were analyzed: (i) new and outdated plasticized PVC (containing 40% of diethylhexyl phthalate DEHP); and (ii) tri-laminate polyethylene-polyamide-polypropylene, a multilayer material presumably exempt from DEHP. In addition, we evaluated the migration of plasticizers from PVC raw materials (film and grain) under controlled conditions to compare the migration levels according to Regulation 2011/10. Solid phase extraction and liquid-liquid extraction with gas-chromatography coupled to mass spectrometry were used in all tests. The migration of DEHP in PVC grain exceeded the maximum regulated level of 5000 μg/kg, whereas the levels were much lower in films. In new PVC bags, DEHP was the only compound detected at 4.31 ± 0.5 μg/L in NaCl 0.9% and 4.29 ± 0.25 μg/L in glucose 5% serums, whereas the levels increased 10 times in three-year shelf-life bags. In multilayer bags, DEHP was not found but instead, two plasticizers were detected namely dibuthylphthalate (DBP) and diethylphthalate (DEP) at 0.7 ± 0.1 μg/L and 4.14 ± 0.6 μg/L, respectively. These plasticizers are not mentioned as additives allowed in materials intended for parenteral use (European Pharmacopoeia 8.0, 3.1.5. and 3.1.6.). Caprolactam was tentatively identified and could have stemmed from the polyamide of the multilayer composite. The levels of phthalates remained low but not negligible and might constitute a risk to public health in the case of reiterative infusions. Copyright © 2018. Published by Elsevier B.V.

  5. Aqueous reactions of triplet excited states with allylic compounds

    Science.gov (United States)

    Kaur, R.; Anastasio, C.; Hudson, B. M.; Tantillo, D. J.

    2016-12-01

    Triplet excited states of dissolved organic matter react with several classes of aromatic organics such as phenols, anilines, sulfonamide antibiotics and phenylurea herbicides. Aqueous triplets appear to be among the most important oxidants for atmospheric phenols in regions with biomass burning, with phenol lifetimes on the order of a few hours to a day. However, little is known of the reactions of triplets with other classes of organic compounds. Recent work from our group shows that triplets react rapidly with several biogenic volatile organic compounds (BVOCs), such as methyl jasmonate, cis-3-hexenyl acetate, and cis-3-hexen-1-ol. However, there are only a few rate constants for aqueous reactions between alkenes such as these and triplet excited states. For our work, we refer to these and similar alkenes which have hydrogen(s) attached to a carbon adjacent to the double bond, as allylic compounds. To better assess the importance of triplets as aqueous oxidants, we measured second-order rate constants (kAC+3BP*) for a number of allylic compounds (ACs) with the triplet state of benzophenone; then established a quantitative structure-activity relationship (QSAR) between kAC+3BP* and computed oxidation potential of the ACs (R2 =0.65). Using the QSAR, we estimated the rate constants for triplets with some allylic isoprene and limonene oxidation products that have high Henry's law constants (KH>103 M atm-1). Hydroxylated limonene products and the delta-isomers of isoprene hydroxyhydroperoxides (δ4ISOPOOH) and hydroxynitrates (δ4ISONO2) were faster with predicted kAC+3BP* values ranging between (0.5-3.5) x 109 M-1-s-1 whereas the beta-isomers of ISOPOOH and ISONO2 were slower (kAC+3BP* gas and aqueous hydroxyl radical and ozone, triplets in fog could account for up to 20 % of the measured loss of these compounds in the atmosphere. We are currently evaluating the importance of triplets in particulate matter (PM) which can have much higher concentrations of triplet

  6. Analytical strategy based on the use of liquid chromatography and gas chromatography with triple-quadrupole and time-of-flight MS analyzers for investigating organic contaminants in wastewater.

    Science.gov (United States)

    Pitarch, E; Portolés, T; Marín, J M; Ibáñez, M; Albarrán, F; Hernández, F

    2010-08-01

    pollutants that did not form a part of the previous list of target contaminants were identified in the samples, because of the high sensitivity of TOF MS in full-spectrum acquisition mode and the valuable accurate-mass information provided by these instruments. The insecticide diazinon, the fungicide diphenylamide, the UV filter benzophenone, N-butylbenzenesulfonamide (N-BBSA), the insect repellent diethyltoluamide, caffeine, and the pharmaceuticals erythromycin, benzenesulfonanilide, ibuprofen, atenolol, and paracetamol were some of the compounds identified in the water samples analyzed.

  7. Phytochemical Analysis, Antioxidant, Anti-Hyperglycemic and Antituberculosis Activities of Phylogenetically Related Garcinia mangostana (Mangosteen) and Garcinia hombroniana (Seashore Mangosteen)

    International Nuclear Information System (INIS)

    Jamila, N.; Kim, K.S.; Khan, A.A.; Khan, S.N

    2016-01-01

    Species of genus Garcinia belonging to family Clusiaceae are traditionally known for the treatment of ulcer, gonorrhea, leucorrhoea and abdominal pain. This genus is also reported to be a rich source of xanthones, benzophenones, flavonoids, biflavonoids and triterpenes showing significant pharmacological activities. Garcinia mangostana L. (mangosteen) and Garcinia hombroniana Pierre (seashore mangosteen) are evergreen tropical trees grown in Malaysia, Indonesia, Thailand and other tropical countries. The fruits of G. mangostana (queen of fruits), and roots and leaves decoction of G. hombroniana are commonly used for skin allergies, infections after childbirth, trauma and diarrhea. This study aimed to evaluate the bark and fruit extracts of G. mangostana and G. hombroniana for phytochemicals analysis, total phenolic and flavonoid contents, antioxidant, anti-hyperglycemic and antituberculosis activities. Total phenolic contents were evaluated by Folin-Ciocalteu reagent colorimetric method. For antioxidant activities, radical scavenging assays of 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2-azino-bis-3-ethyl benzthiazoline-6-sulphonic acid (ABTS), and ferric ion reducing antioxidant power (FRAP) were used. Anti-hyperglycemic activity was determined using a-glucosidase and a-amylase enzymes. In quantitative phytochemical analysis, the extracts of G. mangostana showed significantly higher content of phenolics (3498.7 micro M GAE/g (gallic acid equivalent per gram), ethyl acetate; bark), carbohydrates (14.2 g/100g, aqueous; fruit) and reducing sugars (13.9 g/100g, aqueous; fruit). Also, in antioxidant activities, G. mangostana showed comparatively high activities with the ethyl acetate extract as the most potent showing IC50 2.78 micro g/ml in DPPH, 1.19 micro g/ml in ABTS, and 8742.7 micro M TE/g in FRAP assays. G. mangostana was also more potent in anti-hyperglycemic properties (IC50 182.9 micro g/ml, a-glucosidase, 247.8 micro g/ml, a-amylase) compared to G. hombroniana

  8. KAJIAN TERHADAP PROSPEK PENGEMBANGAN BAHAN BIOAKTIF BUAH MAHKOTA DEWA (P. Macrocarpa SEBAGAI KANDIDAT NEW CHEMICAL ENTITY (NCE UNTUK PENGOBATAN KANKER (SITOSTATIKA

    Directory of Open Access Journals (Sweden)

    Vivi Lisdawati

    2012-11-01

    Full Text Available Abstract. In the last few years there are tendency for cancer study to develop in discovery of new chemical entity (NCE for new drugs. The needed of NCE based on reality that cancer therapy reaches a resistant level very fast. By developing NCE, multiply cancer drugs can be used at one therapy and be implemented as a solution to inhibit a resistant level and very useful in recovery time. Natural products are the most important sources of NCE and could be used from plants, animals or minerals. Most of the natural products used in Indonesia are recognized from plants. Plants secondary metabolites show promise for cancer chemoprevention, which has been defined as the use of non cytotoxic nutrient or pharmacological agents to enhance intrinsic physiological mechanism that protect the organism against mutant clones of malignant cells. The study of plants secondary metabolites is nowadays moved from improvement of the empiric activity to meet the relationship between the structures of chemical compounds to its pharmacology activities. Development of study on plants in Indonesia is also pointed on discovery of NCE for new drugs of cancer and the cellular cytotoxic mechanism of the biological activity. Extracts from the fruit of P. macrocarpa is one of the sources for NCE of cancer drug in Indonesia. Some isolates already isolated from the extracts, i.e. lignan compound Ci9H2o06: 5-[4(4-Methoxy-phenyl-tetrahydrofurof3,4-cJfuran-l-yl]-benzene-1,2,3-triol and benzophenon compound: 4', 6-dihiroksi-4-metoksibenzofenon-2-0-glukoside. Using chemotaxonomy Dahlgren and Conqruist system approached indicate that these compounds have anti proliferation and pro apoptotic as their cytotoxic activities. The pharmacology activities from the fruit extracts also have been studied. For cytotoxic activities, the fruit extracts showed ICSo values from 5 to 7.71. jug/ml for leukemia LI 210 cell line; and IC50 values 196.74 jug/ml for HeLa cell line. The extracts also showed

  9. Groundwater-quality characteristics for the Wyoming Groundwater-Quality Monitoring Network, November 2009 through September 2012

    Science.gov (United States)

    Boughton, Gregory K.

    2014-01-01

    , manganese, boron, and selenium exceeded WDEQ Class II agriculture groundwater standards in some samples. Measurements of pH and concentrations of sulfate, dissolved solids, aluminum, boron, and selenium exceeded WDEQ Class III livestock groundwater standards in some samples. The concentrations of dissolved solids in two samples exceeded the WDEQ Class IV industry groundwater standard. Measurements of pH and concentrations of dissolved solids, aluminum, iron, manganese, and selenium exceeded WDEQ Class special (A) fish and aquatic life groundwater standards in some samples. Stable isotopes of hydrogen and oxygen measured in water samples were compared to the Global Meteoric Water Line and Local Meteoric Water Lines. Results indicated that recharge to all of the wells was derived from precipitation and that the water has undergone some fractionation, possibly because of evaporation. Concentrations of organic compounds did not exceed any State or Federal water-quality standards. Few volatile organic compounds were detected in samples, whereas gasoline range organics, diesel range organics, and methane were detected most frequently. Concentrations of wastewater compounds did not exceed any State or Federal water-quality standards. The compounds N,N-diethyl-meta-toluamide (DEET), benzophenone, and phenanthrene were detected most frequently. Bacteria samples were collected, processed, incubated, and enumerated in the field or at the U.S. Geological Survey Wyoming-Montana Water Science Center. Total coliforms and Escherichia coli were detected in some samples.

  10. Identification and quantification of the migration of chemicals from plastic baby bottles used as substitutes for polycarbonate.

    Science.gov (United States)

    Simoneau, C; Van den Eede, L; Valzacchi, S

    2012-01-01

    Community positive list, which means that those should not be found even in the first migration. Such substances included 2,6-di-isopropylnaphthalene (DIPN), found in 4% of the bottles at levels up to 25 µg kg⁻¹, 2,4-di-tert-butyl phenol (in 90% of the bottles at levels up 400 µg kg⁻¹). Moreover, bisphenol A (BPA) was detected and quantified in baby bottles made of PA, but limited to one brand and model specific (but labelled BPA free). Results for baby bottles made of silicone also indicated the presence of components, e.g. potentially coming from inks (benzophenone, diisopropyl naphtahalene - DIPN, which could come for example from the presence of instruction leaflets in the bottles). In the case of silicone, phthalates were also found in relevant concentrations, with levels for DiBP and DBP from the first migration test of 50-150 µg kg⁻¹ and DEHP at levels 25-50 µg kg⁻¹.

  11. Catalytic phosphonation of high performance polymers and POSS. Novel components for polymer blend and nanocomposite fuel cell membranes

    Energy Technology Data Exchange (ETDEWEB)

    Bock, T.R.

    2006-10-15

    Aim of this thesis was the preparation and evaluation of phosphonated high performance (HP) polyelectrolytes and polyhedral oligomeric silsesquioxanes (POSS) for polyelectrolyte membrane fuel cell (PEMFC) application. Brominated derivatives of the commercial high performance (HP) polymers poly(ethersulfone) (PES), poly(etheretherketone) (PEEK), poly(phenylsulfone) (PPSu), poly(sulfone) (PSU) and of octaphenyl-POSS of own production were phosphonated by Ni-catalysed Arbuzov reaction. Phosphonated PSU was cast into pure and blend films with sulfonated PEEK (s-PEEK) to investigate H+-conductivity, water uptake and film morphology. Blend films' properties were referenced to films containing unmodified blend partners. Solution-compounding of phosphonated octaphenyl-POSS and s-PEEK was used to produce novel nanocomposite films. An in-situ zirconisation method was assessed as convenient strategy for novel ionically crosslinked membranes of enhanced swelling resistance. Dibromo isocyanuric acid (DBI) and N-bromo succinimide (NBS) as brominating agents allowed polymer analogous preparation of the novel brominated PES and PEEK with precise reaction control. A random distribution of functional groups, i.e. polyelectrolytes' microstructural homogeneity was revealed as decisive factor concerning solubility of phosphonated PSU. Brominated phT8 was prepared with Br2 by a high temperature approach in tetrachloroethane (TCE). Brominated polymers were phosphonated by Ni-catalysis in non-coordinating high temperature solvents, such as diphenylether, benzophenone and diphenylsulfone without notable solvent influence. The lack of solvent - catalyst complexes and high reaction temperatures of 180-200 C led to halogen-free phosphonates with unprecedented high functionalities. Polymer analogous application of P(OSiMe3)3 offered a novel direct access to easily cleavable disilyl ester derivatives. These were obtained from PEEK and PSU in near quantitative yields at NiCl2-loads as

  12. Migration measurement and modelling from poly(ethylene terephthalate) (PET) into soft drinks and fruit juices in comparison with food simulants.

    Science.gov (United States)

    Franz, R; Welle, F

    2008-08-01

    Poly(ethylene terephthalate) (PET) bottles are widely used for beverages. Knowledge about the migration of organic compounds from the PET bottle wall into contact media is of interest especially when post-consumer recyclates are introduced into new PET bottles. Using migration theory, the migration of a compound can be calculated if the concentration in the bottle wall is known. On the other hand, for any given specific migration limit or maximum target concentration for organic chemical compounds in the bottled foodstuffs, the maximum allowable concentrations in the polymer CP,0 can be calculated. Since a food simulant cannot exactly simulate the real migration into the foodstuff or beverages, a worse-case simulation behaviour is the intention. However, if the migration calculation should not be too overestimative, the polymer-specific kinetic parameter for migration modelling, the so-called AP value, should be established appropriately. One objective of the study was the kinetic determination of the specific migration behaviour of low molecular weight compounds such as solvents with relatively high diffusion rates and, therefore, with high migration potential from the PET bottle wall into food simulants in comparison with real beverages. For this purpose, model contaminants were introduced into the bottle wall during pre-form production. The volatile compounds toluene and chlorobenzene were established at concentrations from about 20-30 mg kg(-1) to 300-350 mg kg(-1). Phenyl cyclohexane was present at concentrations of 35, 262 and 782 mg kg(-1), respectively. The low volatile compounds benzophenone and methyl stearate have bottle wall concentrations of about 100 mg kg(-1) in the low spiking level up to about 1000 mg kg(-1) in the highly spiked test bottle. From these experimental data, the polymer specific parameters (AP values) from mathematical migration modelling were derived. The experimental determined diffusing coefficients were determined, calculated and

  13. Tuning copper-dioxygen reactivity and exogenous substrate oxidations via alterations in ligand electronics.

    Science.gov (United States)

    Zhang, Christiana Xin; Liang, Hong-Chang; Kim, Eun-Il; Shearer, Jason; Helton, Matthew E; Kim, Eunsuk; Kaderli, Susan; Incarvito, Christopher D; Zuberbühler, Andreas D; Rheingold, Arnold L; Karlin, Kenneth D

    2003-01-22

    Copper(I)-dioxygen adducts are important in biological and industrial processes. For the first time we explore the relationship between ligand electronics, CuI-O2 adduct formation and exogenous substrate reactivity. The copper(I) complexes [CuI(R-MePY2)]+ (1R, where R = Cl, H, MeO, Me2N) were prepared; where R-MePY2 are 4-pyridyl substituted bis[2-(2-pyridyl)ethyl]methylamine chelates. Both the redox potential of 1R (ranging from E1/2 = -270 mV for 1Cl to -440 mV for 1MeN vs FeCp2/FeCp2+) and nuCO of the CO adducts of 1R (ranging from 2093 cm-1 for 1Cl-CO to 2075 cm-1 for 1Me2N-CO) display modest but expected systematic shifts. Dioxygen readily reacts with 1H, 1MeO, and 1Me2N, forming the side-on peroxo-CuII2 complexes [{CuII(R-MePY2)}2(O2)]2+ (2R, also containing some bis-mu-oxo-CuIII2 isomer), but there is no reaction with 1Cl. Stopped-flow studies in dichloromethane show that the formation of 2Me2N from dioxygen and 1Me2N proceeds with a k = 8.2(6) x 104 M-2 s-1 (183 K, DeltaH = -20.3(6) kJ mol-1, DeltaS = -219(3) J mol-1 K-1). Solutions of 2R readily oxidize exogenous substrates (9,10-dihydroanthracene --> anthracene, tetrahydrofuran (THF) --> 2-hydroxytetrahydrofuran (THF-OH), N,N-dimethylaniline --> N-methylaniline and formaldehyde, benzyl alcohol --> benzaldehyde, benzhydrol --> benzophenone, and methanol --> formaldehyde), forming the bis-mu-hydroxo-CuII2 complexes [{CuII(R-MePY2)(OH)}2]2+ (3R). Product yields increase as the R-group is made more electron-donating, and in some cases are quantitative with 2Me2N. Pseudo-first-order rate constants for THF and methanol oxidation reactions demonstrate a remarkable R-group dependence, again favoring the strongest ligand donor (i.e., R = Me2N). For THF oxidation to THF-OH a nearly 1500-fold increase in reaction rate is observed (kobs = 2(1) x 10-5 s-1 for 2H to 3(1) x 10-2 s-1 for 2Me2N), while methanol oxidation to formaldehyde exhibits an approximately 2000-fold increase (kobs = 5(1) x 10-5 s-1 for 2H to 1(1) x

  14. Flavonoids of Lonchocarpus montanus A.M.G. Azevedo and biological activity

    Directory of Open Access Journals (Sweden)

    Aderbal F. Magalhães

    2007-09-01

    Full Text Available The analysis of root extracts from Lonchocarpus montanus A.M.G. Azevedo resulted in the isolation of twenty three compounds chiefly flavonoids of which five (four flavonoids and one benzophenone are described for the first time. The molecular structures of the new compounds (1-5 were determined through spectral analysis (UV, IR, MS and NMR as being: 2'-hydroxy-8-(a,a-dimethylallyl-2", 2"-dimethylpyrano-(5",6":3',4'-dibenzoylmethane (1, 2'-methoxy-8-(a, a-dimethylallyl-2", 2"-dimethylpyrano-(5",6":3',4'-dibenzoylmethane (2, 4'-methoxy-2",2"-dimethylpyrano-(5",6":8,7-flavone (3, 2"-(1-hydroxy-1-methylethyl-furano-(4",5":8,7-flavone (4 and [2'-methoxy-furano-(4",5":3',4'-phenyl]-phenylmethanone (5. Additionally, fifteen fatty acids were detected through GC-MS analysis of the corresponding methyl esters [(CH32CH(CH28COOH and CH3(CH2nCOOH (n = 6, 12-24]. Quantitative RP-HPLC showed that the most abundant flavonoids in the petroleum ether and dichloromethane extracts were pongamol (19% and lanceolatine B (8.0%, respectively. In the bioautography assay, the extracts, pongamol (9, lanceolatine B (10, isolonchocarpin (14, derriobtusone A (17 and medicarpine (18 were active against Staphilococus aureus whereas 9 also against Bacillus subtilis and Cladosporium cladosporioides. Compound 1, 2",2"-dimethylpyrano-(5",6":8,7-flavone (11 and furano-(1200,1300:7,8- 4'-methoxy flavone (12 were active against Fusarium oxysporium whereas 11 also against Rhizopus orizae. The extracts, compounds 9, 10, 17 and (E-7-O-methoxypongamol (23 displayed high toxicity in the brine shrimp lethality assay.A análise dos extratos das raízes de L. montanus A.M.G. Azevedo resultou no isolamento de vinte e três compostos principalmente flavonóides dos quais cinco são descritos pela primeira vez. As estruturas moleculares dos novos compostos (1-5 foram propostas através da análise dos espectros de UV, IV, EM e RMN como sendo: 2'-hidroxi-8-(a, a-dimetilalil-2", 2"-dimetilpirano

  15. Application of carbon dioxide towards the development of smart materials, green reaction schemes and metallic nanoparticle synthesis

    Science.gov (United States)

    Mohammed, Fiaz S.

    energy consumption due to a separate deprotection reaction. To solve this dilemma, the reversible protection of amines using CO2 induced carbamates was demonstrated in chapter 3; by reducing n-alkyl benzophenone imine and n-phenyl, nalkylurea yields by up to 67% compared to non-protected amines. The applicability of this chemistry to these classes of nucleophilic substitution reactions and has significant potential to alter the way we approach amine protection in organic synthesis. Another research area that has grown popularity over the last decade is the development of metallic nanoparticles, specifically gold nanoparticles (GNPs), due to their size and shape dependent optical and catalytic properties. Chapter 4 of this dissertation demonstrates the successful application of polyethylene imine (PEI) in the synthesis of cationic GNPs, which are of significant interest for biomedical applications. In this work, we investigated the effect of pH, PEI concentration and reduction method on the size and stability of amine-stabilized gold and silver nanoparticles. Furthermore the potential of carbon dioxide as a stabilizing aid through reversible carbamate formation was explored, leading to a decrease in particle size at ambient temperature along with an increase in stability. In summary, this work has demonstrated the great potential of employing the reversible reaction of carbon dioxide with primary and secondary amines as an effective and greener alternative to conventional methods in a diversity of fields that include "smart" materials, organic chemistry, and functional nanomaterials.

  16. Ionic liquids: radiation chemistry, solvation dynamics and reactivity patterns

    International Nuclear Information System (INIS)

    Wishart, J.F.; Funston, A.M.; Szreder, T.

    2006-01-01

    slow solvation dynamics of the excess electron in ILs (which vary over a wide viscosity range) increases the importance of pre-solvated electron reactivity and consequently alters product distributions. Scavenging of the excess electron before it becomes fully solvated is a significant facet of the overall radiation sensitivity of ionic liquids, possibly due to less competition from slower electron solvation processes. Parallel measurements of excess electron solvation processes and emission dynamics (Stokes shift and polarization anisotropy decay) of solvatochromic coumarin-153 show that the reorganization dynamics of ionic liquids extend to much longer timescales (nanoseconds) than in conventional polar solvents (picoseconds). This phenomenon profoundly influences the reactivity and energetics of radiolytically-generated excess electrons. The slow solvation dynamics would also be expected to significantly alter transition state dynamics and provide a potential means to control product distribution. This becomes particularly important for transition states with a very different polarity from the reactants and/or products. Electron reactions with several aromatic acceptors, acids, and oxygen were measured in (MeBu 3 N + )(NTf 2 - ). Rate constants for solvated electron capture by benzophenone, pyrene and phenanthrene were on the order of 1.6x10 8 M -1 ·s -1 , typically 100 times slower than observed in conventional polar solvents. The reactions of hydrogen atoms with several of the same reactants were measured in the same ionic liquid. H-atoms react very rapidly with pyrene and phenanthrene (∼3 x 10 9 L·mol -1 ·s -1 ) to form H-adduct radicals. The H-atom rate constants are similar to the values measured or estimated for the same reactions in aqueous solutions. The H-atom reactions with the aromatic hydrocarbons must be diffusion-controlled, but are faster than diffusion-controlled reactions for solvated electrons in the same ionic liquid. The results indicate

  17. A Development of Rapid, Practical and Selective Process for Preparation of Z-Oximes

    International Nuclear Information System (INIS)

    Kim, Bo Ram; Sung, Gi Hyeon; Yoon, Yongjin; Kim, Jeumjong

    2013-01-01

    hydrochloride in the presence of potassium carbonate in refluxing 1,4-dioxane to afford the corresponding ketoxime 2a in excellent yield. Acetophenone oxime (2a) was also obtained by the use of ethanol or methanol as the solvent at room temperature or at reflux temperature in excellent yields (Entries 9-12 in Table 1), whereas the side reaction was detected for the reaction of 1a with hydroxylamine hydrochloride in the presence of potassium carbonate in refluxing water. According to our preliminary results, we selected the methanol as the solvent due to short reaction time and low price. As shown in Table 2, aliphatic and aromatic ketones except for benzophenone (1f) were rapidly and selectively converted to the corresponding Z-oximes in good yields. Also, various types of aromatic aldehydes 1g. with electron donating and withdrawing groups were rapidly and selectively converted to the corresponding Zaldoximes in good to excellent yields. In our condition, the oximation of aldehydes is more Z-selective than the oximation of ketones. In order to evaluate the utility of industrial process, we examined the one mole scale reaction. Treatment of one mole acetophenone (1a) and benzaldehyde (1g) with hydroxylamine hydrochloride and potassium carbonate in methanol afforded the corresponding oximes 2a (E/Z ratio = 15:85, 92%) and 2g (E/Z ratio = 10:90, 92%). The structures of the oximes were established by IR and NMR. In the case of ketoximes, we distinguished two isomers by using the carbon chemical shifts of C=NOH, that is, the chemical shifts of the Z-isomer are detected higher field than the chemical shifts of the E-isomer. In the case of aldoximes, E/Z-isomers were distinguished by using the proton chemical shifts of HC=N for aldoximes, that is, the proton chemical shifts of the Z-isomer are detected lower field than the chemical shifts of the E-isomer. In summury, we have demonstrated the rapid and convenient oximation of ketones and aldehydes with potassium carbonate in methanol