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Sample records for benzophenone

  1. Photopolymerization induced by a benzophenone derivative photoinitiator

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A benzophenone derivative photoinitiator, HBP-TDI-HQ-TDI-HBP (HTCTH), was synthesized based on 4-hydroxy benzophenone (HBP), toluene-2,4-diisocyanate (TDI) and hydroquinone (HQ). HTCTH was a more effective photoinitiator which had longer wavelength absorption in the UV-vis absorption spectra than the low molecular counterpart benzophenone (BP). It showed that both rate of polymerization (Rp) and final conversion (P) increased with increase of amine and HTCTH concentration in photopolymerization.

  2. Polyprenylated benzophenones derivatives from Cluisa minor fruits

    OpenAIRE

    Mangas Marín, Raisa; Bello Alarcón, Adonis; Cuesta Rubio, Osmany; Piccinelli, Anna L.; Rastrelli, Luca

    2008-01-01

    Clusia minor fruits were investigated and three polyprenylated benzophenones were isolated using several chromatographic techniques. All the structures assigned (propolone D, hyperibone B and garcinielliptone I), including relative configuration, were elucidated by spectroscopic methods. These three benzophenones are reported for the first time in Clusia genus.

  3. Prenylated benzophenones from Triadenum japonicum.

    Science.gov (United States)

    Oya, Atsushi; Tanaka, Naonobu; Kusama, Taishi; Kim, Sang-Yong; Hayashi, Shigeki; Kojoma, Mareshige; Hishida, Atsuyuki; Kawahara, Nobuo; Sakai, Kanae; Gonoi, Tohru; Kobayashi, Jun'ichi

    2015-02-27

    Six new prenylated benzophenones, (-)-nemorosonol (1) and trijapins A-E (2-6), were isolated from the aerial parts of Triadenum japonicum. (-)-Nemorosonol (1) and trijapins A-C (2-4) have a common tricyclo[4.3.1.0(3,7)]decane skeleton, while 1 is an enantiomer of (+)-nemorosonol previously isolated from Clusia nemorosa. The absolute configuration of (-)-nemorosonol (1) was assigned by ECD spectroscopy. Trijapins A-C (2-4) are analogues of 1 possessing an additional tetrahydrofuran ring. Trijapins D (5) and E (6) are prenylated benzophenones with a 1,2-dioxane moiety and a hydroperoxy group, respectively. (-)-Nemorosonol (1) exhibited antimicrobial activity against Escherichia coli (MIC, 8 μg/mL), Staphylococcus aureus (MIC, 16 μg/mL), Bacillus subtilis (MIC, 16 μg/mL), Micrococcus luteus (MIC, 32 μg/mL), Aspergillus niger (IC50, 16 μg/mL), Trichophyton mentagrophytes (IC50, 8 μg/mL), and Candida albicans (IC50, 32 μg/mL), while trijapin D (5) showed antimicrobial activity against C. albicans (IC50, 8 μg/mL). PMID:25602977

  4. Polyprenylated benzophenone derivatives from Cuban propolis.

    Science.gov (United States)

    Hernández, Ingrid Márquez; Fernandez, Mercedes Campo; Cuesta-Rubio, Osmany; Piccinelli, Anna Lisa; Rastrelli, Luca

    2005-06-01

    Three new polyprenylated benzophenone derivatives, propolones B-D (5-7), together with garcinielliptone I (8) and hyperibone B (9), were isolated from Cuban propolis. All the structures, including relative configurations, were elucidated by spectroscopic methods and computer-generated molecular modeling. PMID:15974622

  5. A New Benzophenone from Garcinia benthamiana

    OpenAIRE

    Irene See; Gwendoline Cheng Lian Ee; Soek Sin Teh; Siau Hui Mah; Roghayeh Abedi Karjiban; Shaari Daud; Vivien Yi Mian Jong

    2015-01-01

    A detailed phytochemical study on the stem bark of Garcinia benthamiana has afforded a new benzophenone, benthamianone (1), together with congestiflorone (2), a mixture of stigmasterol (3) and γ-sitosterol (4) as well as a mixture of phloroglucinol (5) and methyl palmitate (6). The structural elucidation of these compounds was performed through analysis of their spectroscopic data (NMR spectra and MS). This is the first report on the phytochemistry of Garcinia benthamiana.

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

    OpenAIRE

    Georges C. Accrombessi; Jacques Poupaert; Raymond H. Fatondji; Salomé D. S. Kpoviessi; Gbaguidi, Fernand A.; Bienvenu Glinma

    2011-01-01

    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 a...

  7. 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)

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

    International Nuclear Information System (INIS)

    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)

  9. Quenching of the triplet state of benzophenone by lanthanide 1,3-diketonate chelates in solutions

    International Nuclear Information System (INIS)

    The phosphorescence of benzophenone in benzene and acetonitrile was quenched by several lanthanide (Sm, Eu, Gd, Tb and Dy) acetylacetonate chelates. The results of Stern-Volmer analysis including the quenching of benzophenone triplet and sensitization of lanthanide emission indicate that the quenching process occurs by the energy transfer mechanism via the excited triplet state of the ligand. (Author)

  10. 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.

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

    Directory of Open Access Journals (Sweden)

    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.

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

    Directory of Open Access Journals (Sweden)

    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.

  13. Photopolymerization property of a novel benzophenone derivative photoinitiator containing Si

    Energy Technology Data Exchange (ETDEWEB)

    Sun, F. [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029 (China); College of Science, Beijing University of Chemical Technology, Beijing 100029 (China); Zhang, L. [College of Science, Beijing University of Chemical Technology, Beijing 100029 (China); Jiang, S.L. [College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029 (China); Du, H.G. [College of Science, Beijing University of Chemical Technology, Beijing 100029 (China); Nie, J., E-mail: niejun-buct@163.co [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029 (China) and College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029 (China)

    2009-11-15

    The photopolymerzation property of a novel benzophenone derivative photoinitiator containing Si (HBSiBH) was investigated by real-time FTIR (RTIR) and X-ray photoelectron spectroscopy (XPS). It is noted that both of the polymerization rate and final conversion of the system increased with increase concentration of HBSiBH. Addition of small amount of HBSiBH can greatly improved the photopolymerization rate of radical photopolymerization. XPS experiment showed that the new photoinitiator containing Si had ability to float up to the surface of UV-curable system. It could more effectively mitigate inhibition of oxygen in radical photopolymerization and provide a new approach to improving surface performance of UV-curable materials.

  14. Photopolymerization property of a novel benzophenone derivative photoinitiator containing Si

    International Nuclear Information System (INIS)

    The photopolymerzation property of a novel benzophenone derivative photoinitiator containing Si (HBSiBH) was investigated by real-time FTIR (RTIR) and X-ray photoelectron spectroscopy (XPS). It is noted that both of the polymerization rate and final conversion of the system increased with increase concentration of HBSiBH. Addition of small amount of HBSiBH can greatly improved the photopolymerization rate of radical photopolymerization. XPS experiment showed that the new photoinitiator containing Si had ability to float up to the surface of UV-curable system. It could more effectively mitigate inhibition of oxygen in radical photopolymerization and provide a new approach to improving surface performance of UV-curable materials.

  15. Bioremediation of Bisphenol A and Benzophenone by Glycosylation with Immobilized Marine Microalga Pavlova sp.

    OpenAIRE

    Kei Shimoda; Hiroki Hamada

    2009-01-01

    Cultured cells of Pavlova sp. glycosylated bisphenol A to its mono-glucoside, 2-(4-β-D-glucopyranosyloxyphenyl)-2- hydroxyphenylpropane (9%). Use of immobilized Pavlova cells in sodium alginate gel improved yield of the product (17%). On the other hand, Pavlova cell cultures converted benzophenone into diphenylmethanol (49%) and diphenylmethyl β-D-glucopyranoside (6%). Incubation of benzophenone with immobilized Pavlova cells gave products in higher yields; the yields of diphenylmethanol and ...

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

    OpenAIRE

    Kei Shimoda; Hatsuyuki Hamada; Hiroki Hamada

    2009-01-01

    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-...

  17. Study on synthesis, application and mechanism of benzophenone/amine initiator

    International Nuclear Information System (INIS)

    Through Michael addition reaction of trimethylolpropane triacrylate (TMPTA) with diethylamine (DEA), a new kind of tertiary amine derivative was synthesized and its structure was identified by 'H-NMR. When used in combination with benzophenone, this amine presented excellent curing speed and could be a substitute for initiator Darocur R 1173, which is effective but expensive. If so, the cost of UV-curable coatings can descend apparently. The functioning mechanism of benzophenone/amine bimolecular initiator was studied

  18. Cytotoxic and leishmanicidal properties of garcinielliptone FC, a prenylated benzophenone from Platonia insignis.

    Science.gov (United States)

    Costa Júnior, Joaquim S; de Almeida, Antonia Amanda Cardoso; de Barros Falcão Ferraz, Alexandre; Rossatto, Raíssa Rebés; Silva, Teresinha G; Silva, Paulo B N; Militão, Gardenia C G; das Graças Lopes Citó, Antonia Maria; Santana, Lorena Citó Lopes Resende; de Amorim Carvalho, Fernando Aécio; Freitas, Rivelilson M

    2013-03-01

    Garcinielliptone FC (GFC), a natural prenylated benzophenone, was extracted from Platonia insignis Mart. (Clusiaceae), a native plant commonly known as bacuri and used in traditional Brazilian medicine for the treatment of skin diseases. The aim of this study was to evaluate the cytotoxic and leishmanicidal effects of GFC using in vitro models. The experimental data demonstrated that the polyisoprenylated benzophenone GFC possesses cytotoxic and leishmanicidal activities. PMID:22708546

  19. 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.

  20. Urinary benzophenone concentrations and their association with demographic factors in a South Korean population.

    Science.gov (United States)

    Kang, Hui-Seung; Ko, Ahra; Kwon, Ji-Eun; Kyung, Min-Sik; Moon, Gui Im; Park, Jae-Hong; Lee, Hee-Seok; Suh, Jin-Hyang; Lee, Jung-Mi; Hwang, Myung-Sil; Kim, Kisok; Hong, Jin-Hwan; Hwang, In Gyun

    2016-08-01

    Benzophenone (BP) and its derivatives are widely used in various cosmetics, personal care products, and food packaging ink. The use of BP has raised concerns about the potential health risks associated with its endocrine-disrupting effects. This study evaluated urinary concentrations of BP derivatives in a national sample of the South Koreans population aged 6-89 years. From July to September in each 2010 and 2011, 1576 urine samples were collected. Urinary concentrations of benzophenone-1 (BP-1), benzophenone-2 (BP-2), benzophenone-3 (BP-3), benzophenone-4 (BP-4), benzophenone-8 (BP-8), and 4-hydroxybenzophenone (4-OH-BP) were analyzed using liquid chromatography-mass spectrometry. The detection rate for BP-1 and 4-OH-BP were 56% [limit of detection (LOD) 0.59ng/mL] and 88% (LOD 0.04ng/mL), respectively, whereas those for BP-2, BP-3, BP-4, and BP-8 were all below 25%. The geometric means of urinary BP-1 and 4-OH-BP concentrations were 1.24ng/mL and 0.45ng/mL, respectively. Multiple linear regression analysis indicated that concentrations of BP-1 in and of 4-OH-BP in adults were associated with sex and age. The BP-1 and 4-OH-BP concentration of children and adolescents was associated with sex, age, income, and current area of residence. The correlation was observed between urinary concentrations of BP derivatives, which is an important indication of exposure biomarkers and the metabolic pathways from BP-3. This is the first national study to evaluate the presence of BP derivatives in urine samples from the South Korean population, stratified by demographic factors. PMID:27155137

  1. Resolving the Benzophenone DNA-Photosensitization Mechanism at QM/MM Level.

    Science.gov (United States)

    Dumont, Elise; Wibowo, Meilani; Roca-Sanjuán, Daniel; Garavelli, Marco; Assfeld, Xavier; Monari, Antonio

    2015-02-19

    Benzophenone, the parent of the diarylketone family, is a versatile compound commonly used as a UV blocker. It may also trigger triplet-based DNA photosensitization. Therefore, benzophenone is involved in DNA photodamage induction. In the absence of experimentally resolved structure, the mechanism of DNA damage production remains elusive. Employing a hybrid quantum mechanics/molecular mechanics approach, here we address the spin transfer mechanism between this drug and proximal thymine, that is, the DNA nucleobase most prone to suffer triplet damages. PMID:26262469

  2. Urinary levels of bisphenol A, benzophenones and parabens in Tunisian women: A pilot study.

    Science.gov (United States)

    Jiménez-Díaz, I; Artacho-Cordón, F; Vela-Soria, F; Belhassen, H; Arrebola, J P; Fernández, M F; Ghali, R; Hedhili, A; Olea, N

    2016-08-15

    Bisphenol A (BPA), benzophenones and parabens are commonly used in the production of polycarbonate plastics, as UV-filters and as antimicrobial preservatives, respectively, and they are thought to exhibit endocrine disrupting properties. Exposure to these compounds remains poorly characterized in developing countries, despite the fact that certain behaviors related to westernization have the potential to influence exposure. The aim of this pilot study was to measure urinary concentrations of BPA, six different benzophenones and four parabens in 34 Tunisian women. In addition, we identified some socio-demographic and dietary predictors of exposure to these compounds. Chemical analyses were carried out by dispersive liquid-liquid microextraction (DLLME) and ultra-high performance liquid chromatography with tandem mass spectrometry detection (UHPLC-MS/MS). Detection frequencies of methylparaben (MP), ethylparaben (EP) and propylparaben (PP) ranged between 67.6 and 94.1%. Butylparaben (BP) was found in 38.2% of the analyzed samples; BPA in 64.7%; and benzophenone-1 (BP-1) and benzophenone-3 (BP-3) were detected in 91.2 and 64.7% of the analyzed samples, respectively. Urinary geometric mean concentrations of MP, EP, PP, and BP were 30.1, 1.4, 2.0 and 0.5ngmL(-1), respectively. Geometric mean concentrations of BPA, BP-1, and BP-3 were 0.4, 1.3 and 1.1ngmL(-1), respectively. Our results suggest that Tunisian women are widely exposed to BPA, parabens and some benzophenones. Further studies on the general Tunisian population are needed in order to assess the levels of exposure to these compounds and to identify sources of exposure and population groups at higher risk. PMID:27096629

  3. UPLC-QTOFMS(E)-Guided Dereplication of the Endangered Chinese Species Garcinia paucinervis to Identify Additional Benzophenone Derivatives.

    Science.gov (United States)

    Li, Ping; Anandhi Senthilkumar, Harini; Figueroa, Mario; Wu, Shi-Biao; Fata, Jimmie E; Kennelly, Edward J; Long, Chunlin

    2016-06-24

    A number of Garcinia species accumulate benzophenone derivatives that may be useful for the treatment of breast cancer. The dereplication of new benzophenone derivatives from Garcinia species is challenging due to the occurrence of multiple isomers and the known compounds found in their extracts. In the current study, a strategy is described using the UPLC-QTOFMS(E) technique to identify tentatively the known and uncharacterized benzophenones of interest based upon the characteristic fragmentation ions. Several UPLC-QTOFMS peaks (a-ee) appeared to contain benzophenone derivatives, and 12 of these peaks contained compounds with MS ionization profiles not consistent with previously identified compounds from the seeds of Garcinia paucinervis, an endangered Chinese species. The targeted isolation of unidentified compounds of interest afforded five new benzophenones, paucinones E-I (1-5), which were determined by MS and NMR analysis and ECD spectroscopy. These compounds were evaluated for cytotoxicity against three breast cancer cell lines inclusive of MDA-MB-231, SKBR3, and MCF-7. These results indicate that the UPLC-QTOFMS(E)-guided isolation procedure is an efficient strategy for isolating new benzophenones from Garcinia species. PMID:27266714

  4. 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; Minghlani, Mite; Awad, Suad Mohamud; Holbech, Bente Frost; Green, John W.; Bjerregaard, Poul; Holbech, Henrik

    2015-01-01

    The chemical ultraviolet (UV) filter benzophenone-3 (BP-3) is suspected to be an endocrine disruptor based on results from in vitro and in vivo testing. However, studies including endpoints of endocrine adversity are lacking. The present study investigated the potential endocrine-disrupting effects...... mechanism as well as a marker of adversity and therefore the conclusion of the investigation is that BP-3 is an endocrine-disrupting chemical in accordance with the World Health Organization's definition....

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

    OpenAIRE

    Lucas Dewalque; Catherine Pirard; Corinne Charlier

    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 metabolite...

  6. Preventing false negatives with high-resolution mass spectrometry: the benzophenone case

    OpenAIRE

    Gallart Ayala, Hèctor; Núñez Burcio, Oscar; Moyano Morcillo, Encarnación; Galcerán Huguet, M. Teresa; Martins, Cláudia P. B.

    2011-01-01

    Benzophenone (BP) is one of the many contaminants reported as present in foodstuff due to its migration from food packaging materials. Liquid chromatography tandem mass spectrometry (LC-MS/MS) is acknowledged in the literature as the method of choice for this analysis. However, cases have been reported where the use of this methodology was not enough to unambiguously confirm the presence of a contaminant. In previous work performed by the authors, the unequivocal identification of BP in packa...

  7. Investigation of the Stabilizing Effects of Antioxidants and Benzophenone-3 on Desonide Photostability

    OpenAIRE

    Rosa, Priscila; Snovarski Salla, Ana Paula; de Bona da Silva, Cristiane; Bueno Rolim, Clarice Madalena; Horn Adams, Andréa Inês

    2014-01-01

    Desonide is a topical corticoid used in the treatment of skin diseases and is marketed in different pharmaceutical dosage forms. Recently, the poor photostability of a commercially available hair solution after direct exposure to UVA light was verified. In this study, we investigated the ability of the antioxidants ascorbic acid, butylhydroxyanisole (BHA), butylhydroxytoluene (BHT), α-tocopherol, and the UV filter benzophenone-3 (BP-3) to prevent the photodegradation of desonide in hair solut...

  8. Garcinia xanthochymus Benzophenones Promote Hyphal Apoptosis and Potentiate Activity of Fluconazole against Candida albicans Biofilms

    OpenAIRE

    Jackson, Desmond N.; Yang, Lin; Wu, ShiBiao; Kennelly, Edward J.; Lipke, Peter N.

    2015-01-01

    Xanthochymol and garcinol, isoprenylated benzophenones purified from Garcinia xanthochymus fruits, showed multiple activities against Candida albicans biofilms. Both compounds effectively prevented emergence of fungal germ tubes and were also cytostatic, with MICs of 1 to 3 μM. The compounds therefore inhibited development of hyphae and subsequent biofilm maturation. Xanthochymol treatment of developing and mature biofilms induced cell death. In early biofilm development, killing had the char...

  9. Novel one-component polymeric benzophenone photoinitiator containing poly (ethylene glycol) as hydrogen donor

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Kemin, E-mail: wangkm61@gmail.com; Lu, Yuhui; Chen, Penghui; Shi, Jingsong; Wang, Hongning; Yu, Qiang, E-mail: yuqiang@cczu.edu.cn

    2014-02-14

    Benzophenone (BP) is a common initiator which is often used in the UV-curing production and related fields. However, the shortcomings such as toxicity, odor, and migration always limit the development of the traditional BP photoinitiator. Polymeric benzophenone photoinitiator (PEG-BP) was synthesized basing on polyethylene glycol (PEG), succinic anhydride, 4-hydroxybenzophenone and epichlorohydrin. The structure of PEG-BP was characterized by IR and {sup 1}H NMR. The radiation absorption of PEG-BP was detected by UV spectrophotometer with the maximum absorption wavelength at 283 nm in acetonitrile solvent, undergone significant redshift corresponding to small molecule photoinitiator BP, thus enhanced the photosensitive efficiency of UV-curing system in the long wavelength region. Besides, PEG-BP has better water solubility than BP, thus could be used in both oil and aqueous solution. The obvious advantage of this initiator was the elimination of amine based hydrogen donors and to provide alternative hydrogen donors with easily availability and non-toxicity. The effects of molecular weights of PEG-BP, photoinitiator concentration, UV-radiation intensity and different monomers on photopolymerization kinetics were investigated in detail. The synthesized polymeric photoinitiators are attractive to be used as type II photoinitiators. - Highlights: • Novel one-component polymeric benzophenone photoinitiator was synthesized. • This photoinitiator contained poly (ethylene glycol) as hydrogen donor. • This photoinitiator was the elimination of amine based hydrogen donors.

  10. Solvation of benzophenone anion radical in ethanol and ethanol/2-methyltetrahydrofuran mixture

    International Nuclear Information System (INIS)

    The electron spin-echo modulations and the absoprtion spectra of benzophenone anion radicals generated by γ-irradiation in the glassy matrices of ethanol and ethanol2-methyltetrahydrofuran mixtures have been measured for elucidating the mechanism of spectral shift observed during the solvation of the anion radicals in alcohols. The anion radical generated at 4.2 K in the ethanol matrix maintains the same solvation structure as that of neutral benzophenone. At 77 K ethanol molecules solvate the anion radical by orienting the O-H dipoles toward the anion radical. The anion radical is hydrogen-bonded by two ethanol molecules through the p/sub z/ orbital on the benzophenone oxygen which composes the π orbitals of anion radical. Three kinds of anion radicals are observed in the mixed matrix at 77 K. Two of them are essentially the same as those observed in the ethanol matrix at 4.2 and 77 K. The third has the absorption maximum at 700 nm and is attributed to the anion radical hydrogen-bonded by one ethanol molecule through the p/sub z/ orbital. It is concluded that the spectral shift observed in alcohols is caused by the stabilization of a SOMO π* orbital induced by the hydrogen bonding with the (RO)H--O--H(OR) angle perpendicular to the molecular plane of the anion radical

  11. Novel one-component polymeric benzophenone photoinitiator containing poly (ethylene glycol) as hydrogen donor

    International Nuclear Information System (INIS)

    Benzophenone (BP) is a common initiator which is often used in the UV-curing production and related fields. However, the shortcomings such as toxicity, odor, and migration always limit the development of the traditional BP photoinitiator. Polymeric benzophenone photoinitiator (PEG-BP) was synthesized basing on polyethylene glycol (PEG), succinic anhydride, 4-hydroxybenzophenone and epichlorohydrin. The structure of PEG-BP was characterized by IR and 1H NMR. The radiation absorption of PEG-BP was detected by UV spectrophotometer with the maximum absorption wavelength at 283 nm in acetonitrile solvent, undergone significant redshift corresponding to small molecule photoinitiator BP, thus enhanced the photosensitive efficiency of UV-curing system in the long wavelength region. Besides, PEG-BP has better water solubility than BP, thus could be used in both oil and aqueous solution. The obvious advantage of this initiator was the elimination of amine based hydrogen donors and to provide alternative hydrogen donors with easily availability and non-toxicity. The effects of molecular weights of PEG-BP, photoinitiator concentration, UV-radiation intensity and different monomers on photopolymerization kinetics were investigated in detail. The synthesized polymeric photoinitiators are attractive to be used as type II photoinitiators. - Highlights: • Novel one-component polymeric benzophenone photoinitiator was synthesized. • This photoinitiator contained poly (ethylene glycol) as hydrogen donor. • This photoinitiator was the elimination of amine based hydrogen donors

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

    International Nuclear Information System (INIS)

    The aim of this work is to estimate the antioxidant activity of β-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). β-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 β-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 β-carotene antioxidant activity in the presence of benzophenone, implying the same cause: increase in (phospholipids peroxidation) chain-breaking activities.

  13. 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.

  14. 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.

  15. Photolytic fate and genotoxicity of benzophenone-derived compounds and their photodegradation mixtures in the aqueous environment.

    Science.gov (United States)

    Kotnik, Kristina; Kosjek, Tina; Žegura, Bojana; Filipič, Metka; Heath, Ester

    2016-03-01

    This study investigates the environmental fate of eight benzophenone derivatives (the pharmaceutical ketoprofen, its phototransformation products 3-ethylbenzophenone and 3-acetylbenzophenone, and five benzophenone-type UV filters) by evaluating their photolytic behaviour. In addition, the genotoxicity of these compounds and the produced photodegradation mixtures was studied. Laboratory-scale irradiation experiments using a medium pressure UV lamp revealed that photodegradation of benzophenones follows pseudo-first-order kinetics. Ketoprofen was the most photolabile (t1/2 = 0.8 min), while UV filters were more resistant to UV light with t1/2 between 17 and 99 h. The compounds were also exposed to irradiation by natural sunlight and showed similar photostability as predicted under laboratory conditions. Solar photodegradation experiments were performed in distilled water, lake and seawater, and revealed that photosensitizers present in natural waters significantly affect the photolytic behaviour of the investigated compounds. In this case, the presence of lake water resulted in accelerated photodecomposition, while seawater showed different effects on photodegradation, depending on a compound. Further, it was shown that the transformation products of ketoprofen 3-ethylbenzophenone and 3-acetylbenzophenone were formed under environmental conditions when ketoprofen was exposed to natural sunlight. Genotoxicity testing of parent benzophenone compounds using the SOS/umuC assay revealed that UV filters exhibited weak genotoxic activity in the presence of a metabolic activation system, however the concentrations tested were much higher than found in the environment (≥125 μg mL(-1)). After irradiation of benzophenones, the produced photodegradation mixtures showed that, with the exception of benzophenone that exhibited weak genotoxic activity, all the other compounds tested did not elicit any activity when exposed to UV light. PMID:26766022

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

    International Nuclear Information System (INIS)

    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/cm2. 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-O3 and Si-O4 bonding at the expense of Si-C and Si-O2 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

  17. 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%.

  18. Palladium catalysed asymmetric alkylation of benzophenone Schiff base glycine esters in ionic liquids

    Indian Academy of Sciences (India)

    Dae Hyun Kim; Jin Kyu Im; Dae Won Kim; Minserk Cheong; Hoon Sik Kim; Deb Kumar Mukherjee

    2011-07-01

    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 enhanced reactivity and selectivity for phase transfer catalytic (PTC) glycine alkylation. It has been found that there is an anionic influence of the ionic liquids that modify the steric environment around the enolate ion. A computer-assisted molecular design of enantioselective phase-transfer catalysis with the palladium complex and the ionic liquid has been done.

  19. In vivo Anticancer Activities of Benzophenone Semicarbazone against Ehrlich Ascites Carcinoma Cells in Swiss Albino Mice

    International Nuclear Information System (INIS)

    Benzophenone semicarbazone (BSC) was synthesized and characterized to identify compounds with anticancer activities. Anticancer activities were studied against Ehrlich Ascites Carcinoma (EAC) cells in Swiss albino mice by monitoring parameters such as tumor weight measurement, survival time of tumor bearing mice, tumor cell growth inhibition, and so on. Some hematological parameters, such as red blood cells, white blood cells, and hemoglobin content, were also measured. The results showed that BSC has a positive effect against EAC cells. An assessment was conducted by comparing these results with those obtained using the standard drug bleomycin. The BSC compound can be considered as a potent anticancer agent

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

    DEFF Research Database (Denmark)

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

    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......-beta-glucopyranoside (3) isolated from G. verna subsp. pontica. Among the benzophenone glucosides 1 and 2 exhibited significant inhibition of MAO-A (IC50 = 31.3 +/- 4 microM and 41 +/- 4.7 microM resp.)....

  1. Synthesis of Benzophenone Hydrazone Analogs and their DPPH Radical Scavenging and Urease Inhibitory Activates

    International Nuclear Information System (INIS)

    Benzophenone hydrazone analogs 1-25 were synthesized and evaluated for antioxidant (DPPH radical scavenging), and urease inhibitory activities. Out of twenty-five analogs, compounds 8, 23, and 1 showed potent free radical scavenging activities with IC50 values 19.45 ± 1.25, 21.72 ± 1.49, and 26.0 ± 0.52 μM, respectively, while compound 8 (IC50 = 36.36 ± 0.94 μ M), and 15 (IC50 = 55.5 ± 0.69 μ M), showed good to moderate urease inhibitory potential. (author)

  2. Efficient Access to Chiral Benzhydrols via Asymmetric Transfer Hydrogenation of Unsymmetrical Benzophenones with Bifunctional Oxo-Tethered Ruthenium Catalysts.

    Science.gov (United States)

    Touge, Taichiro; Nara, Hideki; Fujiwhara, Mitsuhiko; Kayaki, Yoshihito; Ikariya, Takao

    2016-08-17

    A concise asymmetric transfer hydrogenation of diaryl ketones, promoted by bifunctional Ru complexes with an etherial linkage between 1,2-diphenylethylenediamine (DPEN) and η(6)-arene ligands, was successfully developed. Because of the effective discrimination of substituents at the ortho position on the aryl group, unsymmetrical benzophenones were smoothly reduced in a 5:2 mixture of formic acid and triethylamine with an unprecedented level of excellent enantioselectivity. For the non-ortho-substituted benzophenones, the oxo-tethered catalyst electronically discerned biased substrates, resulting in attractive performance yielding chiral diarylmethanols with >99% ee. PMID:27463264

  3. 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.

  4. Photoinitiating Characteristics of Benzophenone Derivatives as Type Ⅱ Macromolecular Photoinitiators Used for UV Curable Resins

    Institute of Scientific and Technical Information of China (English)

    CHENG Liang-liang; ZHANG Yong; SHI Wen-fang

    2011-01-01

    Dodecyl-benzophenone(DBP) and hexadecoxyl-benzophenone(HDBP) as type Ⅱ photoinitiators used for radical photopolymerization systems were synthesized by Friedel-Crafts reaction, and characterized by 1H NMR and FTIR spectroscopy. The UV-Vis absorption spectra of DBP and HDBP, propitious to photopolymerization under a commercial mercury UV bulb are centered at 345 and 335 nm, respectively. HDBP has higher extinction coefficient than DBP, but lower photoinitiating efficiency. Their photoinitiating performances for EB605, a bisphenol A epoxy acrylate with 40%(mass fraction) tripropyleneglycol diacrylate (TPGDA), resin consisting of bisphenol A epoxy acrylate and tripropyleneglycol diacrylate in the presence of triethanolamine as a coinitiator were investigated by photo-differential scanning calorimetry(photo-DSC). DBP initiates the curing of acrylate more efficiently than HDBP,showing higher photopolymerization rate and unsaturation conversion. resulted from the poor compatibility of HDBP with the resin. The photoinitiating activity of DBP to epoxy acrylate resin is even higher than that of BP at lower loadings.

  5. Synthesis and photopolymerization kinetics of benzophenone sesamol one-component photoinitiator.

    Science.gov (United States)

    Yang, Jinliang; Shi, Suqing; Xu, Fei; Nie, Jun

    2013-02-01

    A benzodioxole derivative, 4-(2-(benzodioxol-5-yloxy)ethoxy)benzophenone (BPC2BDO), based on 4-hydroxybenzophenone and sesamol was synthesized, and used as a one-component Type II photoinitiator. The structure of BPC2BDO was characterized by elementary analysis, APCI-MS, (1)H NMR, and (13)C NMR. The rate of decomposition (R(d)) of BPC2BDO in acetonitrile was studied by UV-Vis spectroscopy and found that R(d) was proportional to light intensity. Real-time near-IR was used to study the kinetics of photopolymerization of the photoinitiator. As the benzophenone (BP) moiety and hydrogen donor were introduced into one molecule in BPC2BDO, radicals could be generated through intra-molecular reaction due to the close vicinity of the hydrogen donor and BP, which might be faster than inter-molecular reaction. The results also showed that the rate of polymerization of acrylates was significantly higher than that of methacrylates at the same polymerization conditions; the functionality of acrylates, concentration of BPC2BDO, and light intensity affected the polymerization rate and the final conversion. PMID:23047776

  6. Phosphorescence induced by pressure and continuous light irradiation of benzophenone and 4,4`-bis(dimethylamino)benzophenone in solid polymers at room temperature

    Energy Technology Data Exchange (ETDEWEB)

    Dreger, Z.A.; Lang, J.M.; Drickamer, H.G. [Univ. of Illinois, Urbana, IL (United States)

    1996-03-14

    We report efficient room temperature phosphorescence induced by pressure (PIP) and/or by continuous light irradiation (light-induced phosphorescence (LIP)) in two ketones: benzophenone (BP) and its p-dimethylamino-substituted (Michler`s ketone (MK)) both dissolved in solid poly(ethyl methacrylate) (PEMA). Under pressure both BP and MK reveal a remarkable growth of the phosphorescence intensity: 2 orders of magnitude (within 5 kbar) and 1 order of magnitude (within 50 kbar) respectively for MK and BP. For MK, above 5 kbar the phosphorescence intensity significantly decreases, but for BP the decrease is negligible even above 50 kbar. A model based on the increase of the amount of {pi},{pi}{sup *} character in the predominately n,{pi}{sup *} triplet state with increasing pressure is proposed to account for the observed features of the PIP. The LIP occurs only at pressures below the maximum in the PIP. With prolonged irradiation, the overall shape of the phosphorescence intensity curve versus time depends on pressure, exciting light intensity, and concentration. A tentative explanation of the LIP effect is given that assumes a creation of the phosphorescent photoproduct via the hydrogen abstraction reaction. 36 refs., 14 figs.

  7. (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.

  8. Structural studies on acetophenone- and benzophenone-derived thiosemicarbazones and their zinc(II) complexes

    Science.gov (United States)

    Ferraz, Karina S. O.; Silva, Nayane F.; Da Silva, Jeferson G.; Speziali, Nivaldo L.; Mendes, Isolda C.; Beraldo, Heloisa

    2012-01-01

    In the present work N(3)- meta-chlorophenyl-(HAc3 mCl, 1) and N(3)- meta-fluorphenyl-(HAc3 mF, 2) acetophenone thiosemicarbazone, and N(3)- meta-chlorophenyl-(HBz3 mCl, 3) and N(3)- meta-fluorphenyl-(HBz3 mF, 4) benzophenone thiosemicarbazone were obtained, as well as their zinc(II) complexes [Zn(Ac3 mCl) 2] ( 5), [Zn(Ac3 mF) 2] ( 6), [Zn(Bz3 mCl) 2] ( 7) and [Zn(Bz3 mF) 2] ( 8). Upon re-crystallization in DMSO:acetone conversion of 8 into [Zn(Bz3 mF) 2]·(DMSO) ( 8a) occurred. The crystal structures of 2, 5 and 8a were determined.

  9. Design and synthesis of diamide-coupled benzophenones as potential anticancer agents.

    Science.gov (United States)

    Zabiulla; Shamanth Neralagundi, H G; Bushra Begum, A; Prabhakar, B T; Khanum, Shaukath Ara

    2016-06-10

    A series of diamide-coupled benzophenone, 2-(4-benzoyl-phenoxy)-N-{2-[2-(4-benzoyl-phenoxy)-acetylamino]-phenyl}-acetamide analogues (9a-l) were synthesized by multistep reactions and all compounds were well characterized. Among the series (9a-l), compound 9k with three methyl groups at ortho position in rings A, B, and D and bromo group at the para position in ring E was selected as a lead compound by screening through multiple cancer cell types by in-vitro cytotoxic and antiproliferative assay systems. Also, the cytotoxic nature of the compound 9k resulted the regression of the tumor growth in-vivo, which could be due to decreased vascularisation in the peritoneum lining of the mice which regress the tumor growth. The results were reconfirmed in-vivo chorioallantoic membrane model which indicates a scope of developing 9k into potent anticancer drug in near future. PMID:27027818

  10. Polyisoprenylated benzophenones and an unusual polyisoprenylated tetracyclic xanthone from the fruits of Garcinia cambogia.

    Science.gov (United States)

    Masullo, Milena; Bassarello, Carla; Suzuki, Hisanori; Pizza, Cosimo; Piacente, Sonia

    2008-07-01

    In light of the wide range of biological activities of garcinol and with the aim of exploring some of them, we carried out its isolation from the fruits of Garcinia cambogia L. (Guttiferae). Surprisingly, the fruits were also found to contain guttiferones I, J, and K, compounds never reported in G. cambogia, along with three new compounds, namely, guttiferone M (1), guttiferone N (2), and the oxidized derivative of guttiferone K (6). Oxy-guttiferone K (6) is the first example of tetracyclic xanthone derived from the oxidation of a polyisoprenylated benzophenone from natural source. The natural formation of oxy-guttiferone K is in agreement with the previously described cyclization of garcinol by DPPH. PMID:18533663

  11. Synthesis and photopolymerization kinetics of a photoinitiator containing in-chain benzophenone and amine structure

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    A photoinitiator HTD bearing in-chain benzophenone (BP) and coinitiator tertiary amine,based on 4-hydroxybenzophenone (HBP),toluene-2,4-diisocyanate (TDI) and N,N-dimethylethanolamine (DMEA),was synthesized and characterized by 1H-NMR and UV-vis absorption spectroscopy.HTD had longer absorption wavelength in the UV-vis absorption spectra than the low molecular counterpart BP.The kinetics of photopolymerization was studied by real-time Fourier transformation infrared (FTIR) spectroscopy.It showed that HTD was a more effective photoinitiator than BP.When this photointiator was used to initiate polymerization of acrylates,both rate of polymerization and final conversion increased with increase of initiator concentration and light intensity.UV-vis extract analysis showed that the extractability of HTD was much lower than BP/DMEA on the same environment condition.

  12. Antiplasmodial benzophenone derivatives from the root barks of Symphonia globulifera (Clusiaceae).

    Science.gov (United States)

    Marti, Guillaume; Eparvier, Véronique; Moretti, Christian; Prado, Soizic; Grellier, Philippe; Hue, Nathalie; Thoison, Odile; Delpech, Bernard; Guéritte, Françoise; Litaudon, Marc

    2010-06-01

    In an effort to find antimalarial drugs, a systematic in vitro evaluation on a chloroquine-resistant strain of Plasmodium falciparum (FcB1) was undertaken on sixty plant extracts collected in French Guiana. The ethyl acetate extract obtained from the root barks of Symphonia globulifera exhibited a strong antiplasmodial activity (97% at 10 microg/ml). The phytochemical investigation of this extract led to the isolation of nine polycyclic polyprenylated acylphloroglucinol (PPAPs) compounds and two oxidized derivatives. All compounds showed antiplasmodial activity with IC(50)s ranged from 2.1 to 10.1 microM. A LC/ESI-MS(n) study performed on polyprenylated benzophenones previously isolated from Moronobea coccinea provided a reliable method for their detection in the extract and structural elucidation. PMID:20356612

  13. Bisphenol A, benzophenone-type ultraviolet filters, and phthalates in relation to uterine leiomyoma.

    Science.gov (United States)

    Pollack, A Z; Buck Louis, G M; Chen, Z; Sun, L; Trabert, B; Guo, Y; Kannan, K

    2015-02-01

    Bisphenol A, benzophenone-type UV filters, and phthalates are chemicals in high production and use including in a range of personal care products. Exposure of humans to these chemicals has been shown to affect endocrine function. Although short-lived, widespread exposure may lead to continual opportunity for these chemicals to elicit health effects in humans. The association of these chemicals with incident uterine leiomyoma, an estrogen sensitive disease, is not known. Urinary concentrations of bisphenol A (BPA), five benzophenone-type UV filters (2-hydroxy-4-methoxybenzophenone (2OH-4MeO-BP), 2,4-dihydroxybenzophenone (2,4OH-BP), 2,2׳-dihydroxybenzophenone (2,2׳OH-4MeO-BP), 2,2׳4,4׳-tetrahydroxybenzophenone (2,2׳4,4׳OH-BP), and 4-hydroxybenzophenone (4OH-BP), and 14 phthalate monoesters were quantified in 495 women who later underwent laparoscopy/laparotomy at 14 clinical sites for the diagnosis of fibroids. Significantly higher geometric mean creatinine-corrected concentrations of BPA, 2,4OH-BP, and 2OH-4MeO-BP were observed in women with than without fibroids [BPA: 2.09µg/g vs. 1.46µg/g p=0.004; 2,4OH-BP:11.10µg/g vs. 6.71µg/g p=0.01; 2OH-4MeO-BP: 11.31µg/g vs. 6.10µg/g p=0.01]. Mono-methyl phthalate levels were significantly lower in women with than without fibroids (1.78µg/g vs. 2.40µg/g). However, none of the exposures were associated with a significant odds ratio even when adjusting for relevant covariates. There was a lack of an association between select nonpersistent chemicals and the odds of a fibroid diagnosis. PMID:25531814

  14. 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. PMID:26368661

  15. Degradation of benzophenone in aqueous solution by Mn-Fe-K modified ceramic honeycomb-catalyzed ozonation

    Institute of Scientific and Technical Information of China (English)

    HOU Yan-jun; MA Jun; SUN Zhi-zhong; YU Ying-hui; ZHAO Lei

    2006-01-01

    Comparative studies of ozonation alone, ceramic honeycomb-catalyzed and Mn-Fe-K modified ceramic honeycomb catalyzed ozonafion processes have been undertaken with benzophenone as the model organic pollutant. The experimental results showed that the presence of Mn-Fe-K modified ceramic honeycombs significantly increased the removal rate of benzophenone and TOC compared with that achieved by ozonation alone or ceramic honeycomb-catalyzed ozonation. The electron paramagnetic resonance (EPR) experiments verified that higher benzophenone removal rate was attribute to more hydroxyl radicals generated in the Mn-Fe-K modified ceramic honeycomb-catalyzed ozonation. Under the conditions of this experiment, the degradation rate of all the three ozonation processes are increasing with the amount of catalyst, temperature and value of pH increased in the solution. We also investigated the effects of different process of ozone addition, the optimum conditions for preparing catalyst and influence of the Mn-Fe-K modified ceramic honeycomb after multiple-repeated use.

  16. Anti-inflammatory and analgesic activities of acetophenone semicarbazone and benzophenone semicarbazone

    Institute of Scientific and Technical Information of China (English)

    Shaikh M Mohsin Ali; Mele Jesmin; M Abul Kalam Azad; M Khairul Islam; Ronok Zahan

    2012-01-01

    Objective: To study anti-inflammatory and analgesic activities in swiss albino mice, two schiff bases namely acetophenone semicarbazone (ASC) and benzophenone semicarbazone (BSC) were synthesized and characterized. Methods: Two doses of the test compounds 25 and 50 mg/kg (p.o) for each were selected throughout the research work. The anti-inflammatory activity of the test compounds was determined by ‘carragenan induced mice paw edema inhibition’ method. The analgesic activity was determined by both, ‘acetic acid induced writhing’ and ‘tail immersion' methods. All such data were compared with standard drugs at the dose of 10 mg/kg (p.o.). Results:Both ASC and BSC have showed positive effects as anti-inflammatory and analgesic agents. Anti-inflammatory and analgesic activities of the test compounds at 50 mg/kg (p.o.) were quite comparable to those of standard drugs at 10 mg/kg (p.o.). Conclusion: Both ASC and BSC can be considered as potent anti-inflammatory and analgesic agents.

  17. Garcinia xanthochymus Benzophenones Promote Hyphal Apoptosis and Potentiate Activity of Fluconazole against Candida albicans Biofilms.

    Science.gov (United States)

    Jackson, Desmond N; Yang, Lin; Wu, ShiBiao; Kennelly, Edward J; Lipke, Peter N

    2015-10-01

    Xanthochymol and garcinol, isoprenylated benzophenones purified from Garcinia xanthochymus fruits, showed multiple activities against Candida albicans biofilms. Both compounds effectively prevented emergence of fungal germ tubes and were also cytostatic, with MICs of 1 to 3 μM. The compounds therefore inhibited development of hyphae and subsequent biofilm maturation. Xanthochymol treatment of developing and mature biofilms induced cell death. In early biofilm development, killing had the characteristics of apoptosis, including externalization of phosphatidyl serine and DNA fragmentation, as evidenced by terminal deoxynucleotidyltransferase-mediated dUTP-biotin nick end labeling (TUNEL) fluorescence. These activities resulted in failure of biofilm maturation and hyphal death in mature biofilms. In mature biofilms, xanthochymol and garcinol caused the death of biofilm hyphae, with 50% effective concentrations (EC50s) of 30 to 50 μM. Additionally, xanthochymol-mediated killing was complementary with fluconazole against mature biofilms, reducing the fluconazole EC50 from >1,024 μg/ml to 13 μg/ml. Therefore, xanthochymol has potential as an adjuvant for antifungal treatments as well as in studies of fungal apoptosis. PMID:26195512

  18. Preventing false negatives with high-resolution mass spectrometry: the benzophenone case.

    Science.gov (United States)

    Gallart-Ayala, H; Nuñez, O; Moyano, E; Galceran, M T; Martins, C P B

    2011-10-30

    Benzophenone (BP) is one of the many contaminants reported as present in foodstuffs due to its migration from food packaging materials. Liquid chromatography/tandem mass spectrometry (LC/MS/MS) is acknowledged in the literature as the method of choice for this analysis. However, cases have been reported where the use of this methodology was insufficient to unambiguously confirm the presence of a contaminant. In previous work performed by the authors, the unequivocal identification of BP in packaged foods was not possible even when monitoring two m/z transitions (precursor ion - product ion), since ion ratio errors higher than 20% were obtained. In order to overcome this analytical problem a fast, sensitive and selective liquid chromatography/high-resolution mass spectrometry (LC/HRMS) methodology has been developed and applied to the analysis of BP in packaged foods. A direct comparison between LC/HRMS and LC/MS/MS data indicated better selectivity when working with LC/HRMS at a resolving power of 50,000 FWHM (full width at half maximum) than when monitoring two m/z transitions by LC/MS/MS. The resolving power used enabled the detection and identification of Harman as the compound impeding the confirmation of BP by LC-MS/MS. Similar quantitative results were obtained by an Orbitrap mass analyser (Exactive™) and a triple quadrupole mass analyser (TSQ Quantum Ultra AM™). PMID:21953972

  19. Percutaneous absorption of benzophenone-3 loaded lipid nanoparticles and polymeric nanocapsules: A comparative study.

    Science.gov (United States)

    Gilbert, E; Roussel, L; Serre, C; Sandouk, R; Salmon, D; Kirilov, P; Haftek, M; Falson, F; Pirot, F

    2016-05-17

    For the last years, the increase of the number of skin cancer cases led to a growing awareness of the need of skin protection against ultraviolet (UV) radiations. Chemical UV filters are widely used into sunscreen formulations as benzophenone-3 (BP-3), a usually used broad spectrum chemical UV filter that has been shown to exercise undesirable effects after topical application. Innovative sunscreen formulations are thus necessary to provide more safety to users. Lipid carriers seem to be a good alternative to formulate chemical UV filters reducing their skin penetration while maintaining good photo-protective abilities. The aim of this work was to compare percutaneous absorption and cutaneous bioavailability of BP-3 loaded into solid lipid nanoparticles (SLN), nanostructured lipid carriers (NLC), nanostructured polymeric lipid carriers (NPLC) and nanocapsules (NC). Particle size, zeta potential and in vitro sun protection factor (SPF) of nanoparticle suspensions were also investigated. Results showed that polymeric lipid carriers, comprising NPLC and NC, significantly reduced BP-3 skin permeation while exhibiting the highest SPF. This study confirms the interesting potential of NPLC and NC to formulate chemical UV filters. PMID:26976501

  20. Exposures to environmental phenols in Southern California firefighters and findings of elevated urinary benzophenone-3 levels.

    Science.gov (United States)

    Waldman, Jed M; Gavin, Qi; Anderson, Meredith; Hoover, Sara; Alvaran, Josephine; Ip, Ho Sai Simon; Fenster, Laura; Wu, Nerissa T; Krowech, Gail; Plummer, Laurel; Israel, Leslie; Das, Rupali; She, Jianwen

    2016-03-01

    Firefighters are at increased risk for exposure to toxic chemicals compared to the general population, but few studies of this occupational group have included biomonitoring. We measured selected phenolic chemicals in urine collected from 101 Southern California firefighters. The analytes included bisphenol A (BPA), triclosan, benzophenone-3 (BP-3), and parabens, which are common ingredients in a range of consumer products. BP-3, BPA, triclosan, and methyl paraben were detected in almost all study subjects (94-100%). The BP-3 geometric mean for firefighters was approximately five times higher than for a comparable National Health and Nutrition Examination Survey (NHANES) subgroup. Demographic and exposure data were collected from medical records and via a questionnaire, and covariates were examined to assess associations with BP-3 levels. BP-3 levels were elevated across all firefighter age groups, with the highest levels observed in the 35 to 39year old group. Body fat percentage had a significant inverse association with BP-3 concentrations. Our results indicate pervasive exposure to BP-3, BPA, triclosan, and methyl paraben in this population of firefighters, consistent with studies of other populations. Further research is needed to investigate possible explanations for the higher observed BP-3 levels, such as occupational or California-specific exposures. PMID:26821331

  1. Garcinielliptone FC, a polyisoprenylated benzophenone from Platonia insignis Mart., promotes vasorelaxant effect on rat mesenteric artery.

    Science.gov (United States)

    Arcanjo, Daniel Dias Rufino; da Costa-Júnior, Joaquim Soares; Moura, Lucas Henrique Porfírio; Ferraz, Alexandre Barros Falcão; Rossatto, Raíssa Rebés; David, Jorge Maurício; Quintans-Júnior, Lucindo José; Oliveira, Rita de Cássia Meneses; Citó, Antônia Maria das Graças Lopes; de Oliveira, Aldeídia Pereira

    2014-01-01

    Polyisoprenylated benzophenones represent a group of chemical compounds commonly identified in Clusiaceae species and are responsible for a large amount of biological activities. In this work, the vasorelaxant effect induced by garcinielliptone FC (GFC) isolated from Platonia insignis Mart. (Clusiaceae), a monotype species from Platonia genus, was investigated. GFC promoted an endothelium-independent vasorelaxation on phenylephrine (PHE, 10(-5) mol L(-1))-induced vasoconstriction, but not on KCl (80 mmol L(-1))-induced vasoconstriction, on rat superior mesenteric artery rings. In addition, a concentration-dependent decrease of PHE- or serotonin-induced cumulative concentration-response curves was observed for GFC, and a slight decrease of pD₂ value on CaCl₂-induced vasoconstriction. In a Ca(2+)-free medium, GFC interfered in calcium mobilisation from PHE (10(-5) mol L(-1))-sensitive intracellular stores. GFC-induced vasorelaxant effect is probably mediated by a dual effect on mobilisation of calcium intracellular stores and attenuation of transmembrane calcium influx. PMID:24579922

  2. In vivo anticancer activity of vanillin, benzophenone and acetophenone thiosemicarbazones on Swiss albino mice

    Institute of Scientific and Technical Information of China (English)

    Sha Md. Shahan Shahriar; Shaikh M Mohsin Ali; Mele Jesmin; Md. Khairul Islam; Sarozit Mondal

    2014-01-01

    Objective: To study the anticancer activities of three schiff bases viz. vanillin thiosemicarbazone, benzophenone thiosemicarbazone and acetophenone thiosemicarbazone against Ehrlich ascites carcinoma (EAC) cells in Swiss albino mice. Methods: Synthesized compounds have administrated into the intraperitoneal cavity of the EAC inoculated mice at two doses. The anticancer activities have studied by monitoring the parameters such as cell growth inhibition, tumor weight measurement, survival time of EAC bearing mice as well as the changes in depleted hematological parameters due to tumorgenesis. All such data have been compared with those of a known standard drug bleomycin at the dose of 0.3 mg/kg (i.p.).Results:It has been found that these bases enhanced life span, reduced average tumor weight and inhibited tumor cell growth of EAC cell bearing mice remarkably. The results were similar in potency to those obtained with bleomycin. It was also found that the depleted hematological parameters (red blood count, white blood count and haemoglobin content) were found to be restored gradually towards normal within few weeks after ceasing the treatment.Conclusions:The compounds can be primarily considered more or less as potent anticancer agents.

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

    Science.gov (United States)

    Li, Jian; Ma, Li-Yun; Xu, Li

    2016-07-01

    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 975M(-1)s(-1) for oxybenzone, 49.6-261.7M(-1)s(-1) for 4-hydroxybenzophenone and 51.7-540M(-1)s(-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. PMID:27035274

  4. Rapid multi-analyte quantification of benzophenone, 4-methylbenzophenone and related derivatives from paperboard food packaging.

    Science.gov (United States)

    Koivikko, R; Pastorelli, S; Rodríguez-Bernaldo de Quirós, A; Paseiro-Cerrato, R; Paseiro-Losada, P; Simoneau, C

    2010-10-01

    Photo-initiators are used in printing inks hardened with UV light and one of the most commonly used photo-initiators is benzophenone (BP). Recent notifications under the Rapid Alert System for Food and Feed have shown migration of 4-methylbenzophenone (4-MBP) from packaging into cereals. A specific migration limit exists for BP of 0.6 mg kg(-1) for its use as an additive in plastics. There is no specific European legislation covering cardboard boxes and/or printing inks for food contact use. However, due to the high levels detected, the European Food Safety Authority (EFSA) published recommendations and the Standing Committee for the Food Chain and Animal Health endorsed a limit of 0.6 mg kg(-1) for the sum of BP and 4-MBP. While studies have been published on photo-initiators in the past, there is a fundamental lack of data on 4-MBP especially for its combined analysis with others. We present an HPLC method with diode array detector to simultaneously determine the levels of BP, 4-MBP as well as 7 other possible derivatives from secondary packaging for food applications. The method was tested and applied to 46 samples of paperboard for secondary packaging collected both from supermarkets and directly from a paperboard supplier. In addition, a survey was conducted on recycled paperboard (n = 19) collected from a supplier, to evaluate the background quantity of BP and other derivatives in recycled board. The most abundant photo-initiator found in the survey was BP, in 61% of samples, and 4-MBP was found in 30% of the samples. It seems that these compounds are used to replace one another. Other derivatives were found in minor quantities. Traces of BP were also found in 42% of the samples of recycled, unprinted board. PMID:20640959

  5. The Association Between Urinary Benzophenone Concentrations and Personal Care Product Use in Korean Adults.

    Science.gov (United States)

    Ko, Ahra; Kang, Hui-Seung; Park, Jae-Hong; Kwon, Ji-Eun; Moon, Gui Im; Hwang, Myung-Sil; Hwang, In Gyun

    2016-05-01

    Benzophenone (BP) derivatives are widely used in personal care products (PCPs) for protection from ultraviolet radiation. Because of their broad applications, BP derivatives have been found in various human bodily fluids. In the present study, we investigated the relationship between urinary concentrations of BP derivatives and PCP use in Korean adults. A urinary BP biomonitoring survey was conducted in Korea by the Ministry of Food and Drug Safety in 2014. BP derivatives (BP-1, BP-3, and 4-OH-BP) were measured in urine samples from 168 Korean adults (mean age, 43.2 ± 15.4 years) by high-performance liquid chromatography coupled with triple quadrupole tandem mass spectrometry. Information about the use of PCPs in the past 7 days was obtained by direct interviews. The mean levels of BP-1, BP-3, and 4-OH-BP were 0.87, 5.87, and 0.13 ng/g creatinine, respectively. The geometric mean levels of BP-1, BP-3, and 4-OH-BP were significantly higher in female than those in male. The medians of the urinary concentration of BP derivatives were significantly higher among users of the following PCPs than those in non-users; the PCPs included sunscreen, skin care products, functional cosmetics, makeup base, makeup, lip cosmetics, eye cosmetics, color cosmetics, perfume products, and nail products. A regression analysis revealed a significant linear association between urinary BP-3 concentrations and the number of additional cosmetic products used. These findings provide evidence of a positive association between exposure to PCPs and urinary BP derivative concentrations in Korean adults. PMID:26626599

  6. Molecular dynamics and simulations study on the vibrational and electronic solvatochromism of benzophenone

    International Nuclear Information System (INIS)

    Solvent plays a key role in diverse physico-chemical and biological processes. Therefore, understanding solute-solvent interactions at the molecular level of detail is of utmost importance. A comprehensive solvatochromic analysis of benzophenone (Bzp) was carried out in various solvents using Raman and electronic spectroscopy, in conjunction with Density Functional Theory (DFT) calculations of supramolecular solute-solvent clusters generated using classical Molecular Dynamics Simulations (c-MDSs). The >C=O stretching frequency undergoes a bathochromic shift with solvent polarity. Interestingly, in protic solvents this peak appears as a doublet: c-MDS and ad hoc explicit solvent ab initio calculations suggest that the lower and higher frequency peaks are associated with the hydrogen bonded and dangling carbonyl group of Bzp, respectively. Additionally, the dangling carbonyl in methanol (MeOH) solvent is 4 cm−1 blue-shifted relative to acetonitrile solvent, despite their similar dipolarity/polarizability. This suggests that the cybotactic region of the dangling carbonyl group in MeOH is very different from its bulk solvent structure. Therefore, we propose that this blue-shift of the dangling carbonyl originates in the hydrophobic solvation shell around it resulting from extended hydrogen bonding network of the protic solvents. Furthermore, the 11nπ∗ (band I) and 11ππ∗ (band II) electronic transitions show a hypsochromic and bathochromic shift, respectively. In particular, these shifts in protic solvents are due to differences in their excited state-hydrogen bonding mechanisms. Additionally, a linear relationship is obtained for band I and the >C=O stretching frequency (cm−1), which suggests that the different excitation wavelengths in band I correspond to different solvation states. Therefore, we hypothesize that the variation in excitation wavelengths in band I could arise from different solvation states leading to varying solvation dynamics. This will

  7. Molecular dynamics and simulations study on the vibrational and electronic solvatochromism of benzophenone

    Science.gov (United States)

    Ravi Kumar, Venkatraman; Verma, Chandra; Umapathy, Siva

    2016-02-01

    Solvent plays a key role in diverse physico-chemical and biological processes. Therefore, understanding solute-solvent interactions at the molecular level of detail is of utmost importance. A comprehensive solvatochromic analysis of benzophenone (Bzp) was carried out in various solvents using Raman and electronic spectroscopy, in conjunction with Density Functional Theory (DFT) calculations of supramolecular solute-solvent clusters generated using classical Molecular Dynamics Simulations (c-MDSs). The >C=O stretching frequency undergoes a bathochromic shift with solvent polarity. Interestingly, in protic solvents this peak appears as a doublet: c-MDS and ad hoc explicit solvent ab initio calculations suggest that the lower and higher frequency peaks are associated with the hydrogen bonded and dangling carbonyl group of Bzp, respectively. Additionally, the dangling carbonyl in methanol (MeOH) solvent is 4 cm-1 blue-shifted relative to acetonitrile solvent, despite their similar dipolarity/polarizability. This suggests that the cybotactic region of the dangling carbonyl group in MeOH is very different from its bulk solvent structure. Therefore, we propose that this blue-shift of the dangling carbonyl originates in the hydrophobic solvation shell around it resulting from extended hydrogen bonding network of the protic solvents. Furthermore, the 11nπ∗ (band I) and 11ππ∗ (band II) electronic transitions show a hypsochromic and bathochromic shift, respectively. In particular, these shifts in protic solvents are due to differences in their excited state-hydrogen bonding mechanisms. Additionally, a linear relationship is obtained for band I and the >C=O stretching frequency (cm-1), which suggests that the different excitation wavelengths in band I correspond to different solvation states. Therefore, we hypothesize that the variation in excitation wavelengths in band I could arise from different solvation states leading to varying solvation dynamics. This will have

  8. Benzotriazole, benzothiazole, and benzophenone compounds in indoor dust from the United States and East Asian countries.

    Science.gov (United States)

    Wang, Lei; Asimakopoulos, Alexandros G; Moon, Hyo-Bang; Nakata, Haruhiko; Kannan, Kurunthachalam

    2013-05-01

    Organic corrosion inhibitors (OCIs), including ultraviolet light filters, are widely used in plastics, rubbers, colorants, and coatings to increase the performance of products. Derivatives of benzotriazole (BTR), benzothiazole (BTH), and benzophenone (BP) are high-production volume OCIs that have been detected in the environment and human tissues. However, knowledge of their occurrence in indoor environments, as well as human exposure to them, is still lacking. In this study, BTR, BTH, BP and their 12 derivatives were determined in indoor dust for the first time. All three groups of OCIs were found in all 158 indoor dust samples from the U.S. and three East Asian countries (China, Japan, and Korea). The geometric mean (GM) concentration of the sum of six BTRs (GM CΣBTRs) ranged from 20 to 90 ng/g among the four countries studied, with a maximum CΣBTRs of ∼2000 ng/g found in a dust sample from China. Tolyltriazole was the major derivative of BTR measured in dust. GM CΣBTHs in indoor dust from the four countries ranged from 600 to 2000 ng/g. 2-OH-BTH was the predominant BTH in dust from the U.S., Japan, and Korea. GM CΣBPs in dust ranged from 80 to 600 ng/g, with 2-OH-4-MeO-BP and 2,4-2OH-BP, contributing to the majority of ∑BP concentrations. Based on the concentrations of three types of OCIs in indoor dust, human exposure through dust ingestion was calculated. Daily intake of OCIs through dust ingestion was higher for people in the U.S., Japan, and Korea than in China; the residents in urban China are exposed to higher levels of OCIs via dust ingestion than are those in rural China. PMID:23544437

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

    International Nuclear Information System (INIS)

    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 (E2). Unlike E2, 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

  10. Transformation pathways and acute toxicity variation of 4-hydroxyl benzophenone in chlorination disinfection process.

    Science.gov (United States)

    Liu, Wei; Wei, Dongbin; Liu, Qi; Du, Yuguo

    2016-07-01

    Benzophenones compounds (BPs) are widely used as UV filters, and have been frequently found in multiple environmental matrices. The residual of BPs in water would cause potential threats on ecological safety and human health. Chlorination disinfection is necessary in water treatment process, in which many chemicals remained in water would react with disinfectant chlorine and form toxic by-products. By using ultra performance liquid phase chromatography quadrupole time of flight mass spectrometer (UPLC-QTOF-MS), nuclear magnetic resonance (NMR), the transformation of 4-hydroxyl benezophenone (4HB) with free available chlorine (FAC) was characterized. Eight major products were detected and seven of them were identified. Transformation pathways of 4HB under acid, neutral, and alkaline conditions were proposed respectively. The transformation mechanisms involved electrophilic chlorine substitution of 4HB, Baeyer-Villiger oxidation of ketones, hydrolysis of esters and oxidative breakage of benzene ring. The orthogonal experiments of pH and dosages of disinfectant chlorine were conducted. The results suggested that pH conditions determined the occurrence of reaction types, and the dosages of disinfectant chlorine affected the extent of reactions. Photobacterium assay demonstrated that acute toxicity had significant increase after chlorination disinfection of 4HB. It was proved that 3,5-dichloro-4HB, one of the major transformation products, was responsible for the increasing acute toxicity after chlorination. It is notable that, 4HB at low level in real ambient water matrices could be transformed during simulated chlorination disinfection practice. Especially, two major products 3-chloro-4HB and 3,5-dichloro-4HB were detected out, implying the potential ecological risk after chlorination disinfection of 4HB. PMID:27085063

  11. UV-filter benzophenone-3 inhibits agonistic behavior in male Siamese fighting fish (Betta splendens).

    Science.gov (United States)

    Chen, Te-Hao; Wu, Yea-Ting; Ding, Wang-Hsien

    2016-03-01

    Benzophenone-3 (BP-3) is a widely used organic UV-filter compound. Despite the frequent occurrence of BP-3 in aquatic environments, little is known about its effect on fish behavior. The aim of this study was to investigate the endocrine disrupting effects of BP-3 in male fighting fish (Betta splendens) with a focus on agonistic behavior. Male fighting fish were exposed to 10, 100, and 1000 μg/L BP-3, as well as a solvent control (0.1 % ethanol) and a positive control (100 ng/L 17α-ethynylestradiol, EE2), for 28 days. At the beginning and the end of exposure, standard length and body mass of the fish were measured for calculating the condition factor (CF). In addition, spontaneous swimming activity (total distance moved) and agonistic behavior (maximum velocity and duration of opercular display in front of a mirror) were also quantified. At the end of exposure, the fish gonads were sampled for gonadosomatic index (GSI) measurement and histology. After the exposure, CF was significantly decreased in the 1000 μg/L BP-3 groups. Spontaneous swimming activity was not affected. However, maximum velocity was significantly reduced in the EE2 and 1000 μg/L BP-3 treatments; duration of opercular display was significantly decreased in the EE2 and 10 and 1000 μg/L BP-3 treatments. GSI was not significantly different between groups. There was a slight but statistically significant decrease of relative proportion of mature spermatozoa in testicular tissue in the 100 μg/L BP-3 treatment. Collectively, our results demonstrate that BP-3 can disrupt agonistic behavior of male fighting fish, indicating the endocrine disrupting activity of this compound. PMID:26589946

  12. Synthesis and characterization of sulfonated polyphenylene containing benzophenone moiety via nickel catalyzed polymerization

    International Nuclear Information System (INIS)

    Graphical abstract: Synthesis and characterization of sulfonated polyphenylene containing benzophenone moiety via nickel catalyzed polymerization. - Highlights: • The active new monomer, 1,6-dichloro-2,5-dibenzoylbenzene, was synthesized. • The sulfonated polyphenylenes containing benzoyl moiety were synthesized with high molecular weight using Ni(II) and Zn catalysts. • Carbon-carbon structures membranes showed good performance with high proton conductivity. - Abstract: The synthesis of polyphenylenes containing benzoyl moiety (PPBP), their functionalization with sulfonic acid groups, and the measurement of properties for PEMs are described. The new monomer was synthesized from an oxidation reaction of 2,5-dichloro-p-xylene, followed by Fridel-craft reaction with benzene. The polymerization was performed by a Ni-catalyzed carbon-carbon coupling reaction of 1,6-dichloro-2,5-dibenzoylbenzene, followed by a sulfonation reaction with chlorosulfuric acid. Compared with Nafion 211® membrane, these SPPBPs showed rational IECs from 1.47 to 2.51 meq./g, water uptake from 54.1 to 88.4%, proton conductivity from 80.6 to 108.6 mS/cm, and high thermal stability. The proton conductivity was higher than Nafion 211®. These results showed that the morphology of the polymer matrix was greatly affected by the membranes’ properties and stability. Membranes, including benzoyl segments without ether linkage, also provided good dimensional stability in spite of high IEC values. The properties of SPPBPs were very remarkable for fuel cell membrane application. This research demonstrated the possibility of promising SPPBP membranes for excellent proton conductivity

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

    International Nuclear Information System (INIS)

    Dimethyltin dichloride react with 2-ac ethylpyridine benzophenone azine (apba) in refluxing dry hexane to give (SnMe2 Cl2 (apba)) where the azine ligand acts as a bidentate N-N chelating ligand. The complex has been characterized by IR spectroscopy, 1H and 13C 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

  14. 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)

  15. Heavy atom effects in the Paternò–Büchi reaction of pyrimidine derivatives with 4,4’-disubstituted benzophenones

    OpenAIRE

    Qin-Hua Song; Jian-Bo Wang; Feng-Feng Kong

    2011-01-01

    The regioselectivity and the photochemical efficiency were investigated in the Paternò–Büchi reaction of 1,3-dimethylthymine (DMT) and 1,3-dimethyluracil (DMU) with benzophenone (1b) and some 4,4’-disubstituted derivatives (dimethoxy (1a), difluoro (1c), dichloro (1d), dibromo (1e) and dicyano benzophenone (1f)) that gives rise to two regioisomeric oxetanes, 2 and 3. The regioselectivity (the ratio of 2/3) decreased gradually for both DMT/DMU photochemical systems from 1...

  16. 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. PMID:26874345

  17. Vibrational, NMR and UV-Visible spectroscopic investigation, VCD and NLO studies on Benzophenone thiosemicarbazone using computational calculations

    Science.gov (United States)

    Moorthy, N.; Jobe Prabakar, P. C.; Ramalingam, S.; Periandy, S.; Parasuraman, K.

    2016-04-01

    In order to explore the unbelievable NLO property of prepared Benzophenone thiosemicarbazone (BPTSC), the experimental and theoretical investigation has been made. The theoretical calculations were made using RHF and CAM-B3LYP methods at 6-311++G(d,p) basis set. The title compound contains Cdbnd S ligand which helps to improve the second harmonic generation (SHG) efficiency. The molecule has been examined in terms of the vibrational, electronic and optical properties. The entire molecular behavior was studied by their fundamental IR and Raman wavenumbers and was compared with the theoretical aspect. The molecular chirality has been studied by performing vibrational circular dichroism (circularly polarized infrared radiation). The Mulliken charge levels of the compound ensure the perturbation of atomic charges according to the ligand. The molecular interaction of frontier orbitals emphasizes the modification of chemical properties of the compound through the reaction path. The enormous amount of NLO activity was induced by the Benzophenone in thiosemicarbazone. The Gibbs free energy was evaluated at different temperature and from which the enhancement of chemical stability was stressed. The VCD spectrum was simulated and the optical dichroism of the compound has been analyzed.

  18. Molecular dynamics and simulations study on the vibrational and electronic solvatochromism of benzophenone

    Energy Technology Data Exchange (ETDEWEB)

    Ravi Kumar, Venkatraman; Umapathy, Siva, E-mail: umapathy@ipc.iisc.ernet.in, E-mail: chandra@bii.a-star.edu.sg [Inorganic and Physical Chemistry Department, Indian Institute of Science, Bangalore 560012 (India); Verma, Chandra, E-mail: umapathy@ipc.iisc.ernet.in, E-mail: chandra@bii.a-star.edu.sg [Bioinformatics Institute - A*STAR, 30 Biopolis Street, # 07-01 Matrix, Singapore 138671 (Singapore); School of Biological Sciences, Nanyang Technological University, 60 Nanyang Drive, Singapore 637551 (Singapore); Department of Biological Sciences, National University of Singapore, 14 Science Drive 4, Singapore 117543 (Singapore)

    2016-02-14

    Solvent plays a key role in diverse physico-chemical and biological processes. Therefore, understanding solute-solvent interactions at the molecular level of detail is of utmost importance. A comprehensive solvatochromic analysis of benzophenone (Bzp) was carried out in various solvents using Raman and electronic spectroscopy, in conjunction with Density Functional Theory (DFT) calculations of supramolecular solute-solvent clusters generated using classical Molecular Dynamics Simulations (c-MDSs). The >C=O stretching frequency undergoes a bathochromic shift with solvent polarity. Interestingly, in protic solvents this peak appears as a doublet: c-MDS and ad hoc explicit solvent ab initio calculations suggest that the lower and higher frequency peaks are associated with the hydrogen bonded and dangling carbonyl group of Bzp, respectively. Additionally, the dangling carbonyl in methanol (MeOH) solvent is 4 cm{sup −1} blue-shifted relative to acetonitrile solvent, despite their similar dipolarity/polarizability. This suggests that the cybotactic region of the dangling carbonyl group in MeOH is very different from its bulk solvent structure. Therefore, we propose that this blue-shift of the dangling carbonyl originates in the hydrophobic solvation shell around it resulting from extended hydrogen bonding network of the protic solvents. Furthermore, the 1{sup 1}nπ{sup ∗} (band I) and 1{sup 1}ππ{sup ∗} (band II) electronic transitions show a hypsochromic and bathochromic shift, respectively. In particular, these shifts in protic solvents are due to differences in their excited state-hydrogen bonding mechanisms. Additionally, a linear relationship is obtained for band I and the >C=O stretching frequency (cm{sup −1}), which suggests that the different excitation wavelengths in band I correspond to different solvation states. Therefore, we hypothesize that the variation in excitation wavelengths in band I could arise from different solvation states leading to

  19. Occurrences, toxicities, and ecological risks of benzophenone-3, a common component of organic sunscreen products: a mini-review.

    Science.gov (United States)

    Kim, Sujin; Choi, Kyungho

    2014-09-01

    Benzophenone-3 (BP-3) has been widely used in sunscreens and many other consumer products, including cosmetics. The widespread use of BP-3 has resulted in its release into the water environment, and hence its potential impact on aquatic ecosystem is of concern. To better understand the risk associated with BP-3 in aquatic ecosystems, we conducted a thorough review of available articles regarding the physicochemical properties, toxicokinetics, environmental occurrence, and toxic effects of BP-3 and its suspected metabolites. BP-3 is lipophilic, photostable, and bioaccumulative, and can be rapidly absorbed via oral and dermal routes. BP-3 is reported to be transformed into three major metabolites in vivo, i.e., benzophenone-1 (BP-1), benzophenone-8 (BP-8), and 2,3,4-trihydroxybenzophenone (THB). BP-1 has a longer biological half-life than its parent compound and exhibits greater estrogenic potency in vitro. BP-3 has been detected in water, soil, sediments, sludge, and biota. The maximum detected level in ambient freshwater and seawater is 125ng/L and 577.5ng/L, respectively, and in wastewater influent is 10,400ng/L. The major sources of BP-3 are reported to be human recreational activities and wastewater treatment plant (WWTP) effluents. BP-3 and its derivatives have been also detected in fish lipid. In humans, BP-3 has been detected in urine, serum, and breast milk samples worldwide. BP-1 has also been detected in placental tissues of delivering women. While sunscreens and cosmetics are known to be major sources of exposure, the fact that BP-3 has been detected frequently among young children and men suggests other sources. An increasing number of in vitro studies have indicated the endocrine disrupting capacity of BP-3. Based on a receptor binding assay, BP-3 has shown strong anti-androgenic and weak estrogenic activities but at the same time BP-3 displays anti-estrogenic activity as well. Predicted no effect concentration (PNEC) for BP-3 was derived at 1.32

  20. (±-Pestalachloride D, an Antibacterial Racemate of Chlorinated Benzophenone Derivative from a Soft Coral-Derived Fungus Pestalotiopsis sp.

    Directory of Open Access Journals (Sweden)

    Dong-Sheng Deng

    2013-03-01

    Full Text Available A new antibacterial chlorinated benzophenone derivative, (±-pestalachloride D (1, along with a related analog, (±-pestalachloride C (2, was recently isolated from the marine-derived fungus Pestalotiopsis sp. isolated from a soft coral Sarcophyton sp. collected from Yongxing Island in the South China Sea. Both chiral HPLC analysis and single-crystal X-ray data indicated that 1 is a racemic mixture. Interestingly, 1 did not exhibit any effect in the zebrafish embryo teratogenicity assay, while 2 led to abnormal growth. The potential impact on zebrafish embryo growth is discussed based on their crystal structures. The main difference of crystal structures between 1 and 2 is that the six-member non-aromatic ring (O4, C10, C9, C8, C2′, and C3′ in 1 exhibits a distorted chair conformation, while 2 shows a distorted boat conformation. Moreover, compounds 1 and 2 both exhibited moderate antibacterial activity.

  1. 1D Ladder-like Chain and 1D Channeled 3D Supramolecular Architectures Based on Benzophenone-2,4'-dicarboxylic Acid

    Institute of Scientific and Technical Information of China (English)

    YANG Xiao-Gang; LI Dong-Sheng; FU Feng; WU Ya-Pan; WANG Ji-Jiang; WANG Yao-Yu

    2008-01-01

    The hydrothermal reactions of AgNO3, 2,2'-bipyridyl, and benzophenone-2,4'-dicarboxylic acid gave rise to two benzophenone-2,4'-dicarboxylic acid). The two compounds are extended by hydrogen bonds in two different apbonding between H2L ligands and water molecules, then extended to a 3D supramolecular architecture. Compound 2 possesses 3D supramolecular architecture containing 1D open channels, which are driven due to the strong H-bonding interactions occurring between the HL anions and water molecules; interestingly, [Ag(bpy)2]+ cations vestigated, the emission maxima for 2 exhibits red-shift compared with that of free ligand and 1 due to chelating effect of the 2,2'-bipyridine ligand to the silver ion and the presence of aromatic π-packing.

  2. Concentrations of the Sunscreen Agent Benzophenone-3 in Residents of the United States: National Health and Nutrition Examination Survey 2003–2004

    OpenAIRE

    Calafat, Antonia M.; Wong, Lee-Yang; Ye, Xiaoyun; Reidy, John A; Needham, Larry L.

    2008-01-01

    Background The capability of benzophenone-3 (BP-3) to absorb and dissipate ultraviolet radiation facilitates its use as a sunscreen agent. BP-3 has other uses in many consumer products (e.g., as fragrance and flavor enhancer, photoinitiator, ultraviolet curing agent, polymerization inhibitor). Objectives Our goal was to assess exposure to BP-3 in a representative sample of the U.S. general population ≥ 6 years of age. Methods Using automated solid-phase extraction coupled to high-performance ...

  3. Ozonation and peroxone oxidation of benzophenone-3 in water: Effect of operational parameters and identification of intermediate products

    Energy Technology Data Exchange (ETDEWEB)

    Gago-Ferrero, Pablo [Department of Environmental Chemistry, IDAEA-CSIC, Jordi Girona 18-26, 08034 Barcelona (Spain); Demeestere, Kristof, E-mail: Kristof.Demeestere@UGent.be [Research Group EnVOC, Department of Sustainable Organic Chemistry and Technology, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, B-9000 Ghent (Belgium); Silvia Díaz-Cruz, M. [Department of Environmental Chemistry, IDAEA-CSIC, Jordi Girona 18-26, 08034 Barcelona (Spain); Barceló, Damià [Department of Environmental Chemistry, IDAEA-CSIC, Jordi Girona 18-26, 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)

    2013-01-15

    The goal of this study was to bring forward new data and insights with respect to the effect of operational variables and reaction pathways during ozonation and peroxone oxidation of the UV filter compound benzophenone-3 (BP3) in water. A systematic parameter study, investigating the effect of the ozone inlet concentration, temperature, pH, H{sub 2}O{sub 2} and t-butanol addition in a lab-scale bubble reactor, showed the promising potential of ozonation towards BP3 degradation. pH showed to be a major process parameter, with half-life times (5.1–15.0 min) being more than two times shorter at pH 10 compared to neutral and acid conditions. This indicates the important role of hydroxyl radicals as supported by the addition of H{sub 2}O{sub 2} and t-butanol as HO· promoter and scavenger, respectively. Ozonation intermediate products were identified by liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry (HPLC–QqTOF-MS/MS). Demethylation and non-selective HO· attack proved to be the major reaction mechanisms. Where available, identified intermediates were confirmed using analytical standards, and concentration profiles along the ozonation process were determined through selective targeted MS/MS analysis. Benzophenone-1 (BP1), also being a UV-filter compound, and 2,2′-dihydroxy-4-methoxybenzophenone (DHMB) revealed to be the major BP3 degradation products, showing a maximum concentration at about the half-life time of BP3. Highlights: ► Ozonation shows to be a promising technology for the elimination of BP3. ► New data are obtained on the effect of process parameters on BP3 removal. ► Conditions favoring hydroxyl radical formation accelerate the degradation process. ► The reactivity is higher through radicalar pathways compared to direct ozonation. ► Seven major transformation products of BP3, including BP1 and DHMB, are identified.

  4. 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

    2016-06-01

    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. PMID:26905612

  5. G2/M Cell Cycle Arrest and Tumor Selective Apoptosis of Acute Leukemia Cells by a Promising Benzophenone Thiosemicarbazone Compound.

    Science.gov (United States)

    Cabrera, Maia; Gomez, Natalia; Remes Lenicov, Federico; Echeverría, Emiliana; Shayo, Carina; Moglioni, Albertina; Fernández, Natalia; Davio, Carlos

    2015-01-01

    Anti-mitotic therapies have been considered a hallmark in strategies against abnormally proliferating cells. Focusing on the extensively studied family of thiosemicarbazone (TSC) compounds, we have previously identified 4,4'-dimethoxybenzophenone thiosemicarbazone (T44Bf) as a promising pharmacological compound in a panel of human leukemia cell lines (HL60, U937, KG1a and Jurkat). Present findings indicate that T44Bf-mediated antiproliferative effects are associated with a reversible chronic mitotic arrest caused by defects in chromosome alignment, followed by induced programmed cell death. Furthermore, T44Bf selectively induces apoptosis in leukemia cell lines when compared to normal peripheral blood mononuclear cells. The underlying mechanism of action involves the activation of the mitochondria signaling pathway, with loss of mitochondrial membrane potential and sustained phosphorylation of anti-apoptotic protein Bcl-xL as well as increased Bcl-2 (enhanced phosphorylated fraction) and pro-apoptotic protein Bad levels. In addition, ERK signaling pathway activation was found to be a requisite for T44Bf apoptotic activity. Our findings further describe a novel activity for a benzophenone thiosemicarbazone and propose T44Bf as a promising anti-mitotic prototype to develop chemotherapeutic agents to treat acute leukemia malignancies. PMID:26360247

  6. G2/M Cell Cycle Arrest and Tumor Selective Apoptosis of Acute Leukemia Cells by a Promising Benzophenone Thiosemicarbazone Compound.

    Directory of Open Access Journals (Sweden)

    Maia Cabrera

    Full Text Available Anti-mitotic therapies have been considered a hallmark in strategies against abnormally proliferating cells. Focusing on the extensively studied family of thiosemicarbazone (TSC compounds, we have previously identified 4,4'-dimethoxybenzophenone thiosemicarbazone (T44Bf as a promising pharmacological compound in a panel of human leukemia cell lines (HL60, U937, KG1a and Jurkat. Present findings indicate that T44Bf-mediated antiproliferative effects are associated with a reversible chronic mitotic arrest caused by defects in chromosome alignment, followed by induced programmed cell death. Furthermore, T44Bf selectively induces apoptosis in leukemia cell lines when compared to normal peripheral blood mononuclear cells. The underlying mechanism of action involves the activation of the mitochondria signaling pathway, with loss of mitochondrial membrane potential and sustained phosphorylation of anti-apoptotic protein Bcl-xL as well as increased Bcl-2 (enhanced phosphorylated fraction and pro-apoptotic protein Bad levels. In addition, ERK signaling pathway activation was found to be a requisite for T44Bf apoptotic activity. Our findings further describe a novel activity for a benzophenone thiosemicarbazone and propose T44Bf as a promising anti-mitotic prototype to develop chemotherapeutic agents to treat acute leukemia malignancies.

  7. 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.

  8. Mesoporous silica aerogel as a drug carrier for the enhancement of the sunscreen ability of benzophenone-3.

    Science.gov (United States)

    Li, C C; Chen, Y T; Lin, Y T; Sie, S F; Chen-Yang, Y W

    2014-03-01

    In the present study, about 45 and 34 wt% of benzophenone-3 (BP-3), an organic UV filter, was adsorbed on a high surface area mesoporous silica (MS) drug carrier to prepare BP-3-bearing MS (MSBP) sunscreen materials MSBP-1 and MSBP-2, respectively. The effect of the adsorption of BP-3 by MS on the UV protection ability of MSBP was demonstrated and a synergistic UV protection effect was observed in the as-prepared MSBP UV filters. Compared with free BP-3, adsorbed BP-3 had greatly reduced crystallinity and the dispersion of MSBP was significantly improved in the sunscreen. The in vitro sun protection factor (SPF) and in vitro UV-A values of the MSBP-2-based sunscreen was about 17.3% and 17.0% higher than that of free BP-3-based sunscreen, respectively, indicating that the ability of the sunscreen to protect against UV-B and UV-A improved because of the BP-3 content of the MS matrix. In addition, the decrease in SPF and UV-A values over time was significantly less in the MSBP-based sunscreens than in free BP-3-based sunscreen. Results of this study reveal that MS is a promising organic sunscreen carrier as well as a potential carrier for other topical drugs. PMID:24362058

  9. Heterogeneous photocatalytic degradation of the endocrine-disrupting chemical Benzophenone-3: Parameters optimization and by-products identification.

    Science.gov (United States)

    Zúñiga-Benítez, Henry; Aristizábal-Ciro, Carolina; Peñuela, Gustavo A

    2016-02-01

    Benzophenone-3 (BP3) is one of the most used UV filters. Its disruptive effect on the endocrine system of different living beings has been demonstrated by several research groups. Present work addresses on a photocatalytic degradation of BP3 using particles of titanium dioxide in aqueous solutions considering the effect of operating parameters such as pH, catalyst and pollutant initial concentrations, and the presence of hydrogen peroxide, acetonitrile and isopropanol in the solution. In this way, a face centered, central composite design was carried out for the identification of significant factors or interactions that allow the determination of the conditions under which the pollutant suffers the highest rates of degradation. A solution initial pH of 9.0, a TiO2 concentration of 1.184 g L(-1) and an H2O2 concentration of 128.069 mg L(-1) were established as the optimal conditions for the substrate removal. In aqueous solutions and low concentrations of the pollutant (photocatalysis with TiO2 is a potential method to remove BP3 from water. Additionally, tests using acetonitrile as solvent and isopropanol as hydroxyl radical (OH(.)) scavenger suggested that, OH(.) was the main agent responsible of substrate degradation. Finally, ten process by-products were identified and a degradation route was proposed. PMID:26686077

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

    International Nuclear Information System (INIS)

    The synthesis of photosensitive urethane dimethacrylate that contains poly(ethylene oxide) sequence (PEG, Mw: 400), carboxylic and benzophenone moieties, and its characterization by specific methods (1H and 13C 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 (RmaxP: 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 (AgNO3 and AuBr3) 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Buruiana, Emil C., E-mail: emilbur@icmpp.ro; Chibac, Andreea Laura; Buruiana, Tinca; Melinte, Violeta [Petru Poni Institute of Macromolecular Chemistry (Romania); Balan, Lavinia [Institut de Science des Materiaux de Mulhouse CNRS LRC 7228 (France)

    2013-01-15

    The synthesis of photosensitive urethane dimethacrylate that contains poly(ethylene oxide) sequence (PEG, M{sub w}: 400), carboxylic and benzophenone moieties, and its characterization by specific methods ({sup 1}H and {sup 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{sub max}{sup P}: 0.108 s{sup -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{sup -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{sub 3} and AuBr{sub 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.

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

    OpenAIRE

    Sobańska, Anna W.; Katarzyna Kałębasiak; Jarosław Pyzowski; Elżbieta Brzezińska

    2015-01-01

    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 a...

  13. Effect of Zn/Al Layered Double Hydroxide Containing 2-Hydroxy-4-n-octoxy-benzophenone on UV Aging Resistance of Asphalt

    OpenAIRE

    Chao Peng; Jianying Yu; Jing Dai; Jian Yin

    2015-01-01

    UV radiation is a main factor to reduce the service life of asphalt pavement due to the UV aging of asphalt binder. To obtain enhanced UV aging resistance, an organic UV absorber called 2-hydroxy-4-n-octoxy-benzophenone (HNOB) had been intercalated into an inorganic UV absorber called Zn/Al layered double hydroxide (LDH) to play a combined anti-UV role in asphalt binder. Fourier transform infrared spectroscopy revealed that HNOB anions have been intercalated into the interlayer galleries of Z...

  14. Heavy atom effects in the Paternò–Büchi reaction of pyrimidine derivatives with 4,4’-disubstituted benzophenones

    Directory of Open Access Journals (Sweden)

    Qin-Hua Song

    2011-01-01

    Full Text Available The regioselectivity and the photochemical efficiency were investigated in the Paternò–Büchi reaction of 1,3-dimethylthymine (DMT and 1,3-dimethyluracil (DMU with benzophenone (1b and some 4,4’-disubstituted derivatives (dimethoxy (1a, difluoro (1c, dichloro (1d, dibromo (1e and dicyano benzophenone (1f that gives rise to two regioisomeric oxetanes, 2 and 3. The regioselectivity (the ratio of 2/3 decreased gradually for both DMT/DMU photochemical systems from 1a to 1f. That is, a halogen atom as an electron-withdrawing group (EWG has a pronounced effect on the regioselectivity. However, the photochemical efficiency of the 1e systems did not show the expected increase, but decreased relative to systems with 1b. Temperature effects on the regioselectivity of 1b–e systems showed some interesting features for systems with heavy atoms (including the 1d and 1e systems, such as higher inversion temperatures, and an entropy-controlled regioselectively whereas the regioselectivity for two other systems (1b and 1c is enthalpy–entropy controlled. A heavy atom effect is suggested to be responsible for these unusual phenomena based on the triplet-diradical mechanism of the Paternò–Büchi reaction.

  15. Determination of selected parabens, benzophenones, triclosan and triclocarban in agricultural soils after and before treatment with compost from sewage sludge: A lixiviation study.

    Science.gov (United States)

    Camino-Sánchez, F J; Zafra-Gómez, A; Dorival-García, N; Juárez-Jiménez, B; Vílchez, J L

    2016-04-01

    An accurate and sensitive method for the determination of selected EDCs in soil and compost from wastewater treatment plants is developed and validated. Five parabens, six benzophenone-UV filters and the antibacterials triclosan and triclocarban were selected as target analytes. The parameters for ultrasound-assisted extraction were thoroughly optimized. After extraction, the analytes were detected and quantified using ultra-high performance liquid chromatography tandem mass spectrometry. Ethylparaben (ring-(13)C6 labelled) and deuterated benzophenone (BP-d10) were used as internal standards. The method was validated using matrix-matched calibration and recovery assays with spiked samples. The limits of detection ranged from 0.03 to 0.40 ng g(-1) and the limits of quantification from 0.1 to 1.0 ng g(-1), while precision in terms of relative standard deviation was between 9% and 21%. Recovery rates ranged from 83% to 107%. The validated method was applied for the study of the behavior of the selected compounds in agricultural soils treated and un-treated with compost from WWTP. A lixiviation study was developed in both agricultural soil and treated soil and first order kinetic models of their disappearance at different depths are proposed. The application of organic composts in the soil leads to an increase of the disappearance rate of the studied compounds. The lixiviation study also shows the risk of pollution of groundwater aquifers after disposal or waste of these EDCs in agricultural soils is not high. PMID:26838425

  16. Bioassay and ultraperformance liquid chromatography/mass spectrometry guided isolation of apoptosis-inducing benzophenones and xanthone from the pericarp of Garcinia yunnanensis Hu.

    Science.gov (United States)

    Xu, Gang; Feng, Chao; Zhou, Yan; Han, Quan-Bin; Qiao, Chun-Feng; Huang, Sheng-Xiong; Chang, Donald C; Zhao, Qin-Shi; Luo, Kathy Q; Xu, Hong-Xi

    2008-12-10

    Bioassay and ultraperformance liquid chromatography/photodiode array/mass spectrometry (UPLC/PDA/MS) guided isolation of the apoptosis-inducing active metabolites on HeLa-C3 cells from the pericarp of Garcinia yunnanensis (Guttiferae) yielded five active compounds, including the new garciyunnanins A (1) and B (2). The structures of the compounds were elucidated by comprehensive nuclear magnetic resonance and mass spectrometry analysis. Garciyunnanin B (2), featured with a natural tetracyclic xanthone skeleton derived from a polyisoprenylated benzophenone, is structurally interesting since it can be seen as an evidence of the previously described cyclization of garcinol by 2,2-diphenyl-1-picrylhydrazyl (DPPH). Garciyunnanin A (1) contains a 3-monohydroxy benzophenone skeleton, which is rarely found in Garcinia species. Both new compounds induce HeLa-C3 cells into apoptosis after 72 h of incubation at 15 microM. It is noteworthy that oblongifolin C (4), the major constituent of this plant, has proved to be the most active one among the isolates for inducing apoptotic cell death in cervical cancer derived HeLa-C3 sensor cells. PMID:19007298

  17. 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 endogenous...

  18. 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.

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

    Science.gov (United States)

    Sobańska, Anna W; Kałębasiak, Katarzyna; Pyzowski, Jarosław; Brzezińska, Elżbieta

    2015-01-01

    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. PMID:25734022

  20. THE EFFECTS OF MAGNETIC FIELD ON GRAFT COPOLYMERIZATION OF METHYL METHACRYLATE ONTO POLYVINYL ALCOHOL IN THE PRESENCE OF BENZOPHENONE DURING UV IRRADIATION

    Institute of Scientific and Technical Information of China (English)

    HUANG Junlian; WU Qingfong

    1990-01-01

    The effects of magnetic field on the graft ratio and stereoregularity of grafts of PVA-g-MMA in the presence of benzophenone during UV irradiation are discussed. By means of IR, it was found that the graft ratio was increased with the increment of magnetic field strength. Furthermore, application of relative weak magnetic field of 0.4 Tesla had been shown to substantially enhance the stereo-regularity of graft copolymer. The maximum stereo-regularity appeared when the graft ratio approached to 85% with the magnetic field of 1.2 Tesla (T). The resistance to moisture and heat resistance of the grafted copolymer in the presence of magnetic field were also improved.

  1. Ultrasound-assisted dispersive liquid-liquid microextraction plus simultaneous silylation for rapid determination of salicylate and benzophenone-type ultraviolet filters in aqueous samples.

    Science.gov (United States)

    Wu, Jen-Wen; Chen, Hsin-Chang; Ding, Wang-Hsien

    2013-08-01

    A rapid procedure, using minimal amounts of solvent, for the reliable determination of five salicylate and benzophenone-type ultraviolet (UV) filters: ethylhexyl salicylate (EHS), 3,3,5-trimethyl-cyclohexyl salicylate (HMS), 2-hydroxy-4-methoxybenzophenone (BP-3), 2,4-dihydroxy-benzophenone (BP-1) and 2,2'-dihydroxy-4-methoxybenzophenone (BP-8), in aqueous samples is described. The method involves an ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME) plus simultaneous silylation prior to their determination by gas chromatography-mass spectrometry (GC-MS). The parameters affecting the extraction and derivatization efficiency of the target UV filters from aqueous samples were systematically investigated and the conditions optimized. The optimal silylation and extraction conditions involved the rapid injection of a mixture of 750μL of acetone (as a dispersant), 15μL of tetrachloroethylene (as an extractant), and 20μL of BSTFA (as a derivatizing agent) into a 10-mL volume of aqueous samples (pH 7.0) containing 0.5g of sodium chloride in a glass tube with a conical bottom. After ultrasonication for 2.0min and centrifugation at 5000rpm (10min), the sedimented phase 5.0μL was directly introduced into the GC-MS. The limits of quantitation (LOQs) were less than 6ng/L. The precision for these analytes, as indicated by the relative standard deviations (RSDs), was less than 9% for both intra- and inter-day analysis. Accuracy, expressed as the mean extraction recovery, was between 74 and 92%. The method was then applied to environmental aqueous samples, using a standard addition method, showing the occurrence of BP-3 in samples of both river water and municipal wastewater treatment plant (MWTP) effluents. PMID:23831000

  2. Direct interaction of garcinol and related polyisoprenylated benzophenones of Garcinia cambogia fruits with the transcription factor STAT-1 as a likely mechanism of their inhibitory effect on cytokine signaling pathways.

    Science.gov (United States)

    Masullo, Milena; Menegazzi, Marta; Di Micco, Simone; Beffy, Pascale; Bifulco, Giuseppe; Dal Bosco, Martina; Novelli, Michela; Pizza, Cosimo; Masiello, Pellegrino; Piacente, Sonia

    2014-03-28

    Garcinol (1), a polyisoprenylated benzophenone occurring in Garcinia species, has been reported to exert anti-inflammatory activity in LPS-stimulated macrophages, through inhibition of NF-κB and/or JAK/STAT-1 activation. In order to provide deeper insight into its effects on the cytokine signaling pathway and to clarify the underlying molecular mechanisms, 1 was isolated from the fruits of Garcinia cambogia along with two other polyisoprenylated benzophenones, guttiferones K (2) and guttiferone M (3), differing from each other in their isoprenyl moieties and their positions on the benzophenone core. The affinities of 1-3 for the STAT-1 protein have been evaluated by surface plasmon resonance and molecular docking studies and resulted in KD values in the micromolar range. Consistent with the observed high affinity toward the STAT-1 protein, garcinol and guttiferones K and M were able to modulate cytokine signaling in different cultured cell lines, mainly by inhibiting STAT-1 nuclear transfer and DNA binding, as assessed by an electrophorectic mobility shift assay. PMID:24417609

  3. 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

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

    International Nuclear Information System (INIS)

    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

  5. 7-Epiclusianone, a Benzophenone Extracted from Garcinia brasiliensis (Clusiaceae, Induces Cell Cycle Arrest in G1/S Transition in A549 Cells

    Directory of Open Access Journals (Sweden)

    Marisa Ionta

    2015-07-01

    Full Text Available Lung cancer is the leading cause of cancer deaths in the world. Disease stage is the most relevant factor influencing mortality. Unfortunately, most patients are still diagnosed at an advanced stage and their five-year survival rate is only 4%. Thus, it is relevant to identify novel drugs that can improve the treatment options for lung cancer. Natural products have been an important source for the discovery of new compounds with pharmacological potential including antineoplastic agents. We have previously isolated a prenylated benzophenone (7-epiclusianone from Garcinia brasiliensis (Clusiaceae that has several biological properties including antiproliferative activity against cancer cell lines. In continuation with our studies, the present work aimed to investigate the mechanisms involved with antiproliferative activity of 7-epiclusianone in A549 cells. Our data showed that 7-epiclusianone reduced the viability of A549 cells in a concentration-dependent manner (IC50 of 16.13 ± 1.12 μM. Cells were arrested in G1/S transition and apoptosis was induced. In addition, we observed morphological changes with cytoskeleton disorganization in consequence of the treatment. Taken together, the results showed that cell cycle arrest in G1/S transition is the main mechanism involved with antiproliferative activity of 7-epiclusianone. Our results are promising and open up the prospect of using this compound in further anticancer in vivo studies.

  6. Photoallergic contact dermatitis due to combined UVB (4-methylbenzylidene camphor/octyl methoxycinnamate) and UVA (benzophenone-3/butyl methoxydibenzoylmethane) absorber sensitization.

    Science.gov (United States)

    Schmidt, T; Ring, J; Abeck, D

    1998-01-01

    In a 71-year-old male Caucasian patient with persistent eczema on light-exposed skin, photocontact allergy was demonstrated to the UV filter substances 4-methylbenzylidene camphor (UVB), octyl methoxycinnamate (UVB), benzophenone-3 (UVA) and butyl methoxydibenzoylmethane (UVA) present in sunscreen products used by the patient over several years. A significantly reduced UVB sensitivity of 25 mJ/cm2 in this patient (normal minimal erythema dose in our laboratory = 70-130 mJ/cm2) was considered an early indication of a persistent light reaction. Topical anti-inflammatory treatment over 2 weeks together with consequent application of a sunscreen containing Mexoryl SX/titanium dioxide led to complete remission. Taking into account the widespread use of the above UV filter substances not only in sun protection products, but also in cosmetics such as antiaging lotions and day care products, the possible risk of allergy to these chemicals has to be taken seriously. The substitution of known photocontact sensitizers in UV filters by photostable compounds and detailed product information are the basis of preventive strategies. PMID:9621150

  7. Flavonoids, benzophenones and a new euphane derivative from Clusia columnaris Engl. Flavonóides, benzofenonas e um novo eufano de Clusia columnaris Engl.

    Directory of Open Access Journals (Sweden)

    Reinaldo S. Compagnone

    2008-03-01

    Full Text Available The polyisoprenylated benzophenones machuone and clusiachromene A have been isolated from the fruits of Clusia columnaris. The hexane extract of the young branches with leaves afforded a new euphane derivative, whose structure was elucidated by spectroscopic methods. On the contrary, the most polar EtOAc and ButOH extracts were constituted of flavonoid C-glucosides (isovitexin, vitexin and vitexin-2"-xyloside and seven biflavonoids of the so-called Garcinia group.Dos frutos de Clusia columnaris foram isoladas as benzofenonas poliisopreniladas machuona e clusiacromeno A. Do extrato em hexano obtido de galhos e folhas novas, um novo triterpeno do tipo eufano foi isolado. Sua estrutura foi elucidada através de métodos espectroscópicos. Por outro lado, dos extratos mais polares - em acetato de etila e em butanol, foram isolados os flavonóides C-glicosilados isovitexina, vitexina e vitexina-2"-xilosídeo, além de sete bisflavonóides conhecidos como bisflavonóides do grupo da Garcinia.

  8. Continuous irradiation induced luminescence from benzophenone, 4,4{prime}-dichlorobenzophenone, and 4-(dimethylamino)benzaldehyde in solid environments and its pressure dependence

    Energy Technology Data Exchange (ETDEWEB)

    Dreger, Z.A.; Drickamer, H.G. [Univ. of Illinois, Urbana, IL (United States)

    1997-02-20

    We report a strong emission change induced by continuous light irradiation in two ketones, benzophenone and 4,4{prime}-dichlorobenzophenone, and an aldehyde, 4-(dimethylamino)benzaldehyde, in their crystalline state as well as dissolved in solid polymers. With prolonged laser irradiation, a time evolution of the emission intensity shows complex features, but two clear competing trends can be distinguished: an increase and/or decrease of the emission intensity. It is shown that these trends may be a result of creation of either an emissive or a nonemissive species. The relative importance of these two pathways is significantly dependent on the type of medium and external pressure. The most characteristic feature of these dependencies is the fact that in crystalline environments, in contrast to polymers, the emission intensity at all pressures only decreases. A kinetic model is developed that assumes the lowest triplet state as the origin of the high photoreactivity of these molecules, causing their emission intensity change. This model embraces the observations either in crystalline or polymeric environments and is solved for two limiting cases: a predominance of the hydrogen abstraction reaction from the polymer or a predominance of the ionization due to biphotonic excitation of the triplet state. These processes are assumed responsible, respectively, for the creation of emissive and nonemissive photoproducts. 29 refs., 19 figs., 2 tabs.

  9. Effect of environment on pressure-induced emission of benzophenone, 4,4{prime}-dichlorobenzophenone, and 4-(dimethylamino)benzaldehyde in solid media

    Energy Technology Data Exchange (ETDEWEB)

    Dreger, Z.A.; Drickamer, H.G. [Univ. of Illinois, Urbana, IL (United States)

    1997-02-20

    The pressure-induced emission of three aromatic carbonyls - benzophenone (BP), 4,4{prime}-dichlorobenzophenone (DCBP), and 4-(dimethylamino)benzaldehyde (DMABA) - dissolved in solid polymers and also in their crystalline state has been studied. Under pressure all compounds dissolved in polymers reveal a significant enhancement of the luminescence emission in the low-pressure region. The degree of increase is strongly dependent on the type of polymer. DMABA exhibits both fluorescence and phosphorescence, whereas BP and DCBP molecules show only phosphorescence. For all these molecules a model based on the increase with increasing pressure of the amount of {pi},{pi}{sup *} character in the initially predominately n,{pi}{sup *} triplet state is proposed to account for the observed increase of the emission intensity. In the case of DMABA it is proposed that the increase of the {pi},{pi}{sup *} character in the triplet state increases the emission intensity in two concurrent steps: by an increase of the radiative rate from the triplet state and by a decrease of the intersystem crossing rate between singlet and triplet states. The first factor increases phosphorescence intensity, and the second one effects the fluorescence. In the case of BP and DCBP, where the intersystem crossing process is very fast, the increase of pressure increases mainly the radiative rate of the lowest triplet state. 22 refs., 8 figs.

  10. Major benzophenone concentrations and influence of food consumption among the general population in Korea, and the association with oxidative stress biomarker.

    Science.gov (United States)

    Kim, Bokyung; Kwon, Bareum; Jang, Sol; Kim, Pan-Gyi; Ji, Kyunghee

    2016-09-15

    Benzophenones (BPs) have been used as sunscreen agents and as ultraviolet stabilizers in plastic surface coatings for food packaging. However, few studies have been performed to examine the level of human exposure to BPs and the potential sources of such exposure. We evaluated the exposure levels to six major BPs (BP-1, BP-2, BP-3, BP-4, BP-8, and 4-hydroxybenzophenone (4-OH-BP)) among the adult population in two cities in Korea, and investigated the potential dietary sources of the BPs. Urinary levels of malondialdehyde (MDA) as an oxidative stress biomarker as well as their association with the levels of BPs were also analyzed. Among the six BPs analyzed, 4-OH-BP, BP-1, BP-3, and BP-4 were detected in 77%, 49%, 27%, and 21% of the population, respectively. BP concentrations were relatively higher in younger (people in their 20s and 30s) cosmetic users and leaner women. Even after the adjustment of age, body mass index, and cosmetic use, the consumption of frozen storage food, instant noodles, and instant coffee was significantly correlated with urinary BPs, and these associations were sex-dependent. No significant correlation was observed between the levels of BPs and levels of MDA. The results of the present study will be useful for developing plans of public health management of BPs. PMID:27208722

  11. Improvement in UV protection retention capability and reduction in skin penetration of benzophenone-3 with mesoporous silica as drug carrier by encapsulation.

    Science.gov (United States)

    Li, C C; Lin, Y T; Chen, Y T; Sie, S F; Chen-Yang, Y W

    2015-07-01

    In this study, various amounts of benzophenone-3 (BP-3), a solid-type of organic UV-filter, were encapsulated in mesoporous silica (MS) to form the BP-3 encapsulated by MS UV-filters (BESs), BES-1 and BES-2, via in-situ sol-gel process. The characterization of BESs was completed using Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results showed that of the BES filters, BES-2 containing emulsion (BES-2-E) exhibited about 2 times and 1.64 times higher SPF and erythemal UV-A PF values, respectively, and after 3 months about 7-8 times higher protection retention capability than the free BP-3 containing emulsion (BP-3-E). Moreover, the result of the in vitro skin penetration test using Franz glass diffusion cell indicated that the skin permeation of BP-3 from BESs was about 3 times lower than from BP-3-E. This property is particularly important for sunscreens because the amount of sunscreen penetration inside the stratum corneum directly correlates to its UV protection ability, and consequently its ability to reduce phototoxic and photo-allergic reactions that are damaging to the skin. The results of this study demonstrated the potential of as-prepared BES-2 as a UV-filter for cosmetic products. PMID:25985148

  12. 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 260nm) expressed as garcinol, a commercially available guttiferone E diastereoisomer. The method showed to be specific, precise, accurate, and linear (0.1-10μg/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. PMID:26930582

  13. An examination of polymorphic stability and molecular conformational flexibility as a function of crystal size associated with the nucleation and growth of benzophenone.

    Science.gov (United States)

    Hammond, Robert B; Pencheva, Klimentina; Roberts, Kevin J

    2007-01-01

    The polymorphic behaviour of the aromatic ketone, benzophenone, which is a conformationally flexible molecule and forms crystal structures dominated by van der Waals intermolecular interactions, is examined. Crystallization of this material from the undercooled molten state yields the two known polymorphic forms, i.e. the stable alpha-form and the metastable beta-form. The relative, energetic stabilities are examined using both crystal lattice and molecular conformational modelling techniques. Examination of nano-sized faceted molecular clusters of these forms, with cluster sizes ranging from 3 to 100 molecules, reveals that at very small cluster size (< 5 molecules) the relative energetic stability of clusters representative for the two forms become very similar, indicating that for high melting undercooling (i.e. small critical cluster size for nucleation) crystallization of the metastable beta-phase becomes more likely. Detailed analysis of the variation in molecular conformations within the simulated molecular clusters reveals more disordered three-dimensional structures at small compared to larger cluster sizes. The conformational disorder was found to be higher for the metastable beta-form. This observation, together with the lower stability of clusters for this form is indicative of the difficulty in achieving crystallization of the metastable beta-form from the melt, which requires a considerable undercooling. PMID:17955805

  14. Prediction of the metabolic clearance of benzophenone-2, and its interaction with isoeugenol and coumarin using cryopreserved human hepatocytes in primary culture.

    Science.gov (United States)

    de Sousa, Georges; Teng, Sophie; Salle-Siri, Romain; Pery, Alexandre; Rahmani, Roger

    2016-04-01

    Benzophenone-2 (BP2) is widely used as a UV screen in both industrial products and cosmetic formulations, where it is frequently found associated with fragrance compounds, such as isoeugenol and coumarin. BP2 is now recognized as an endocrine disruptor, but to date, no information has been reported on its fate in humans. The intrinsic clearance (Clint) and metabolic interactions of BP2 were explored using cryopreserved human hepatocytes in primary cultures. In vitro kinetic experiments were performed to estimate the Michaelis-Menten parameters. The substrate depletion method demonstrated that isoeugenol was cleared more rapidly than BP2 or coumarin (Clint = 259, 94.7 and 0.40 μl/min/10(6) cells respectively). This vitro model was also used to study the metabolic interactions between BP2 and isoeugenol and coumarin. Coumarin exerted no effects on either isoeugenol or BP2 metabolism, because of its independent metabolic pathway (CYP2A6). Isoeugenol appeared to be a potent competitive substrate inhibitor of BP2 metabolism, equivalent to the specific UGT1A1 substrate: estradiol. Despite the fact that inhibition of UGT by xenobiotics is not usually considered to be a major concern, the involvement of UGT1A1 in BP2 metabolism may have pharmacokinetic and pharmacological consequences, due to the its polymorphisms in humans and its pure estrogenic effect. PMID:26829614

  15. Up-and-down shaker-assisted ionic liquid-based dispersive liquid-liquid microextraction of benzophenone-type ultraviolet filters.

    Science.gov (United States)

    Ku, Yu-Chien; Leong, Mei-I; Wang, Wan-Ting; Huang, Shang-Da

    2013-04-01

    Sun protection is an important part of our lives. UV filters are widely used to absorb solar radiation in sunscreens. However, excess UV filters constitute persistent groups of organic micropollutants present in the environment. An environmentally friendly ionic-liquid-based up-and-down shaker-assisted dispersive liquid-liquid microextraction device combined with ultra-performance liquid chromatography coupled with photodiode-array detection has been developed to preconcentrate three UV filters (benzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone) from field water samples. In this method, the optimal conditions for the proposed extraction method were: 40 μL [C8MIM][PF6 ] as extraction solvent and 200 μL methanol as disperser solvent were used to extract the UV filters. After up-and-down shaking for 3 min, the aqueous solution was centrifuged at 5000 rpm speed, then using microtube to collect the settled extraction solvent and using ultra-performance liquid chromatography for further analysis. Quantification results indicated that the linear range was 2-1000 ng/mL. The LOD of this method was in the range 0.2-1.3 ng/mL with r(2) ≥ 0.9993. The relative recovery in studies of different types of field water samples was in the range 92-120%, and the RSD was 2.3-7.1%. The proposed method was also applied to the analysis of field samples. PMID:23495210

  16. 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

    2016-10-01

    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. PMID:27235827

  17. 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. PMID:24246946

  18. 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. PMID:26320959

  19. 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%). PMID:24588714

  20. Effect of benzophenone-1 and octylphenol on the regulation of epithelial-mesenchymal transition via an estrogen receptor-dependent pathway in estrogen receptor expressing ovarian cancer cells.

    Science.gov (United States)

    Shin, Sam; Go, Ryeo-Eun; Kim, Cho-Won; Hwang, Kyung-A; Nam, Ki-Hoan; Choi, Kyung-Chul

    2016-07-01

    Epithelial-mesenchymal transition (EMT) is an important process in embryonic development and cancer progression and metastasis. EMT is influenced by 17β-estradiol (E2), an endogenous estrogen. Benzophenone-1 (2,4-dihydroxybenzophenone, BP-1) and 4-tert-octylphenol (OP) are suspected endocrine disrupting chemicals (EDCs) because they can exhibit estrogenic properties. In this study, we examined whether BP-1 and OP can lead to EMT of BG-1 ovarian cancer cells expressing estrogen receptors (ERs). A wound healing assay and western blot assay were conducted to show the effect of BP-1 and OP on the migration of BG-1 cells and protein expression of EMT-related genes. BP-1 (10(-6) M) and OP (10(-6) M) significantly enhanced the migration capability of BG-1 cells by reducing the wounded area in the cell monolayer relative to the control, similar to E2 (10(-9) M). However, when BG-1 cells were co-treated with ICI 182,780, an ER antagonist, the uncovered area was maintained at the level of the control. N-cadherin, snail, and slug were increased by BP-1 and OP while E-cadherin was reduced compared to the control. However, this effect was also restored by co-treatment with ICI 182,780. Taken together, these results indicate that BP-1 and OP, the potential EDCs, may have the ability to induce ovarian cancer metastasis via regulation of the expression of EMT markers and migration of ER-expressing BG-1 ovarian cancer cells. PMID:27145024

  1. 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

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

    International Nuclear Information System (INIS)

    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

  3. Synthesis and characterization of the 1:1 adducts of copper(I) halides with bidentate N,N′-bis(benzophenone)-1,2-diiminoethane Schiff base: Crystal structures of [Cu(bz2en)2][CuX2] (X = Br, I) complexes

    NARCIS (Netherlands)

    Kia, Reza; Mirkhani, Valiollah; Harkema, Sybolt; Hummel, van Gerrit 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

  4. 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

  5. 可聚合二苯甲酮类光引发剂的合成及其光聚合性能研究%Synthesis and Photopolymerization Properties of Curable Benzophenone Derivative Photoinitiator

    Institute of Scientific and Technical Information of China (English)

    朱晓丹; 路健; 韩银峰; 王克敏

    2013-01-01

    以4-(2,3-环氧丙氧基)二苯甲酮(EBP)和丙烯酸为原料,通过开环反应合成了含有不饱和双键的可聚合光引发剂4-(丙烯酸-2-羟基丙酯-3-氧基)二苯甲酮(AEBP).采用红外光谱(FT-IR)、核磁共振氢谱(1HNMR)对其结构进行表征,利用紫外吸收光谱对AEBP的紫外吸收波长进行表征,通过实时红外(RT-IR)研究了AEBP引发丙烯酸酯单体的光聚合动力学.采用萃取法对比了BP与AEBP引发固化体系后的迁移性.结果表明,随AEBP浓度增加,单体最终转化率增加;当助引发剂N,N-二甲氨基苯甲酸-乙酯(EDAB)浓度为1.2%时,单体最终双键转化率最高;AEBP对双官能度单体的引发效率较之三官能度单体的好;聚合速率随光照强度的增强而变快;固化后AEBP的迁移性比传统的BP大大降低.%The curable photoinitiator of 4-(acrylate-2-hydroxypropylate-3-oxy) benzophenone (AEBP) containing unsaturated double bond was synthesized by 4-(2, 3-epoxypropoxy) benzophenone (EBP) and acrylic acid through ring-open reaction method. The chemical structure was characterized by FT-IR and 1HNMR. The UV absorption wavelength of AEBP was characterized by UV-Vis spectrum. The photopolymerization kinetics of AEBP were investigated by RT-IR, extraction method was applied to compare the migration of BP with AEBP after cured. The results showed that double bond conversion increased with the increase of AEBP concentration, when EDAB concentration was 1. 2%, the final double bond conversion was the optimum, the initiating efficiency of AEBP with diacrylate monomer were better than that with triacrylate monomer. The rate of polymerization increased with light intensity. After cured with monomers, the migration of AEBP reduced greatly compared with that of traditional BP.

  6. 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)

    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

  7. 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)

    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 G1 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

  8. A multi-class bioanalytical methodology for the determination of bisphenol A diglycidyl ethers, p-hydroxybenzoic acid esters, benzophenone-type ultraviolet filters, triclosan, and triclocarban in human urine by liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

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

    2014-01-10

    A liquid-liquid extraction (LLE; ethyl acetate) protocol, followed by liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) methodology, was developed for the determination of 19 compounds, including bisphenol A diglycidyl ethers (BADGEs; industrial ethers), benzophenone-type UV filters (BP-UV filters; precursors and metabolites), p-hydroxybenzoic acid esters (parabens; preservatives), triclosan (TCS) and triclocarban (TCC) in human urine. Urine specimens were enzymatically deconjugated with β-glucuronidase (from Helix pomatia) and extracted by a LLE procedure for the measurement of total concentrations (i.e., free+conjugated forms) of target analytes. Absolute recoveries of BADGEs, BP-UV filters, parabens, TCS and TCC ranged 25-135%, 84-125%, 52-126%, 75-118% and 90-124%, respectively. Method precision (absolute values; N=5 replicate analyses at the fortification level of 10 ng, k=5 days) ranged from 5.8 (ethyl paraben) to 24.0% (TCS). The limits of quantification (LOQs) varied depending on the target compound and generally ranged from 0.2 to 2.0 ng/mL. The matrix effects ranged from +11 (2,3,4-trihydroxybenzophenone) to -86% (2,4-dihydroxybenzophenone). A total of 30 urine specimens collected from Athens, Greece, were analyzed for the 19 target compounds to demonstrate the applicability of the developed method. The concentrations of target chemicals in urine were presented on volume-, specific gravity (SG)-, and creatinine-normalization bases. MeP, EtP, PrP, OH-EtP, BADGE·2H2O, BP-1 and TCS were found frequently in urine at concentrations in the range of 2.7-436 ng/mL, <0.5-25.4 ng/mL, <0.5-575 ng/mL, <2-18.4 ng/mL, <0.5-13.8 ng/mL, <1-14.6 ng/mL and <0.5-95.3 ng/mL, respectively. PMID:24315674

  9. Determination of Benzophenone and 4-methylbenzophenone Photoinitia-tors in Printing Inks for Food Packaging Material by Gas Chromatography-mass Spectrometry%GC-MS法测定食品包装材料印刷油墨中光引发剂二苯甲酮和4-甲基二苯甲酮

    Institute of Scientific and Technical Information of China (English)

    文韵漫; 张亚宁; 杨坚

    2012-01-01

    建立了气相色谱-质谱(GC-MS)检测食品包装材料表面印刷油墨中光引发剂二苯甲酮(BP)和4-甲基二苯甲酮(MBP)迁移量的方法。样品以正己烷为提取溶剂进行振荡提取和超声波辅助萃取,提取液用GC-MS分析检测。结果表明:该方法线性范围为0.02~0.1mg/mL,检测限为0.004~0.005mg/mL,在0.01,0.02,0.10mg/mL 3个添加水平下,2种光引发剂的平均回收率为88.2%~114.5%,相对标准偏差(n=6)为5.13%~7.95%。该方法简单快速,适用于食品包装材料的日常检测需要。%An analytical method based on gas chromatography-mass spectrometry (GC-MS) tech-niques was developed for determination of benzophenone and 4-methylbenzophenone photoini-tiators in printing inks used for food packaging materials. The test samples were extracted from selected food packaging materials using oscillating extraction and ultrasonic assisted extraction with n-Hexane as the extraction solvent, and the extracts was analyzed by GC-MS. The results showed that the linearity range of the method is 0.02-0. 1 mg/mL and the limits of detection for benzophenone and 4-methylbenzophenone are 0. 004 mg/mL and 0. 005 mg/mL; the average re-coveries of the three adding levels(0.01, 0.02, 0.10 mg/mL) are 88.2 % - 114.5 %, with the relative standard deviations(n=6)of 5.13-7.95%. It was concluded that the method is simple and rapid, which is applicable for routine determination of food packaging materials.

  10. Antiplasmodial benzophenones from the trunk latex of Moronobea coccinea (Clusiaceae)

    OpenAIRE

    Marti, G; Eparvier, V.; Moretti, Christian; Susplugas, S.; Prado, S.; Grellier, P; Retailleau, P; Gueritte, F.; Litaudon, M.

    2009-01-01

    In an effort to find antimalarial drugs, a systematic in vitro evaluation on a chloroquine-resistant strain of Plasmodium falciparum (FcB1) was undertaken on sixty plant extracts collected in French Guiana. The methanol extract obtained from the latex of Moronobea coccinea exhibited a strong antiplasmodial activity (95% at 10 mu g/ml). The phytochemical investigation of this extract led to the isolation of eleven polycyclic polyprenylated acylphloroglucinols (PPAPs), from which eight showed p...

  11. Antiplasmodial benzophenones from the trunk latex of Moronobea coccinea (Clusiaceae).

    Science.gov (United States)

    Marti, Guillaume; Eparvier, Véronique; Moretti, Christian; Susplugas, Sophie; Prado, Soizic; Grellier, Philippe; Retailleau, Pascal; Guéritte, Françoise; Litaudon, Marc

    2009-01-01

    In an effort to find antimalarial drugs, a systematic in vitro evaluation on a chloroquine-resistant strain of Plasmodium falciparum (FcB1) was undertaken on sixty plant extracts collected in French Guiana. The methanol extract obtained from the latex of Moronobea coccinea exhibited a strong antiplasmodial activity (95% at 10microg/ml). The phytochemical investigation of this extract led to the isolation of eleven polycyclic polyprenylated acylphloroglucinols (PPAPs), from which eight showed potent antiplasmodial activity with IC50 ranged from 3.3microM to 37.2microM. PMID:19054532

  12. Uterotrophic effects of benzophenone derivatives and a p-hydroxybenzoate used in ultraviolet screens

    International Nuclear Information System (INIS)

    Ultraviolet (UV) sunscreen products are popular because of concerns about UV radiation and skin cancer. Unfortunately, some of these products contain agents with estrogenic activity. We used an ovariectomized rat uterotrophic assay to measure the estrogenic activities of 2,4-dihydroxybenzophenone (2,4-DHBP), 2,2',4,4'-tetrahydroxybenzophenone (2,2',4,4'-THBP), and 4-hydroxybenzoic acid isobutyl ester (isobutyl-paraben), which are agents in UV sunscreens, and ethynyl estradiol (EE) and bisphenol A (BPA), which are positive controls. All chemicals increased rat uterine weights. The 10% effective doses (ED10, mg/kg/day) of EE, BPA, 2,4-DHBP, 2,2',4,4'-THBP, and isobutyl-paraben, as determined by Hill equation analysis, where 5E-5, 41.1, 544.6, 33.0, and 230.9, respectively, and their relative potencies against EE were about 1/800,000, 1/10,000,000, 1/600,000, and 1/4,000,000, respectively. Our findings indicated that UV screens contain weak estrogenic compounds

  13. BIOACTIVE MAMMEA-TYPE COUMARINS AND BENZOPHENONES FROM TWO CLUSIACEAE PLANTS

    OpenAIRE

    Magadula; Joseph Jangu

    2012-01-01

    The phytochemical isolation of the ethanol extract of the stem bark of Allanblackia ulugurensis led to the isolation and identification of two polycyclic polyprenylated acylphloroglucinols (PPAPs), named guttiferone F (1) and 30-epi-cambogin (2) and a biphenyl compound, 3-hydroxy-5-methoxybiphenyl (3). The ethanolic crude extract of A. ulugurensis exhibited high activity in anti-HIV protease assay with IC50 of 4.1 g/ml, while the standard drug has IC50 of 2.2 g/ml. However, compounds 1 and ...

  14. BIOACTIVE MAMMEA-TYPE COUMARINS AND BENZOPHENONES FROM TWO CLUSIACEAE PLANTS

    Directory of Open Access Journals (Sweden)

    Magadula

    2012-10-01

    Full Text Available The phytochemical isolation of the ethanol extract of the stem bark of Allanblackia ulugurensis led to the isolation and identification of two polycyclic polyprenylated acylphloroglucinols (PPAPs, named guttiferone F (1 and 30-epi-cambogin (2 and a biphenyl compound, 3-hydroxy-5-methoxybiphenyl (3. The ethanolic crude extract of A. ulugurensis exhibited high activity in anti-HIV protease assay with IC50 of 4.1 g/ml, while the standard drug has IC50 of 2.2 g/ml. However, compounds 1 and 2 indicated lower activity in anti-HIV protease assay with IC50 values of 11.3 and 22.7 g/ml respectively. The ethanolic crude extract of the stem bark of Mammea usambarensis indicated potent antioxidant activity in the DPPH assay with a value of 6,165 ± 152 μmol TE/g, which is more than twice as higher as that of the standard (Chlorogenic acid; 3,056 ± 157 μmol TE/g. Two compounds namely mammea B/BB (4 and mammea B/BD (5 were isolated from the stem bark extract of M. usambarensis showing antioxidant activities in DPPH assay at 4,012 ± 117 and 2,176 ± 102 μmol TE/g respectively. The lower activities of the isolated compounds compared to the crude extracts may be attributed by the synergistic effect. Interestingly, the activities of the isolated compounds were higher than the corresponding standard compounds.

  15. Antiplasmodial benzophenone derivatives from the root barks of Symphonia globulifera (Clusiaceae)

    OpenAIRE

    Marti, G; Eparvier, V.; Moretti, Christian; Prado, S.; Grellier, P; Hue, N.; Thoison, O.; Delpech, B; Gueritte, F.; Litaudon, M.

    2010-01-01

    In an effort to find antimalarial drugs, a systematic in vitro evaluation on a chloroquine-resistant strain of Plasmodium falciparum (FcB1) was undertaken on sixty plant extracts collected in French Guiana. The ethyl acetate extract obtained from the root barks of Symphonia globulifera exhibited a strong antiplasmodial activity (97% at 10 mu g/ml). The phytochemical investigation of this extract led to the isolation of nine polycyclic polyprenylated acylphloroglucinol (PPAPs) compounds and tw...

  16. Synthesis and spectral feature of benzophenone-substituted thiosemicarbazones and their Ni(II) and Cu(II) complexes

    Science.gov (United States)

    El-Asmy, A. A.; Al-Hazmi, G. A. A.

    2009-01-01

    The ligational behavior of 2-hydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone N-substituted thiosemicarbazones towards Ni(II) and Cu(II) ions has been investigated. The isolated complexes were identified by elemental analyses, molar conductance, magnetic moment, IR, UV-vis and ESR spectral studies. The IR spectra indicated that the investigated thiosemicarbazones lost the N 2 proton or the N 2 and OH protons and act as mononegative or binegative tridentate ligands. The ligands containing methoxy group facilitate the deprotonation of OH by resonance more than the SH. Most of the Ni(II) complexes measured subnormal magnetic moments due to square-planar + tetrahedral configuration and supported by the electronic spectra. The percentage of square-planar to tetrahedral was calculated and found in agreement with the ligand splitting energy (10Dq). Also, Cu(II) complexes measured subnormal values due to the interaction between copper centers; the lower the value the higher the interaction. It was found that the substitutent has a noticeable effect on the distortion of the complex. The ESR spectra of some solid Cu(II) complexes at room temperature exhibit g|| > g⊥ > 2.0023 confirming a square-planar structure.

  17. G2/M Cell Cycle Arrest and Tumor Selective Apoptosis of Acute Leukemia Cells by a Promising Benzophenone Thiosemicarbazone Compound

    OpenAIRE

    Cabrera, Maia; Gomez, Natalia; Remes Lenicov, Federico; Echeverría, Emiliana; Shayo, Carina; Moglioni, Albertina; Fernández, Natalia; Davio, Carlos

    2015-01-01

    Anti-mitotic therapies have been considered a hallmark in strategies against abnormally proliferating cells. Focusing on the extensively studied family of thiosemicarbazone (TSC) compounds, we have previously identified 4,4’-dimethoxybenzophenone thiosemicarbazone (T44Bf) as a promising pharmacological compound in a panel of human leukemia cell lines (HL60, U937, KG1a and Jurkat). Present findings indicate that T44Bf-mediated antiproliferative effects are associated with a reversible chronic ...

  18. 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

    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...

  19. Preparation and Characterization of Inclusion Complex of Benzophenone with β-Cyclodextrin%二苯甲酮-β-环糊精包合物的制备表征

    Institute of Scientific and Technical Information of China (English)

    宫红; 罗维巍; 姜恒

    2006-01-01

    采用研磨法合成了二苯甲酮-β-环糊精包合物,经差示量热扫描分析、热重分析、红外分析、X射线衍射分析、对包合物进行了鉴定,证明二苯甲酮-β-环糊精确实形成了一种新的体系.

  20. Comprehensive Phenolic Profiling of Cyclopia genistoides (L.) Vent. by LC-DAD-MS and -MS/MS Reveals Novel Xanthone and Benzophenone Constituents

    OpenAIRE

    Theresa Beelders; Dalene de Beer; Maria A. Stander; Elizabeth Joubert

    2014-01-01

    A high-performance liquid chromatographic (HPLC) method coupled with diode-array detection (DAD) was optimized for the qualitative analysis of aqueous extracts of Cyclopia genistoides. Comprehensive insight into the phenolic profile of unfermented and fermented sample extracts was achieved with the identification of ten compounds based on comparison with authentic reference standards and the tentative identification of 30 additional compounds by means of electrospray ionization mass spectrome...

  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. Garcinol, a polyisoprenylated benzophenone modulates multiple proinflammatory signaling cascades leading to the suppression of growth and survival of head and neck carcinoma.

    Science.gov (United States)

    Li, Feng; Shanmugam, Muthu K; Chen, Luxi; Chatterjee, Snehajyoti; Basha, Jeelan; Kumar, Alan Prem; Kundu, Tapas K; Sethi, Gautam

    2013-08-01

    Constitutive activation of proinflammatory transcription factors such as STAT3 and NF-κB plays a pivotal role in the proliferation and survival of squamous cell carcinoma of the head and neck (HNSCC). Thus, the agents that can modulate deregulated STAT3 and NF-κB activation have a great potential both for the prevention and treatment of HNSCC. In the present report, we investigated the potential effects of garcinol, an active component of Garcinia indica on various inflammatory mediators involved in HNSCC progression using cell lines and xenograft mouse model. We found that garcinol inhibited constitutively activated STAT3 in HNSCC cells in a time- and dose-dependent manner, which correlated with the suppression of the upstream kinases (c-Src, JAK1, and JAK2) in HNSCC cells. Also, we noticed that the generation of reactive oxygen species is involved in STAT3 inhibitory effect of garcinol. Furthermore, garcinol exhibited an inhibitory effect on the constitutive NF-κB activation, mediated through the suppression of TGF-β-activated kinase 1 (TAK1) and inhibitor of IκB kinase (IKK) activation in HNSCC cells. Garcinol also downregulated the expression of various gene products involved in proliferation, survival, and angiogenesis that led to the reduction of cell viability and induction of apoptosis in HNSCC cells. When administered intraperitoneally, garcinol inhibited the growth of human HNSCC xenograft tumors in male athymic nu/nu mice. Overall, our results suggest for the first time that garcinol mediates its antitumor effects in HNSCC cells and mouse model through the suppression of multiple proinflammatory cascades. PMID:23803415

  3. 蝉翼藤根中的一个新二苯酮%A new benzophenone from the root of Securidaca inappendiculata

    Institute of Scientific and Technical Information of China (English)

    张丽杰; 张琳; 徐丽珍; 杨学东; 邹忠梅; 杨世林

    2005-01-01

    目的对蝉翼藤(Securidaca inappendiculata Hassk.)根的二苯酮成分进行分离和结构鉴定.方法通过硅胶和凝胶反复柱色谱分离得到二苯酮类化合物;利用多种波谱技术鉴定其化学结构.结果分离鉴定了2个二苯酮化合物,其结构分别为2-甲氧基-3,4-亚甲二氧基-二苯酮(I),4-羟基-2,6-二甲氧基-二苯酮(II).结论化合物I为新化合物,命名为蝉翼藤二苯酮B;化合物II为首次自该属植物中分离得到.

  4. 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 vertebrate...

  5. Quantification of the Polyisoprenylated Benzophenones Garcinol and Isogarcinol Using Multiple Reaction Monitoring LC/Electrospray Ionization-MS/MS Analysis of Ultrasound-Assisted Extracts of Garcinia indica Fruits.

    Science.gov (United States)

    Bharate, Jaideep Bibishan; Vishwakarma, Ram Ashrey; Bharate, Sandip Bibishan; Kushwaha, Manoj; Gupta, Ajai Prakash

    2014-01-01

    This paper describes a method that includes an optimized extraction process and identification and quantification of two anticancer compounds (garcinol and isogarcinol) by LC/electrospray ionization (ESI)-MS/MS in the multiple reaction monitoring (MRM) mode. The study aimed to develop a fast, accurate, and sensitive method for the quantification of garcinol and isogarcinol in different extracts of Garcinia indica fruits. The compounds were detected using LC/ESI-MS/MS in the positive-ion mode and quantified in the MRM mode using a transition mass of m/z 603.3/411 taken as the quantifier and 603.3/343.2 as the qualifier for garcinol and isogarcinol. Five point calibration curves were linear in the range of 2 to 10 ng/mL for garcinol and 0.5 to 6 ng/mL for isogarcinol, with a correlation coefficient of ≥0.990 for both. LOQ for garcinol and isogarcinol was 0.06 and 0.05 ng/mL, respectively, while LOD was 0.021 and 0.017 ng/mL respectively. Our work demonstrated optimization of extraction procedure, fast and highly sensitive quantification (pg level LOQ), and validation of the developed method for the investigated compounds in fruit extracts of G. indica. PMID:25902981

  6. Probabilistic simulation of children exposure to migrants from packaging: photoinitiators from printing inks

    OpenAIRE

    Machado, Carla; Fernandes, Conceição; Pereira, Joel; Poças, Maria de Fátima

    2010-01-01

    The present work presents an exercise to simulate exposure of Portuguese consumers to benzophenone, a photoinitiator used in packaging printing inks. The simulation model combined experimental data of benzophenone concentration found in packages collected from market and food consumption and packaging usage data obtained from a database. The model followed a probabilistic approach: the distribution of occurrence data was combined with food consumption data in a probabilistic si...

  7. Benzonphenone-type UV filters in urine of Chinese young adults: Concentration, source and exposure

    International Nuclear Information System (INIS)

    Benzophenone (BP)-type UV filters are commonly used in our daily life. 2-hydroxy-4-methoxy benzophenone (BP-3), 4-hydroxy benzophenone (4-HBP), 2,4-dihydroxy benzophenone (BP-1), 2,2′,4,4′-tetrahydroxy benzophenone (BP-2) and 2,2′-dihydroxy-4-methoxy benzophenone (BP-8) were measured in urine samples from Chinese young adults. The results indicated that Chinese young adults were widely exposed to BP-3, BP-1, and 4-HBP, with the median concentrations of 0.55, 0.21, and 0.08 ng/mL, respectively. No significant difference was found between males and females, between urban and rural population. The correlations between urinary concentrations provided important indications for sources and metabolic pathways of target compounds. The estimated daily excretion doses of BP-3, 4-HBP, BP-1, BP-2 and BP-8 were 27.2, 2.24, 5.86, 0.76 and 0.30 ng/kg-bw/day, respectively. The ratio of exposure to excretion must be considered for the exposure assessment with chemicals based on urine measurement. This is the first nationwide study on BP-derivatives with young adults in China. - Highlights: • Five BP-derivatives in urine were analyzed for Chinese young adults over China. • No difference was found between males and females, between urban and rural groups. • Concentration correlation provide indications for sources and metabolic pathways. • Ratio of exposure to excretion must be considered for the exposure assessment. - Benzophenone (BP)-type UV filters were frequently detected in urine samples from Chinese young adults, indicating their wide applications in China

  8. Photodegradation Mechanisms of Tetraphenyl Butadiene Coatings for Liquid Argon Detectors

    CERN Document Server

    Jones, B J P; Conrad, J M; Pla-Dalmau, A

    2013-01-01

    We report on studies of degradation mechanisms of tetraphenyl butadiene (TPB) coatings of the type used in neutrino and dark matter liquid argon experiments. Using gas chromatography coupled to mass spectrometry we have detected the ultraviolet-blocking impurity benzophenone (BP). We monitored the drop in performance and increase of benzophenone concentration in TPB plates with exposure to ultraviolet (UV) light, and demonstrate the correlation between these two variables. Based on the presence and initially exponential increase in the concentration of benzophenone observed, we propose that TPB degradation is a free radical-mediated photooxidation reaction, which is subsequently confirmed by displaying delayed degradation using a free radical inhibitor. Finally we show that the performance of wavelength-shifting coatings of the type envisioned for the LBNE experiment can be improved by 10-20%, with significantly delayed UV degradation, by using a 20% admixture of 4-tert-Butylcatechol.

  9. Photodegradation mechanisms of tetraphenyl butadiene coatings for liquid argon detectors

    Science.gov (United States)

    Jones, B. J. P.; VanGemert, J. K.; Conrad, J. M.; Pla-Dalmau, A.

    2013-01-01

    We report on studies of degradation mechanisms of tetraphenyl butadiene (TPB) coatings of the type used in neutrino and dark matter liquid argon experiments. Using gas chromatography coupled to mass spectrometry we have detected the ultraviolet-blocking impurity benzophenone. We monitored the drop in performance and increase of benzophenone concentration in TPB plates with exposure to ultraviolet (UV) light, and demonstrate the correlation between these two variables. Based on the presence and initially exponential increase in the concentration of benzophenone observed, we propose that TPB degradation is a free radical-mediated photooxidation reaction, which is subsequently confirmed by displaying delayed degradation using a free radical inhibitor. Finally we show that the performance of wavelength-shifting coatings of the type envisioned for the LBNE experiment can be improved by 10-20%, with significantly delayed UV degradation, by using a 20% admixture of 4-tert-Butylcatechol.

  10. 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 A; Garrison, Virginia H

    2015-12-15

    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 (r(2)=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. PMID:26581812

  11. Photodegradation mechanisms of tetraphenyl butadiene coatings for liquid argon detectors

    International Nuclear Information System (INIS)

    We report on studies of degradation mechanisms of tetraphenyl butadiene (TPB) coatings of the type used in neutrino and dark matter liquid argon experiments. Using gas chromatography coupled to mass spectrometry we have detected the ultraviolet-blocking impurity benzophenone. We monitored the drop in performance and increase of benzophenone concentration in TPB plates with exposure to ultraviolet (UV) light, and demonstrate the correlation between these two variables. Based on the presence and initially exponential increase in the concentration of benzophenone observed, we propose that TPB degradation is a free radical-mediated photooxidation reaction, which is subsequently confirmed by displaying delayed degradation using a free radical inhibitor. Finally we show that the performance of wavelength-shifting coatings of the type envisioned for the LBNE experiment can be improved by 10-20%, with significantly delayed UV degradation, by using a 20% admixture of 4-tert-Butylcatechol.

  12. Photodegradation mechanisms of TPB coatings

    Science.gov (United States)

    VanGemert, J. K.

    2013-10-01

    In these proceedings I discuss results of a degradation mechanism study of tetraphenyl butadiene (TPB) coatings of the type used in neutrino and dark matter liquid argon experiments. Using gas chromatography coupled to mass spectrometry (GCMS) we identified the UV blocking impurity benzophenone. We monitored the drop in performance and increase of benzophenone concentration in TPB plates with exposure to ultraviolet (UV) light, and demonstrate the correlation between these two variables. We show promisng results obtained by adding a free radical inhibiting stabilizing compound, which improves the initial performance of light-guide coatings by up to 20% and significantly improves their UV stability. These proceedings summarize work previously published in JINST [1].

  13. 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.

  14. An air-tolerant approach to the carbonylative Suzuki-Miyaura coupling: applications in isotope labeling.

    Science.gov (United States)

    Ahlburg, Andreas; Lindhardt, Anders T; Taaning, Rolf H; Modvig, Amalie E; Skrydstrup, Troels

    2013-10-18

    Carbonylative Suzuki-Miyaura coupling conditions have been developed that proceed without the exclusion of oxygen and in the presence of nondegassed and nondried solvents. By adapting the method to a two-chamber setup, the direct handling of carbon monoxide, produced from stable CO precursors, is avoided. The protocol afforded the desired benzophenones with excellent functional group tolerance and in good yields. Substituting the CO precursor, in the CO-producing chamber, with its carbon-13 labeled version generated the corresponding carbon-13 labeled benzophenones. Finally, the developed system was applied in the synthesis and isotope labeling of two pharmaceuticals, nordazepam and Tricor. PMID:24004340

  15. Total Synthesis of balanol, Part 2

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Kelly, Nicholas; Tedenborg, Lars;

    1997-01-01

    A convergent enantioselective total synthesis of the natural product (-)-balanol (1) is described. In addition to benzophenone fragment 8, key intermediates are chiral bicyclic aziridine 3 and the corresponding epoxide 4, both of which undergo highly regio- and stereoselective nucleophilic ring...

  16. MIS-based sensors with hydrogen selectivity

    Science.gov (United States)

    Li; ,Dongmei; Medlin, J. William; McDaniel, Anthony H.; Bastasz, Robert J.

    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.

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

    DEFF Research Database (Denmark)

    Städe, Lars W; Wimmer, Reinhard; Stensballe, Allan; Duroux, Meg; Larsen, Kim Lambertsen; Wingren, Christer; Duroux, Laurent; Jensen, Rasmus Lybech

    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...

  18. Constituents of the pericarp of Garcinia subelliptica.

    Science.gov (United States)

    Wu, Chien-Chang; Weng, Jing-Ru; Won, Shen-Jeu; Lin, Chun-Nan

    2005-07-01

    A new benzophenone, garcinielliptone FA (1), and a new benzoylphloroglucinol, garcinielliptone FB (2), along with six known compounds, were isolated from the pericarp of Garcinia subelliptica. The structures and relative configurations of 1 and 2 were elucidated by spectroscopic methods and supported by computer-generated molecular modeling. Compound 2 exhibited cytotoxic activity against several human cancer cell lines. PMID:16038565

  19. Light Induced C-C Coupling of 2-Chlorobenzazoles with Carbamates, Alcohols, and Ethers.

    Science.gov (United States)

    Lipp, Alexander; Lahm, Günther; Opatz, Till

    2016-06-01

    A light induced, transition-metal-free C-C coupling reaction of 2-chlorobenzazoles with aliphatic carbamates, alcohols, and ethers is presented. Inexpensive reagents, namely sodium acetate, benzophenone, water, and acetonitrile, are employed in a simple reaction protocol using a cheap and widely available 25 W energy saving UV-A lamp at ambient temperature. PMID:27128627

  20. 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...

  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 benzopheno

  2. 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...

  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. Method to manufacture moulds from polycarbonates cross-linked by UV and/or other energetic radiation

    International Nuclear Information System (INIS)

    Using benzophenone as photoinitiator and dibenzyl ether as photoreducing agent thermoplastic granular polycarbonate is finally passed through a double shaft extruder and drawn off in strand form. Following irradiation and solvation of non-cross-linked fractions in methylene chloride a tubular, transparent hollow mould is obtained. This hollow mould or film can be used as a membrane in dialysis techniques. (DG)

  5. 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. PMID:24447245

  6. Action of Mercaptan and Disulfide in Hydrogen Atom Exchange Reactions

    International Nuclear Information System (INIS)

    Free- radical, photochemical, and high-energy radiation-induced reactions may be catalysed or inhibited by rapid hydrogen atom exchange reactions of mercaptans and disulfides. The radical-induced, light-initiated, and benzophenone-sensitized decarbonylations of aldehydes are catalysed by mercaptans. The chain-propagating hydrogen transfer reaction, R' + RCH = O -> RH + RC = O , is made more rapid by a similar sequence of hydrogen atom transfers involving the sulfur compound: R' + C6H5CH2SH -> RH + C6H5CH2S'; C6H5CH2S + RCH = 0 -> C6H5CH2SH + RC = 0. The photoreduction of benzophenone in 2-propanol leads to benzpinacol by a non-chain reaction via the radicals (C6H5)2C-OH and (CH3)2COH. The reaction is retarded and inhibited by mercaptan and disulfide, which reconvert the radicals to the starting materials by rapid hydrogen transfer reactions and are themselves regenerated in their alternate valence states, each molecule of sulfur compound negating the chemical consequences of many quanta: (C6H5)2C-OH + AS' -> (C6H5)2C = O + ASH; (CH3)2C-OH + ASH -> (CH3)2C = 0 + AS'. Proof of the mechanism is found in: equilibration of initially present mercaptan or disulfide during inhibition; in racemization of optically active alcohol during inhibition; in deuterium exchange during inhibition. Similar inhibition is seen when only one intermediate radical is formed, as in the benzophenone- benzhydrol and acetophenone-α-methyl-benzyl alcohol systems. Inhibition by sulfur compounds, by the same mechanism, is found in the 60Co γ-ray induced conversion of benzophenone to benzpinacol; naphthalene has no protecting effect on benzophenone in the 60Co system, while quenching the photochemical reaction. The protection by sulfur compounds of solutes against radiation damage thus results from hydrogen atom transfer reactions. The photoreduction of benzophenone in an ether is also inhibited by the sulfur compounds, by hydrogen atom transfer reactions. A mechanism exists in this system

  7. 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.

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

    OpenAIRE

    Irene See; Gwendoline Cheng Lian Ee; Soek Sin Teh; Arifah Abdul Kadir; Shaari Daud

    2014-01-01

    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.

  9. 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...

  10. Synthesis of novel β-aminocyclobutanecarboxylic acid derivatives by a solvent-free aza-Michael addition and subsequent ring closure

    OpenAIRE

    Meiresonne, Tamara; Mangelinckx, Sven; De Kimpe, Norbert

    2011-01-01

    Novel beta-aminocyclobutanecarboxylic acid derivatives were prepared via a sequential solvent-free aza-Michael addition of benzophenone imine across 3-halopropylidenemalonates and base-induced ring closure. These highly substituted cyclobutanedicarboxylic acid derivatives were subjected to a reactivity study which demonstrated the tendency of these donor-acceptor substituted four-membered rings to be converted into their corresponding ring-opened products.

  11. Fluorescência de raios X por dispersão de energia aplicada no controle de qualidade de protetor solar

    OpenAIRE

    Lonni, Audrey; Duarte, José Crispim; Melquiades, Fábio; Ferreira, Diego D.D.; Carlos R Appoloni; Lubini, Greice

    2008-01-01

    The aim of this study was to evaluate sunscreens by Dispersive X-ray Fluorescence (EDXRF) and UV-VIS spectrophotometry, to quantify the sun protection factor (SPF) of the physical filter (micro-fine titanium dioxide) and the organics filters (ethylhexyl methoxycinnamate and benzophenone-3), respectively, in order to obtain the total SPF. Three formulations estimated in SPF-23 using inorganic and organic filters were prepared. The results showed that the system EDXRF portable an...

  12. Voltammetry Study of an Anti-HIV Compound by means of a Thin Organic Membrane

    OpenAIRE

    Achille Nassi; Thiery Christophe Ebelle; Dika Manga, Joseph M.; Jules-Blaise Mabou Leuna; Joel Donkeng Dazie; Emmanuel Ngameni

    2013-01-01

    Cyclic and square wave voltammetries have been used to study electrochemical behaviour of an anti-HIV agent (Guttiferone A) at the liquid-liquid interface. The thin organic membrane is formed by an organic solvent containing redox probe. Guttiferone A, a benzophenone (BP) with appropriate electrolyte. It is demonstrated that BP possesses three reduction systems due to the redox transformation of the three tautomeric forms that lead to the migration of proton between the hydroxyl group in posi...

  13. Garcinol sensitizes human head and neck carcinoma to cisplatin in a xenograft mouse model despite downregulation of proliferative biomarkers

    OpenAIRE

    Li, Feng; Shanmugam, Muthu K.; Siveen, Kodappully Sivaraman; Wang, Fan; Ong, Tina H.; Loo, Ser Yue; Swamy, Mahadeva M.M.; Mandal, Somnath; Kumar, Alan Prem; Goh, Boon Cher; Kundu, Tapas; Ahn, Kwang Seok; Wang, Ling Zhi; Hui, Kam Man; Sethi, Gautam

    2015-01-01

    Platinum compounds such as cisplatin and carboplatin are frequently used as the first-line chemotherapy for the treatment of the head and neck squamous cell carcinoma (HNSCC). In the present study, we investigated whether garcinol, a polyisoprenylated benzophenone can chemosensitize HNSCC to cisplatin. We found that garcinol inhibited the viability of a panel of diverse HNSCC cell lines, enhanced the apoptotic effect of cisplatin, suppressed constitutive as well as cisplatin-induced NF-κB act...

  14. Inhibition of STAT3 dimerization and acetylation by garcinol suppresses the growth of human hepatocellular carcinoma in vitro and in vivo

    OpenAIRE

    Sethi, Gautam; Chatterjee, Snehajyoti; Rajendran, Peramaiyan; Li, Feng; Shanmugam, Muthu K.; Wong, Kwong Fai; Kumar, Alan Prem; Senapati, Parijat; Behera, Amit K; Hui, Kam Man; Basha, Jeelan; Natesh, Nagashayana; Luk, John M; Kundu, Tapas K.

    2014-01-01

    Background Constitutive activation of signal transducer and activator of transcription 3 (STAT3) has been linked with proliferation, survival, invasion and angiogenesis of a variety of human cancer cells, including hepatocellular carcinoma (HCC). Thus, novel agents that can suppress STAT3 activation have potential for both prevention and treatment of HCC. Here we report, garcinol, a polyisoprenylated benzophenone, could suppress STAT3 activation in HCC cell lines and in xenografted tumor of H...

  15. Chemoprevention of 7,12-dimethylbenz[a]anthracene (DMBA)-induced Hamster Cheek Pouch Carcinogenesis by a 5-Lipoxygenase Inhibitor, Garcinol

    OpenAIRE

    Chen, Xin; Zhang, Xinyan; Lu, Ye; Shim, Joong-Youn; Sang, Shengmin; Sun, Zheng; Chen, Xiaoxin

    2012-01-01

    Our previous studies have shown that aberrant arachidonic acid metabolism, especially the 5-lipoxygenase (5-Lox) pathway, is involved in oral carcinogenesis, and can be targeted for cancer prevention. In order to develop potent topical agents for oral cancer chemoprevention, five known 5-Lox inhibitors from dietary and synthetic sources, Zileuton, ABT-761, Licofelone, Curcumin and Garcinol, were evaluated in silico for their potential efficacy. Garcinol, a polyisoprenylated benzophenone from ...

  16. Potential Role of Garcinol as an Anticancer Agent

    OpenAIRE

    Gupta, Smiti V.; Nadia Saadat

    2012-01-01

    Garcinol, a polyisoprenylated benzophenone, is extracted from the rind of the fruit of Garcinia indica, a plant found extensively in tropical regions. Although the fruit has been consumed traditionally over centuries, its biological activities, specifically its anticancer potential is a result of recent scientific investigations. The anticarcinogenic properties of garcinol appear to be moderated via its antioxidative, anti-inflammatory, antiangiogenic, and proapoptotic activities. In addition...

  17. Recent Advance in Light Stabilization

    Institute of Scientific and Technical Information of China (English)

    CHIU; Chris

    2001-01-01

    In order to protect polymers or coatings from the damage by sun light, scientists have created the UV Absorber to complete the task. The first commercialized UV absorber (UVA) is based on a benzophenone structure and was developed by American Cyanamid (UV 531), circa 1955, and is still the leading UVA for flexible PVC. The most powerful UVA is of the triazine type, developed by American Cyanamid (UV 1164) and commercialized in 1987.  ……

  18. Recent Advance in Light Stabilization

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ In order to protect polymers or coatings from the damage by sun light, scientists have created the UV Absorber to complete the task. The first commercialized UV absorber (UVA) is based on a benzophenone structure and was developed by American Cyanamid (UV 531), circa 1955, and is still the leading UVA for flexible PVC. The most powerful UVA is of the triazine type, developed by American Cyanamid (UV 1164) and commercialized in 1987.

  19. 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.

  20. Radiation-induced primary processes in molten polyethylene

    International Nuclear Information System (INIS)

    By means of pulse radiolysis and laser photolysis experiments with detection by optical absorption spectroscopy short-living radical transients in pure PE and in PE doped with additives, e.g., di-tert. butyl-p-cresol, diphenylamine, benzophenone and carbon tetrachloride, were characterized by their optical absorption spectra and kinetics. It was found that the additive radicals were formed in a very fast process probably via exciton migration and subsequent energy transfer and dissociation reactions. (author)

  1. The oxidation of PET track-etched membranes by hydrogen peroxide as an effective method to increase efficiency of UV-induced graft polymerization

    OpenAIRE

    Il'ya Korolkov; Abzal Taltenov; Anastassiya Mashentseva; Olgun Guven

    2015-01-01

    In this article, we report on functionalization of track-etched membrane based on poly(ethylene terephthalate) (PET TeMs) oxidized by advanced oxidation systems and by grafting of acrylic acid using photochemical initiation technique for the purpose of increasing functionality thus expanding its practical application. Among advanced oxidation processes (H2O2/UV) system had been chosen to introduce maximum concentration of carboxylic acid groups. Benzophenone (BP) photo-initiator was first im...

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

    OpenAIRE

    Belal, Tarek S.; Abdel-Hay, Karim M.; C. Randall Clark

    2015-01-01

    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 spec...

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

    OpenAIRE

    Norbert Sewald; Etienne Tsamo; Muhammad Iqbal Choudhary; Qamar Naz; Marcel Kaiser; Joseph Ngoupayo; Krishna Prasad Devkota; Bernard Weniger; Catherine Vonthron-Sénécheau; Bruno Ndjakou Lenta

    2007-01-01

    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 isolat...

  4. Secondary Metabolites of Aspergillus sp. CM9a, an E ndophytic Fungus of Cephalotaxus mannii

    OpenAIRE

    Heng Xue; Chunhua Lu; Lanying Liang; Yuemao Shen

    2012-01-01

    Eleven compounds belonging to eight structure types, namely cyclopentenedione (1), diketopiperazines (2, 9, 10), lactone (3), benzophenone (4, 5), terpene (6), anthraquinone (7), diphenyl ethers (10), and alkaloid (11) were isolated from the cultivation extract of the strain Aspergillus sp. CM9a, which was isolated from the stems of Cephalotaxus mannii. Among them, compounds 1, 2, and 3 were determined to b e new ones on the basis of spectroscopic data including 1D- and 2D - NMR experiments a...

  5. Inhibitorische Wirkung endokriner Disruptoren auf die humane Thyreoperoxidase

    OpenAIRE

    Bacinski, Anja

    2013-01-01

    Endocrine disruptors are synthetic chemicals or natural plant products (like flavonoids) which interfere with or alter the development or function of the endocrine system. This work investigated how 6 different substances (the flavonoids apigenin, genistein, myricetin and xanthohumol, the synthetic flavonoid F21388 and the UV filter benzophenone 2) influence human TPO, the enzyme that plays a key role in thyroid hormone biosynthesis. A novel in vitro assay based on human recombinant TPO s...

  6. Influence of particle size on appearance and in vitro efficacy of sunscreens

    OpenAIRE

    Débora Granemann e Silva; Fernanda Daud Sarruf; Larissa Carolina Diniz de Oliveira; Elizabeth Pinheiro Gomes Arêas; Telma Mary Kaneko; Vladi Olga Consiglieri; Maria Valéria Robles Velasco; André Rolim Baby

    2013-01-01

    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...

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

    OpenAIRE

    Fernanda Maria Pinto Vilela; Yris Maria Fonseca; Vicentini, Fabiana T. M. C.; Maria José Vieira Fonseca; Maria da Penha Henriques do Amaral

    2011-01-01

    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 ...

  8. Photoinduced oxidation of sea salt halides by aromatic ketones: a source of halogenated radicals

    Directory of Open Access Journals (Sweden)

    A. Jammoul

    2009-07-01

    Full Text Available The interactions between triplet state benzophenone and halide anion species (Cl, Br and I have been studied by laser flash photolysis (at 355 nm in aqueous solutions at room temperature. The decay of the triplet state of benzophenone was followed at 525 nm. Triplet lifetime measurements gave rate constants, kq (M−1 s, close to diffusion controlled limit for iodide (~8×109 M−1 s, somewhat less for bromide (~3×108 M−1 s and much lower for chloride (<106 M−1 s. The halide (X quenches the triplet state; the resulting product has a transient absorption at 355 nm and a lifetime much longer than that of the benzophenone triplet state, is formed. This transient absorption feature matches those of the corresponding radical anion (X2. We therefore suggest that such reactive quenching is a photosensitized source of halogen in the atmosphere or the driving force for the chemical oxidation of the oceanic surface micro layer.

  9. 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. PMID:27208882

  10. Mechanistic investigations of novel photoinitiators for radical polymerization

    International Nuclear Information System (INIS)

    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)

  11. Retinyl palmitate polymeric nanocapsules as carriers of bioactives.

    Science.gov (United States)

    Teixeira, Zaine; Dreiss, Cécile A; Lawrence, M J; Heenan, Richard K; Machado, Daisy; Justo, Giselle Z; Guterres, Sílvia S; Durán, Nelson

    2012-09-15

    Nanocapsules containing poly(d,l-lactide) shell and retinyl palmitate core have been prepared by the pre-formed polymer interfacial deposition method. Dynamic light scattering measurements yielded an average hydrodynamic diameter of ∼220nm and a polydispersity index of ∼0.12. Small-angle neutron scattering experiments revealed the presence of two populations of nanocapsules of core diameters ∼192 and 65nm. Freeze fracture transmission electron microscopy showed a polydisperse population of nanocapsules (NC), with a poly(d,l-lactide) shell thickness between 11 and 3nm. For comparison purposes, nanoemulsions (NE, no polymer) and nanospheres (NS, polymer matrix) were also prepared. Each type of nanoparticles exhibited a different morphology (when examined by electron microscopy), in particular NC showed deformability by capillary adhesion. All three types of nanoparticles successfully encapsulated the poorly water-soluble molecules baicalein and benzophenone-3. The thermal behavior of the various nanoparticles was different to a physical mixture of its individual components. Cytotoxicity and phototoxicity assays, performed in human keratinocytes (HaCaT) and murine fibroblasts (BALB/c 3T3), showed that the NC were only cytotoxic at high concentrations. In vitro release studies of benzophenone-3, by the dialysis bag method using NC and NS, showed a sustained release; however, permeation studies using plastic surgery human abdominal skin in Franz diffusion cells showed that a higher amount of benzophenone-3 from NC penetrated into the skin, most probably due to the deformable nature of these nanoparticles. PMID:22738849

  12. 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. PMID:26773895

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

    International Nuclear Information System (INIS)

    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

  14. Migration of photoinitiators from cardboard into dry food: evaluation of Tenax® as a food simulant.

    Science.gov (United States)

    Van Den Houwe, Kathy; Evrard, Caroline; Van Loco, Joris; Lynen, Frederic; Van Hoeck, Els

    2016-05-01

    Photoinitiators are widely used to cure ink on packaging materials used in food applications such as cardboards for the packaging of dry foods. Conventional migration testing for long-term storage at ambient temperature with Tenax(®) was applied to paperboard for the following photoinitiators: benzophenone (BP), 4,4'-bis(diethylamino)benzophenone (DEAB), 2-chloro-9H-thioxanthen-9-one (CTX), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX), 4-(dimethylamino)benzophenone (DMBP), 2-ethylanthraquinone (EA), 2-ethylhexyl-4-dimethylaminobenzoate (EDB), ethyl-4-dimethylaminobenzoate (EDMAB), 4-hydroxybenzophenone (4-HBP), 2-hydroxy-4-methoxybenzophenone (HMBP), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone (HMMP), 2-isopropyl-9H-thioxanthen-9-one (ITX), 4-methylbenzophenone (MBP) and Michler's ketone (MK). Test conditions (10 days at 60°C) were according to Regulation (EU) No. 10/2011 and showed different migration patterns for the different photoinitiators. The results were compared with the migration in cereals after a storage of 6 months at room temperature. The simulation with Tenax at 60°C overestimated actual migration in cereals up to a maximum of 92%. In addition, the effect of a lower contact temperature and the impact of the Tenax pore size were investigated. Analogous simulation performed with rice instead of Tenax resulted in insufficiently low migration rates, showing Tenax is a much stronger adsorbent than rice and cereals. PMID:27146794

  15. Electrochemical reduction of aromatic ketones in 1-butyl-3-methylimidazolium-based ionic liquids in the presence of carbon dioxide: the influence of the ketone substituent and the ionic liquid anion on bulk electrolysis product distribution.

    Science.gov (United States)

    Zhao, Shu-Feng; Horne, Mike; Bond, Alan M; Zhang, Jie

    2015-07-15

    Electrochemical reduction of aromatic ketones, including acetophenone, benzophenone and 4-phenylbenzophenone, has been undertaken in 1-butyl-3-methylimidazolium-based ionic liquids containing tetrafluoroborate ([BF4](-)), trifluoromethanesulfonate ([TfO](-)) and tris(pentafluoroethyl)trifluorophosphate ([FAP](-)) anions in the presence of carbon dioxide in order to investigate the ketone substituent effect and the influence of the acidic proton on the imidazolium cation (C2-H) on bulk electrolysis product distribution. For acetophenone, the minor products were dimers (50%) derived from proton coupled electron transfer reactions involving the electrogenerated radical anions and C2-H. In the cases of both acetophenone and benzophenone, the product distribution is essentially independent of the ionic liquid anion. By contrast, 4-phenylbenzophenone shows a product distribution that is dependent on the ionic liquid anion. Higher yields of carboxylic acids (∼40%) are obtained with [TfO](-) and [FAP](-) anions because in these ionic liquids the C2-H is less acidic, making the formation of alcohol less favourable. In comparison with benzophenone, a higher yield of carboxylic acid (>30% versus ∼15%) was obtained with 4-phenylbenzophenone in all ionic liquids due to the weaker basicity of 4-phenylbenzophenone radical anion. PMID:26136079

  16. Environmental phenols and pubertal development in girls.

    Science.gov (United States)

    Wolff, Mary S; Teitelbaum, Susan L; McGovern, Kathleen; Pinney, Susan M; Windham, Gayle C; Galvez, Maida; Pajak, Ashley; Rybak, Michael; Calafat, Antonia M; Kushi, Lawrence H; Biro, Frank M

    2015-11-01

    Environmental exposures to many phenols are documented worldwide and exposures can be quite high (>1 μM of urine metabolites). Phenols have a range of hormonal activity, but knowledge of effects on child reproductive development is limited, coming mostly from cross-sectional studies. We undertook a prospective study of pubertal development among 1239 girls recruited at three U.S. sites when they were 6-8 years old and were followed annually for 7 years to determine age at first breast or pubic hair development. Ten phenols were measured in urine collected at enrollment (benzophenone-3, enterolactone, bisphenol A, three parabens (methyl-, ethyl-, propyl-), 2,5-dichlorophenol, triclosan, genistein, daidzein). We used multivariable adjusted Cox proportional hazards ratios (HR (95% confidence intervals)) and Kaplan-Meier survival analyses to estimate relative risk of earlier or later age at puberty associated with phenol exposures. For enterolactone and benzophenone-3, girls experienced breast development 5-6 months later, adjusted HR 0.79 (0.64-0.98) and HR 0.80 (0.65-0.98) respectively for the 5th vs 1st quintiles of urinary biomarkers (μg/g-creatinine). Earlier breast development was seen for triclosan and 2,5-dichlorophenol: 4-9 months sooner for 5th vs 1st quintiles of urinary concentrations (HR 1.17 (0.96-1.43) and HR 1.37 (1.09-1.72), respectively). Association of breast development with enterolactone, but not the other three phenols, was mediated by body size. These phenols may be antiadipogens (benzophenone-3 and enterolactone) or thyroid agonists (triclosan and 2,5-dichlorophenol), and their ubiquity and relatively high levels in children would benefit from further investigation to confirm these findings and to establish whether there are certain windows of susceptibility during which exposure can affect pubertal development. PMID:26335517

  17. Preparation and characterization of light-switchable polymer networks attached to solid substrates.

    Science.gov (United States)

    Schenderlein, Helge; Voss, Agnieszka; Stark, Robert W; Biesalski, Markus

    2013-04-01

    Surface-attached polymer networks that carry light-responsive nitrospiropyran groups in a hydrophilic PDMAA matrix were prepared on planar silicon and glass surfaces and were characterized with respect to their switching behavior under the influence of an external light trigger. Functional polymers bearing light-responsive units as well as photo-cross-linkable benzophenone groups were first synthesized using free radical copolymerization. The number of spiropyran groups in the copolymer was controlled by adjusting the concentration of the respective monomer in the copolymerization feed. The polymer films were prepared by spin-coating the functional polymers from solution and by ultraviolet light (UV)-induced cross-linking utilizing benzophenone photochemistry. On substrates with immobilized benzophenone groups, the complete polymer network is linked to the surface. The dry thickness of the films can be controlled over a wide range from a few nanometers up to more than 1 μm. The integration of such light-switchable organic moieties into a surface-attached polymer network allows one to increase the overall number of light-responsive groups per surface area by adjusting the amount of surface-attached polymer networks. The spiropyran's function in dry (solvent-free) and swollen polymer films can be reversibly switched by UV and visible irradiation. In addition, the switching in water is faster than in the dry state. Therefore, implementing light-responsive spiropyran functions in polymer films linked to solid surfaces could allow for switching of the chemical and optical surface properties in a fast and spatially controlled fashion. PMID:23461870

  18. 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.

  19. Synthesis of novel silica-polyimide nanocomposite films using aromatic-amino modified silica nanoparticles: Mechanical, thermal and morphological investigations

    Directory of Open Access Journals (Sweden)

    R. V. Ghorpade

    2015-05-01

    Full Text Available Silica nanoparticles were modified with aromatic amino groups and modified-silica/polyimide composite films were prepared using them. 3,3',4,4'-Benzophenone tetracarboxylic dianhydride (BTDA and 4,4'-oxydianiline (ODA were used as precursors for polyimide matrix. The structures of the modified nanoparticles and hybrid nanocomposites were identified using Fourier Transform Infrared (FTIR spectrometry. The hybrid composite films were evaluated for mechanical, thermal and morphological characteristics. Morphological results describe a uniform dispersion of silica particles in the polymer matrix. The thermal stability and mechanical properties of polyimide composite were improved, and the decomposition temperature was increased when the amount of silica nanoparticles was increased.

  20. Synthesis of tin-containing polyimide films

    Science.gov (United States)

    Ezzell, S. A.; Taylor, L. T.

    1984-01-01

    A series of tin-containing polyimide films derived from either 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride or pyromellitic dianhydride and 4,4'-oxydianiline have been synthesized and their electrical properties examined. Highest quality materials (i.e., homogeneous, smooth surface, flexible) with the best electrical properties were doped with either SnCl2.2H2O or (n-Bu)2SnCl2. In all cases, extensive reactivity of the tin dopant with water, air or polyamic acid during imidization is observed. Lowered electrical surface resistivities appear to be correlatable with the presence of surface tin oxide on the film surface.

  1. Synthesis and characterization of new optically active copoly(amid-imide)s based on N-phthalimido-L-aspartic acid and aromatic diamines

    Institute of Scientific and Technical Information of China (English)

    Khalil; Faghihi; Hamidreza; Alimohammadi

    2010-01-01

    In this article,six new optically active copoly(amide-imide)s(10a-f) were synthesized through the direct polycondensation reaction of N-phthalimido-L-aspartic acid(4) with 1,5-diamino naphthalene(8),3,4-diamino benzophenone(9) in the presence of therphthahc acid(7),fumaric acid(6) and adipic acid(5) as a second diacid in a medium consisting of N-methyl-2-pyrrolidone,triphenyl phosphite, calcium chloride and pyridine.The resulting copolymers were fully characterized by means of FT-IR spectroscopy,elementa...

  2. 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

  3. 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.

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

    International Nuclear Information System (INIS)

    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

  5. 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

  6. The Al(I) molecule, Ph2COAl and its anion

    Science.gov (United States)

    Zhang, Xinxing; Eichhorn, Bryan; Schnöckel, Hansgeorg; Bowen, Kit

    2016-08-01

    We have formed the Al(I)-containing molecule, benzophenone-aluminum, i.e., Ph2COAl, and studied it by conducting density functional theory calculations on both its neutral and anionic forms and by measuring the photoelectron spectrum of its anion. Our calculations identified two nearly iso-energetic anion isomers, (Ph2COAl)-, the vertical detachment energies (VDE) of which are in excellent agreement with our photoelectron spectrum. Natural population analysis (NPA) of Ph2COAl found the Al moiety to be positively charged by +0.81 e, indicating a strongly ionic bond between Al and Ph2CO, i.e., Ph2CO-Al+.

  7. Influence of the donor concentration on the decay kinetics of sensitized phosphorescence of 1,3,5-triphenylbenzene in toluene at 77 K

    Science.gov (United States)

    Suraeva, E. Yu.; Tishchenko, A. B.; Deryabin, M. I.; Avdeev, A. V.

    2012-04-01

    Dependence of the kinetics of sensitized phosphorescence (SP) of 1,3,5-triphenylbenzene (1,3,5-TPB) on the concentration of the energy donor - benzophenone (BP) - is studied in toluene at 77 K. An increase in the SP decay rate of 1,3,5-TPB with concentration is established. It is demonstrated that the reason for the increase in the decay rate is the increased radiative deactivation rate constant of triplet excitations caused by exchange interactions. The coefficient characterizing the exponential dependence of the radiative deactivation rate constant for triplet excitations of 1,3,5-TPB on the intermolecular distance in the donor-acceptor pair is determined.

  8. Sub-nanosecond plastic scintillators

    International Nuclear Information System (INIS)

    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

  9. Merocyanine-type dyes from barbituric acid derivatives

    Science.gov (United States)

    Rezende, Marcos Caroli; Campodonico, Paola; Abuin, Elsa; Kossanyi, Jean

    2001-05-01

    The preparation and the solvatochromic behavior of two dyes, obtained by condensation of N, N'-dimethylbarbituric acid with dimethylaminobenzaldehyde and with 4,4'-bis( N, N-dimethylamino)benzophenone (Michler's ketone) are described. The latter dye is rather sensitive to the polarity of the medium, and in particular, to the hydrogen-bond-donor ability of protic solvents. The solvatochromism of both compounds is discussed in terms of the π* and ET(30) solvent polarity scales and their differences in behavior interpreted with the aid of semiempirical calculations.

  10. One Step Photopolymerization of N, N-Methylene Diacrylamide and Photocuring of Carboxymethyl Starch-Silver Nanoparticles onto Cotton Fabrics for Durable Antibacterial Finishing

    OpenAIRE

    M. A. El-Sheikh; H.M. Ibrahim

    2014-01-01

    The PI/UV system ((4-trimethyl ammonium methyl) benzophenone chloride/UV) was used to synthesize carboxymethyl starch- (CMS-) stabilized silver nanoparticles (AgNPs). AgNPs so prepared had round shape morphology with size of 1–7 nm. The prepared AgNPs were utilized to impart antibacterial finishing for cotton fabrics. The PI/UV system was further utilized to fix AgNPs onto cotton fabrics by photocrosslinking of AgNPs-CMS composite onto cotton fabrics to impart durable antibacterial properties...

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

    International Nuclear Information System (INIS)

    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

  12. A Novel Photosynthesis of Carboxymethyl Starch-Stabilized Silver Nanoparticles

    OpenAIRE

    M. A. El-Sheikh

    2014-01-01

    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...

  13. Structural and conformational investigation of nemorosone: A combined X-ray and quantum mechanical study

    Science.gov (United States)

    Pagano, Bruno; Pavone, Michele; Piccinelli, Anna Lisa; Rastrelli, Luca; Cuesta-Rubio, Osmany; Mattia, Carlo A.; Barone, Vincenzo

    2008-09-01

    Here we report the X-ray crystal structure of nemorosone, a polyprenylated benzophenone derivative that presents biological activity and potential use as antimicrobial, cytotoxic and antioxidant drug. On the basis of crystallographic data, we carried out a theoretical investigation based on state-of-the-art density functional approaches. A remarkable agreement has been found between experimental findings and quantum mechanical results. Furthermore, the theoretical calculations allowed us to dissect the structural and energetic features of the nemorosone molecule, thus paving the route toward the design of new synthetic drugs.

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

    International Nuclear Information System (INIS)

    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

  15. CHARGE-TRANSFER AND ENERGY-TRANSFER IN THE PHOTO-INDUCED COPOLYMERIZATION OF 2-VINYLNAPHTHALENE WITH MALEIC ANHYDRIDE

    Institute of Scientific and Technical Information of China (English)

    LI Tong; LUO Bin; LI Shanjun; CHU Guobei

    1990-01-01

    The initiation mechanism of the copolymerization of 2-vinylnaphthalene with maleic anhydride was studied under irradiation of 365 nm. The excited complex was formed from ( 1 ) the local excitation of 2-vinylnaphthalene followed by the charge-transfer interaction with maleic anhydride and ( 2 ) the excitation of the ground state charge-transfer complex, and then it collapsed to 1,4-tetramethylene biradical for initiation. A 1:1 alternating copolymer was formed in different monomer feeds. Addition of benzophenone could greatly enhance the rate of copolymerization through energy-transfer mechanism.

  16. Reactivity of a base-stabilized germanimine and germathione

    OpenAIRE

    Veith, Michael; Detemple, Astrid

    1992-01-01

    After studying the reactivity of the base-stabilized germanimine (MeSi)2(NtBu)4Ge=NSiMe3 1 and germanethione (MeSi)2(NtBu)4Ge=S 2 towards simple polar molecules, we were interested in their cycloaddition chemistry. 1 gives no reaction with ketones (e. g. benzophenone) and dienes (e. g. 2,3-dimethylbutadiene). The reaction of 1 with an excess of CS2 gives 2 and trimethylsilylisothiocyanate 4. 2 reacts with the dichlorocarbene to give the bis(amino)dichlorogermane 5.

  17. Quantitative analysis of the mixtures of illicit drugs using terahertz time-domain spectroscopy

    Science.gov (United States)

    Jiang, Dejun; Zhao, Shusen; Shen, Jingling

    2008-03-01

    A method was proposed to quantitatively inspect the mixtures of illicit drugs with terahertz time-domain spectroscopy technique. The mass percentages of all components in a mixture can be obtained by linear regression analysis, on the assumption that all components in the mixture and their absorption features be known. For illicit drugs were scarce and expensive, firstly we used common chemicals, Benzophenone, Anthraquinone, Pyridoxine hydrochloride and L-Ascorbic acid in the experiment. Then illicit drugs and a common adulterant, methamphetamine and flour, were selected for our experiment. Experimental results were in significant agreement with actual content, which suggested that it could be an effective method for quantitative identification of illicit drugs.

  18. Protective effects of 2,4-dihydroxybenzophenone against acetaminophen-induced hepatotoxicity in mice

    OpenAIRE

    Yue-Ying He; Bao-Xu Zhang; Feng-Lan Jia

    2011-01-01

    AIM: To examine the effects of 2,4-dihydroxybenzophenone (BP-1), a benzophenone derivative used as an ultraviolet light absorbent, on acetaminophen (APAP)-induced hepatotoxicity in C57BL/6J mice. METHODS: Mice were administered orally with BP-1 at doses of 200, 400 and 800 mg/kg body weight respectively every morning for 4 d before a hepatotoxic dose of APAP (350 mg/kg body weight) was given subcutaneously. Twenty four hours after APAP intoxication, the serum enzyme including serum alaine ami...

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

    International Nuclear Information System (INIS)

    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 (TiO2), or a radical mediator (H2O2). 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)

  20. Field evaluation of three botanical repellents against Psorophora ferox, Aedes atlanticus, and Aedes mitchellae.

    Science.gov (United States)

    Qualls, Whitney A; Xue, Rui-De

    2009-09-01

    Three botanical natural repellents, Swamp Buddy Bug Chaser (AI 12% plant-based essential oils), All Sport (AI plant-based essential oils, benzophenone-3, octinoxate, and octisalate), and Geraniol (AI 25% geraniol oil and lemongrass extract) were evaluated at a field site in Elkton, Florida, to determine the protection time provided against Psorophora ferox, Aedes atlanticus, and Ae. mitchellae. These three products provided different protection times against biting mosquitoes. Geraniol provided the longest protection time from mosquito bites (4 h), followed by All Sport (1.5 h) and Swamp Buddy Bug Chaser (1 h). This study provides the first information about botanical insect repellents against these floodwater mosquito species. PMID:19852232

  1. Secondary Metabolites of Aspergillus sp. CM9a, an E ndophytic Fungus of Cephalotaxus mannii

    Directory of Open Access Journals (Sweden)

    Heng Xue

    2012-01-01

    Full Text Available Eleven compounds belonging to eight structure types, namely cyclopentenedione (1, diketopiperazines (2, 9, 10, lactone (3, benzophenone (4, 5, terpene (6, anthraquinone (7, diphenyl ethers (10, and alkaloid (11 were isolated from the cultivation extract of the strain Aspergillus sp. CM9a, which was isolated from the stems of Cephalotaxus mannii. Among them, compounds 1, 2, and 3 were determined to b e new ones on the basis of spectroscopic data including 1D- and 2D - NMR experiments and HR Q-TOF MS. The structures of the eight known compounds were characterized based on their NMR data and by comparison with those reported.

  2. Direct observation of slow intersystem crossing in an aromatic ketone, fluorenone.

    Science.gov (United States)

    Soep, Benoît; Mestdagh, Jean-Michel; Briant, Marc; Gaveau, Marc-André; Poisson, Lionel

    2016-08-17

    Direct measurements of Single vibronic Level InterSystem Crossing (SLISC) have been performed on the fluorenone molecule in the gas phase, by time resolved photoelectron and photoion spectroscopy. Vibronic transitions above the S1 nπ* origin were excited in the 432-420 nm region and the decay of S1 and growth of T1(3)ππ* could be observed within a 10 ns time domain. The ionization potential is measured as 8.33 ± 0.04 eV. The energy of the first excited triplet state of fluorenone, T1 has been characterized directly at 18 640 ± 250 cm(-1). The internal conversion of S1 to S0 is found to amount to ∼15% of the population decay, thus ISC is the dominant electronic relaxation process. ISC, although favored by the S1(1)nπ*-T1(3)ππ* coupling scheme, is 3 orders of magnitude less efficient than in the similar molecule benzophenone. Thus, the planarity of the fluorenone molecule disfavors the exploration of the configuration space where surface crossings would create high ISC probability, which occurs in benzophenone through surface crossings. The time evolution of S1 fluorenone is well accounted for by the statistical decay of individual levels into a quasi-continuum of T1 vibronic levels. PMID:27485671

  3. 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.

  4. Stereoselective Reduction of Prochiral Ketones by Plant and Microbial Biocatalysts.

    Science.gov (United States)

    Javidnia, K; Faghih-Mirzaei, E; Miri, R; Attarroshan, M; Zomorodian, K

    2016-01-01

    Chiral alcohols are the key chiral building blocks to many enantiomerically pure pharmaceuticals. The biocatalytic approach in asymmetric reduction of corresponding prochiral ketones to the preparation of these optically pure substances is one of the most promising routes. The stereoselective reduction of different kinds of prochiral ketones catalyzed by various plants and microorganisms was studied in this work. Benzyl acetoacetate, methyl 3-oxopentanoate, ethyl 3-oxopentanoate, and ethyl butyryl acetate were chosen as the model substrates for β-ketoesters. Benzoyl acetonitrile, 3-chloro propiophenone, and 1-acetyl naphthalene were chosen as aromatic aliphatic ketones. Finally, 2-methyl benzophenone and 4-chloro benzophenone were selected as diaryl ketones. Plant catalysis was conducted by Daucus carota, Brassica rapa, Brassica oleracea, Pastinaca sativa, and Raphnus sativus. For microbial catalysis, Aspergillus foetidus, Penicillum citrinum, Saccharomyces carlbergensis, Pichia fermentans, and Rhodotrula glutinis were chosen. Chiral alcohols were obtained in high yields and with optical purity. A superiority in the microorganisms' performance in the bioreduction of prochiral ketones was detected. Among microorganisms, Rhodotrula glutinis showed remarkable results with nearly all substrates and is proposed for future studies. PMID:27168684

  5. Stereoselective reduction of prochiral ketones by plant and microbial biocatalysts

    Directory of Open Access Journals (Sweden)

    K Javidnia

    2016-01-01

    Full Text Available Chiral alcohols are the key chiral building blocks to many enantiomerically pure pharmaceuticals. The biocatalytic approach in asymmetric reduction of corresponding prochiral ketones to the preparation of these optically pure substances is one of the most promising routes. The stereoselective reduction of different kinds of prochiral ketones catalyzed by various plants and microorganisms was studied in this work. Benzyl acetoacetate, methyl 3-oxopentanoate, ethyl 3-oxopentanoate, and ethyl butyryl acetate were chosen as the model substrates for β-ketoesters. Benzoyl acetonitrile, 3-chloro propiophenone, and 1-acetyl naphthalene were chosen as aromatic aliphatic ketones. Finally, 2-methyl benzophenone and 4-chloro benzophenone were selected as diaryl ketones. Plant catalysis was conducted by Daucus carota, Brassica rapa, Brassica oleracea, Pastinaca sativa, and Raphnus sativus.For microbial catalysis, Aspergillus foetidus, Penicillum citrinum, Saccharomyces carlbergensis, Pichia fermentans, and Rhodotrula glutinis were chosen. Chiral alcohols were obtained in high yields and with optical purity. A superiority in the microorganisms' performance in the bioreduction of prochiral ketones was detected. Among microorganisms, Rhodotrula glutinis showed remarkable results with nearly all substrates and is proposed for future studies.

  6. 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.

  7. Spectral, thermal, electrochemical and analytical studies on Cd(II) and Hg(II) thiosemicarbazone complexes

    Science.gov (United States)

    El-Asmy, A. A.; El-Gammal, O. A.; Saleh, H. S.

    2008-11-01

    The coordination characteristic of the investigated thiosemicarbazones towards hazard pollutants, Cd(II) and Hg(II), becomes the first goal. Their complexes have been studied by microanalysis, thermal, electrochemical and spectral (electronic, IR and MS) studies. The substitutent (salicylaldehyde, acetophenone, benzophenone, o-hydroxy- p-methoxybenzophenone or diacetylmonoxime) plays an important role in the complex formation. The coordination sites were the S for thiosemicarbazide (HTS); NN for benzophenone thiosemicarbazone (HBTS); NS for acetophenone thiosemicarbazone (HATS) and salicylaldehyde thiosemicarbazone (H 2STS); NNS or NSO for diacetylmonoxime thiosemicarbazone (H 2DMTS). The stability constants of Hg(II) complexes were higher than Cd(II). The kinetic and thermodynamic parameters for the different thermal decomposition steps in the complexes have been evaluated. The activation energy values of the first step ordered the complexes as: [Cd(H 2STS)Cl 2]H 2O > [Cd(H 2DAMTS)Cl 2] > [Cd(HBTS) 2Cl 2]2H 2O > [Cd(HATS) 2Cl 2]. The CV of [Cd(H 2STS)Cl 2]H 2O and [Hg(HBTS)Cl 2] were recorded. The use of H 2DMTS as a new reagent for the separation and determination of Cd(II) ions from water and some synthetic samples using flotation technique is aimed to be discussed.

  8. Design, Synthesis, and Bioevaluation of Novel Strobilurin Derivatives

    Institute of Scientific and Technical Information of China (English)

    朱晓磊; 王福; 李慧; 杨文超; 陈琼; 杨光富

    2012-01-01

    Strobilurins are one of the most important natural products with fungicidal activities and well known for their novel action mode, broad fungicidal spectrum, lower toxicity against mammalian cells, and environmentally benign characteristics. Design and syntheses of strobilurin analogues therefore have attracted great attention in the field of agrochemistry. Previously, we successfully developed a new molecular design method of pharmacophore-linked fragment virtual screening (PFVS) and discovered a lead compound (E)-methyl-2-(2-(((3-(imino-(phenyl)- methyl)phenyl)thio)methyl)phenyl)-3-methoxyacrylate (1). To discover new strobilurin analogues with higher fun- gicidal activity, the structural modification of compound 1 was carried out guided by bioisosterism. A series of benzophenone derivatives 2a--2j were synthesized, among which compound 2j with a Ki value of 1.89 nmol/L was identified as the most promising inhibitor of porcine cytocbrome bcl complex, 157-fold improved binding affinity compared to the commercially available bCl inhibitor Azoxystrobin (AZ). In addition, most of the new compounds displayed excellent fungicidal activity against Sphaerothecafuliginea at the concentration of 200μmol/L. The pre- sent work indicates that strobilurin analogues containing benzophenone side chains may be the ideal leads for future fungicide discovery.

  9. Visible-Light Actinometry and Intermittent Illumination as Convenient Tools to Study Ru(bpy)3Cl2 Mediated Photoredox Transformations

    Science.gov (United States)

    Pitre, Spencer P.; McTiernan, Christopher D.; Vine, Wyatt; Dipucchio, Rebecca; Grenier, Michel; Scaiano, Juan C.

    2015-11-01

    Photoredox catalysis provides many green opportunities for radical-mediated synthetic transformations. However, the determination of the underlying mechanisms has been challenging due to lack of quantitative methods that can be easily implemented in synthetic labs, where this research tends to be centered. We report here on the development, characterization and calibration of a novel actinometer based on the photocatalyst tris(2,2‧-bipyridyl)ruthenium(II) chloride (Ru(bpy)3Cl2). By using the same molecule as the photocatalyst and the actinometer, we eliminate problems associated with matching sample spectral distribution, lamp-sample spectral overlap and other problems intrinsic to doing quantitative photochemistry in a laboratory that has little expertise in this area. In order to validate our actinometer system in determining the quantum yield of a Ru(bpy)3Cl2 photosensitized reaction, we test the Ru(bpy)3Cl2 catalyzed oxidation of benzhydrol to benzophenone as a model chain reaction. We also revive the rotating sector method by updating the technique for modern LED technologies and demonstrate how intermittent illumination on the timescale of milliseconds to seconds can help probe a chain reaction, using the benzhydrol to benzophenone oxidation to validate the technique. We envision these methods to have great implications in the field of photoredox catalysis, providing researchers with valuable research tools.

  10. Photochemistry of aromatic ketones in sodium dodecyl sulphate micelles in the presence of unsaturated fatty acids

    Directory of Open Access Journals (Sweden)

    DEJAN Z. MARKOVIC

    2004-02-01

    Full Text Available Laser-flash photolysis has been employed to characterize the behaviour of the free radicals created in the photochemical reaction of benzophenone (BZP, as well as of its lipoidal derivative, benzophenone-4-heptyl-4’-pentanoic acid (BHPA, with chosen unsaturated fatty acids in sodium dodecyl sulphate micelles. The calculated rate constants were used to study the “cage effect”, i.e., the recombination of the created radical-pairs (BZP, BHPA ketyl radical - lipid radical inside the highly limited space of the SDS micelles. The “cage effect” appears to be the dominant event inside SDS micelles, dependent on the structure of both the reactants-precursors. The fractions of the initially created radical-pairs which escape the “cage effect” and exit into the surrounding aqueous phase do not exceed 16 %. This fact is of enormous importance for the self-control of the pathogenic process of lipid peroxidation.

  11. 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)

    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. 60Co 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

  12. Flame-retardant Cotton Fabric Through Graft Copolymerisation

    Directory of Open Access Journals (Sweden)

    Inderjeet Kaur

    2007-03-01

    Full Text Available In an attempt to impart flame-retarding properties to the cotton fabric, post-graftingphosphorylation reactions on grafted cotton fabric were carried out. Photochemical graftcopolymerisation of 4-vinyl pyridine (4-VP onto cotton fabric using benzophenone asphotosensitiser was carried out. Maximum percentage of grafting Pg, (18.50 % was obtainedunder optimum  conditions; irradiation time 75 min, 0.5 ml of  benzophenone,  [4-VP]=748.71 x10-2 mole/l and 5 ml of water in the reaction mixture. Aliphatic alcohols of varying chain lengthdecreased percentage of grafting. The pendant pyridine rings of the 4-VP grafted cotton fabricwere converted to pyridinium chloride followed by the reaction with acrylamide to give 2-amido-ethylpyridiniumchloride. This was subjected to phosphorylation reaction with PCl3/petroleumether. The phosphorylated grafted cotton fabric burns only in the presence of flame with veryslow propagation of the flame (only 3.8 cm2 was found to burn of the total area of 147 cm2 with0.12 g of the ash content. Characterisation of gray cotton fabric and modified cotton fabric wascarried out by FTIR, thermogravimetric analysis, crease recovery, and moisture absorption studies.

  13. Stereoselective Reduction of Prochiral Ketones by Plant and Microbial Biocatalysts

    Science.gov (United States)

    Javidnia, K.; Faghih-Mirzaei, E.; Miri, R.; Attarroshan, M.; Zomorodian, K.

    2016-01-01

    Chiral alcohols are the key chiral building blocks to many enantiomerically pure pharmaceuticals. The biocatalytic approach in asymmetric reduction of corresponding prochiral ketones to the preparation of these optically pure substances is one of the most promising routes. The stereoselective reduction of different kinds of prochiral ketones catalyzed by various plants and microorganisms was studied in this work. Benzyl acetoacetate, methyl 3-oxopentanoate, ethyl 3-oxopentanoate, and ethyl butyryl acetate were chosen as the model substrates for β-ketoesters. Benzoyl acetonitrile, 3-chloro propiophenone, and 1-acetyl naphthalene were chosen as aromatic aliphatic ketones. Finally, 2-methyl benzophenone and 4-chloro benzophenone were selected as diaryl ketones. Plant catalysis was conducted by Daucus carota, Brassica rapa, Brassica oleracea, Pastinaca sativa, and Raphnus sativus. For microbial catalysis, Aspergillus foetidus, Penicillum citrinum, Saccharomyces carlbergensis, Pichia fermentans, and Rhodotrula glutinis were chosen. Chiral alcohols were obtained in high yields and with optical purity. A superiority in the microorganisms' performance in the bioreduction of prochiral ketones was detected. Among microorganisms, Rhodotrula glutinis showed remarkable results with nearly all substrates and is proposed for future studies.

  14. Development of p-benzoylbenzoylated [N,C,rANP(1-28)]pBNP32 (pBNP1) derivatives and affinity photolabeling of the bovine NPR-A receptor.

    Science.gov (United States)

    Coupal, M; De Léan, A; McNicoll, N; Fournier, A

    1999-04-29

    Two Nalpha-benzophenone-substituted photoprobes, derived from the high affinity NPR-A chimeric agonist [N, C, rANP(1-28)]pBNP32 (pBNP1) were assembled by solid-phase peptide synthesis. [Nalpha-p-benzoylbenzoyl, Tyr2]pBNP1 (probe A), and [Nalpha-p-benzoylbenzoyl, Tyr18]pBNP1 (probe B) were synthesized and their affinity was tested on bovine zona glomerulosa membrane preparations. Both were found to exert ANP-type high affinities (Kd = 20 pM) with Kd of 10 pM and 30 pM for probe A, and probe B, respectively. Photolabeling of NPR-A with both analogs cross-linked specifically the 130 kDa monomeric NPR-A. The maximal irreversible ligand incorporations were estimated at 18% and 41% for probe A, and probe B, respectively. These results show that the N-terminus of the chimeric compound can be acylated with a large chemical function, such as the benzophenone moiety, without loosing its affinity for the NPR-A receptor. Furthermore, Leu2 or Leu18 can be substituted with tyrosine without disturbing the binding capacity of the ligand. Finally, it appears that the pBNP1 N-terminus is close to the receptor structure as irreversible incorporation is observed after photolabeling. PMID:10222239

  15. Effects of garcinol and guttiferone K isolated from Garcinia cambogia on oxidative/nitrative modifications in blood platelets and plasma.

    Science.gov (United States)

    Kolodziejczyk, Joanna; Masullo, Milena; Olas, Beata; Piacente, Sonia; Wachowicz, Barbara

    2009-11-01

    The effects of garcinol and guttiferone K, two polyisoprenylated benzophenones occurring a food plant called Garcinia cambogia, on oxidative/nitrative protein damage (determined by parameters such as levels of protein carbonyl groups and nitrotyrosine residues) in human blood platelets and plasma after treatment with peroxynitrite (ONOO(-)) were studied in vitro. We also investigated the effects of garcinol and guttiferone K on lipid peroxidation in blood platelets and plasma induced by ONOO(-) (100 microM). Exposure of blood platelets or plasma to peroxynitrite (100 microM) resulted in an increased level of carbonyl groups and nitrotyrosine residues in proteins, and an increase of lipid peroxidation measured by the level of thiobarbituric acid reactive species (TBARS). In the presence of garcinol and guttiferone K (0.1-25 microg/ml), a distinct reduction in the formation of carbonyl groups in plasma and platelet proteins together with the decrease of TBARS caused by 100 microM peroxynitrite, was observed. However, garcinol and guttiferone K did not inhibit plasma and platelet protein nitration induced by peroxynitrite. Polyisoprenylated benzophenones present in human diet such as garcinol or guttiferone K in vitro have protective effects against lipid and protein oxidation and may have some promising effects in vivo because they are good antioxidants in the tested models in vitro. Garcinol and guttiferone K can be also useful as protecting factors against diseases associated with oxidative stress. PMID:19852687

  16. Cell resistant zwitterionic polyelectrolyte coating promotes bacterial attachment: an adhesion contradiction.

    Science.gov (United States)

    Martinez, Jessica S; Kelly, Kristopher D; Ghoussoub, Yara E; Delgado, Jose D; Keller Iii, Thomas C S; Schlenoff, Joseph B

    2016-04-22

    Polymers of various architectures with zwitterionic functionality have recently been shown to effectively suppress nonspecific fouling of surfaces by proteins and prokaryotic (bacteria) or eukaryotic (mammalian) cells as well as other microorganisms and environmental contaminants. In this work, zwitterionic copolymers were used to make thin coatings on substrates with the layer-by-layer method. Polyelectrolyte multilayers, PEMUs, were built with [poly(allylamine hydrochloride)], PAH, and copolymers of acrylic acid and either the AEDAPS zwitterionic group 3-[2-(acrylamido)-ethyldimethyl ammonio] propane sulfonate (PAA-co-AEDAPS), or benzophenone (PAABp). Benzophenone allowed the PEMU to be toughened by photocrosslinking post-deposition. The attachment of two mammalian cell lines, rat aortic smooth muscle (A7r5) and mouse fibroblasts (3T3), and the biofilm-forming Gram-negative bacteria Escherichia coli was studied on PEMUs terminated with PAA-co-AEDAPS. Consistent with earlier studies, it is shown that PAH/PAA-co-AEDAPS PEMUs resist the adhesion of mammalian cells, but, contrary to our initial hypothesis, are bacterial adhesive and significantly so after maximizing the surface presentation of PAA-co-AEDAPS. This unexpected contrast in the adhesive behavior of prokaryotic and eukaryotic cells is explained by differences in adhesion mechanisms as well as different responses to the topology and morphology of the multilayer surface. PMID:26872345

  17. 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.

  18. 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. PMID:26519573

  19. 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 camphor (4-MBC) and 3-benzylidene camphor (3-BC) were rarely detected. Additionally, the detection frequencies and measured concentrations of all targets were clearly higher in mussels than in fish. Spatial distribution of studied 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. PMID:27235899

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

    Science.gov (United States)

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

    2016-05-01

    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-ynyloxy)phenyl)(phenyl)methanone at ambient temperature for affording the desired PVC-based UV-absorbers (PVC-UV) with different amounts of benzophenone moieties, which displayed great resistance to photoaging without degradation while exposed to UV irradiation. These polymeric UV-absorbers also showed good solubilities in common organic solvents and no cytotoxicity vs. HaCat cell. Small amounts of PVC-UV were homogeneously mixed with PVC as additive for stabilizing PVC against UV-photoaging without degradation and releasing small molecule even after 200 h while keeping thermal stability. This route of polymeric additive clearly paved an efficient way for solving the puzzle of separation of small molecule additive.

  1. Leishmanicidal and cholinesterase inhibiting activities of phenolic compounds from Allanblackia monticola and Symphonia globulifera.

    Science.gov (United States)

    Lenta, Bruno Ndjakou; Vonthron-Sénécheau, Catherine; Weniger, Bernard; Devkota, Krishna Prasad; Ngoupayo, Joseph; Kaiser, Marcel; Naz, Qamar; Choudhary, Muhammad Iqbal; Tsamo, Etienne; Sewald, Norbert

    2007-01-01

    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 microM and 0.16 microM, respectively) comparable to that of the reference compound, miltefosine (0.46 microM). 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 microM) of garcinol (2) was almost equal to that of the reference compound galanthamine (0.50 microM). Furthermore, guttiferone A (1) and guttiferone F (4) (IC50 = 2.77 and 3.50 microM, respectively) were more active than galanthamine (IC50 = 8.5) against BChE. PMID:17960072

  2. Associations of prenatal exposure to phenols with birth outcomes

    International Nuclear Information System (INIS)

    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 (βadjusted = −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

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

    International Nuclear Information System (INIS)

    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)

  4. 3-D LTCC microfluidic device as a tool for studying nanoprecipitation

    International Nuclear Information System (INIS)

    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.

  5. 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

  6. Excited state evolution towards ligand loss and ligand chelation at group 6 metal carbonyl centres.

    Science.gov (United States)

    Manton, Jennifer C; Amirjalayer, Saeed; Coleman, Anthony C; McMahon, Suzanne; Harvey, Emma C; Greetham, Gregory M; Clark, Ian P; Buma, Wybren Jan; Woutersen, Sander; Pryce, Mary T; Long, Conor

    2014-12-21

    The photochemistry and photophysics of three model "half-sandwich" complexes (η(6)-benzophenone)Cr(CO)3, (η(6)-styrene)Cr(CO)3, and (η(6)-allylbenzene)Cr(CO)3 were investigated using pico-second time-resolved infrared spectroscopy and time-dependent density functional theory methods. The (η(6)-benzophenone)Cr(CO)3 complex was studied using two excitation wavelengths (470 and 320 nm) while the remaining complexes were irradiated using 400 nm light. Two independent excited states were detected spectroscopically for each complex, one an unreactive excited state of metal-to-arene charge-transfer character and the other with metal-to-carbonyl charge transfer character. This second excited state leads to an arrested release of CO on the pico-second time-scale. Low-energy excitation (470 nm) of (η(6)-benzophenone)Cr(CO)3 populated only the unreactive excited state which simply relaxes to the parent complex. Higher energy irradiation (320 nm) induced CO-loss. Irradiation of (η(6)-styrene)Cr(CO)3, or (η(6)-allylbenzene)Cr(CO)3 at 400 nm provided evidence for the simultaneous population of both the reactive and unreactive excited states. The efficiency at which the unreactive excited state is populated depends on the degree of conjugation of the substituent with the arene π-system and this affects the efficiency of the CO-loss process. The quantum yield of CO-loss is 0.50 for (η(6)-allylbenzene)Cr(CO)3 and 0.43 for (η(6)-styrene)Cr(CO)3. These studies provide evidence for the existence of two photophysical routes to CO loss, a minor ultrafast route and an arrested mechanism involving the intermediate population of a reactive excited state. This reactive excited state either relaxes to reform the parent species or eject CO. Thus the quantum yield of the CO-loss is strongly dependent on the excitation wavelength. Time-dependent density functional theory calculations confirm that the state responsible for ultrafast CO-loss has significant metal-centred character while

  7. Conformational study of aromatic ketones: chemical shift reagents: uranium chelates

    International Nuclear Information System (INIS)

    A series of benzophenones, 2-benzoyl thiophenes and 2-benzoyl pyridines, all substituted at the benzene ring by an amino acid chain, have been synthesised with the object of examining to what extent the site of the aminoacid chain and the site and nature of the other substituents modify the electronic structure of the molecule and the orientation of each ring with respect to the plane of the carbonyl group. In the second part a study of paramagnetic cations, in particular of uranium, which is able to form stable chelates with beta-diketones was carried out to study their complexing power. The chelates studied are the (hexafluoropentanedionate)4U, the (heptafluorodimethyloctanedionate)4U and the (trifluorophenylbutanedionate)4U

  8. The examination of berberine excited state by laser flash photolysis

    Science.gov (United States)

    Cheng, Lingli; Wang, Mei; Zhao, Ping; Zhu, Hui; Zhu, Rongrong; Sun, Xiaoyu; Yao, Side; Wang, Shilong

    2009-07-01

    The property of the excited triplet state of berberine (BBR) was investigated by using time-resolved laser flash photolysis of 355 nm in acetonitrile. The transient absorption spectra of the excited triplet BBR were obtained in acetonitrile, which have an absorption maximum at 420 nm. And the ratio of excitation to ionization of BBR in acetonitrile solvent was calculated. The self-decay and self-quenching rate constants, and the absorption coefficient of 3BBR* were investigated and the excited state quantum yield was determined. Furthermore utilizing the benzophenone (BEN) as a triplet sensitizer, and the β-carotene (Car) as an excited energy transfer acceptor, the assignment of 3BBR* was further confirmed and the related energy transfer rate constants were also determined.

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

    International Nuclear Information System (INIS)

    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

  10. Mechanistic Features of the Reactions of Organomagnesium Compounds

    DEFF Research Database (Denmark)

    Holm, Torkil; Crossland, Ingolf

    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 in...... correlations.3.3. Radical probes.3.4. A thermochemical approach.3.5. Kinetic isotope effects.3.5.1. Isotopic carbon and hydrogen in benzophenone.3.5.2. Deuterium substitution in the Grignard reagent.3.5.2.1. Primary isotope effect on the reduction process. 3.5.2.2. Secondary isotope effects on the addition...

  11. Poly (ether ether ketone) derivatives: Synthetic route and characterization of nitrated and sulfonated polymers

    Energy Technology Data Exchange (ETDEWEB)

    Conceicao, T.F.; Bertolino, J.R. [Grupo de Estudo em Materiais Polimericos-Departamento de Quimica, Universidade Federal de Santa Catarina, Florianopolis, SC (Brazil); Barra, G.M.O. [Departamento de Engenharia Mecanica, Universidade Federal de Santa Catarina, Florianopolis, SC (Brazil); Pires, A.T.N. [Grupo de Estudo em Materiais Polimericos-Departamento de Quimica, Universidade Federal de Santa Catarina, Florianopolis, SC (Brazil)], E-mail: alfredotiburcio@pq.cnpq.br

    2009-03-01

    Nitrated and sulfonated poly (ether ether ketone) [SNPEEK] samples were prepared through sulfonation of nitrated PEEK (NPEEK) at different temperatures resulting in polymers with distinct sulfonation degrees (SD). The sulfonation occurred preferentially in the hydroquinone segment even after 81% of this moiety had been nitrated. Sulfonation in the benzophenone moiety was achieved only in 16% of this segment at the reaction temperature of 80 deg. C. The substitution degree was obtained through the TG curves, and values were in agreement with {sup 1}H NMR data when SD is much higher as ND (nitration degree). The highest SD obtained was 72%. Membranes of the sulfonated and nitrated PEEK (SNPEEK) were prepared by casting and showed good ductility depending on the substitution degree, with proton conductivity in the order of 10{sup -2} S cm{sup -1}, an important characteristic in some applications, such as in fuel cells.

  12. One-step polymer surface modification for minimizing drug, protein, and DNA adsorption in microanalytical systems.

    Science.gov (United States)

    Larsen, Esben Kjær Unmack; Larsen, Niels B

    2013-02-21

    The non-specific adsorption of dissolved analytes strongly reduces the sensitivity and reliability in polymer microanalytical systems. Here, a one-step aqueous phase procedure modifies polymer material surfaces to strongly reduce their non-specific adsorption of a broad range of organic analytes including hydrophobic and hydrophilic drugs (0.23 8) in their pharmaceutically relevant concentration range ≤100 nM. The low adsorption is mediated by photochemical conjugation, where polyethylene glycol (PEG) polymers in aqueous solution are covalently bound to the surface by UV illumination of dissolved benzophenone and a functionalized PEG. The method can coat the interior of polymer systems made from a range of materials commonly used in microanalytical systems, including polystyrene (PS), cyclic olefin copolymer (COC), liquid crystalline polymer (LCP), and polyimide (PI). PMID:23254780

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

    DEFF Research Database (Denmark)

    Holm, Torkil

    2000-01-01

    Competition kinetics are useful for estimation of the reactivities of Grignard reagents if the reaction rates do not differ widely and if exact rates are not needed. If the rate of mixing is slower than the rate of reaction the ratios between the rates of fast and slow reagents are found to be too...... may account for almost all the product even when present as only 1 part in 100 parts of the competing agent. In this way allylmagnesium bromide is estimated to react with acetone, benzophenone, benzaldehyde, and diethylacetaldehyde ca. 1.5 x 105 times faster than does butylmagnesium bromide. The rates...... found for the four substrates do not differ significantly and it seems possible that there is a ceiling over the rate of reaction of this reagent, for example caused by diffusion control. This may explain that competition kinetics using allylmagnesium bromide have failed to show kinetic isotope effects...

  14. Neutron and x-ray emission time measurements

    International Nuclear Information System (INIS)

    Laser fusion targets can produce implosions with a delay between the peak compression (neutron emission) and the laser pulse on the order of 0.2 to 2.5 ns. We use a fast detector system to measure x-ray and D-T neutron emission times with a resolution of 100 to 200 ps. An NE111 fluor (quenched with 2% benzophenone) coupled to a microchannel plate photomultiplier tube detects the arrival of neutrons and x rays. A separate biplanar vacuum photodiode detects the arrival of unabsorbed laser light scattered from the target. These signals are mixed, then recorded on a 500 MHz transient digitizer. The discussion includes a description of the time interval system, experimental data, data analysis techniques, and system calibration

  15. Microwave-Assisted Organocatalyzed Rearrangement of Propargyl Vinyl Ethers to Salicylaldehyde Derivatives: An Experimental and Theoretical Study.

    Science.gov (United States)

    Tejedor, David; Cotos, Leandro; Márquez-Arce, Daniel; Odriozola-Gimeno, Mikel; Torrent-Sucarrat, Miquel; Cossío, Fernando P; García-Tellado, Fernando

    2015-12-01

    The microwave-assisted imidazole-catalyzed transformation of propargyl vinyl ethers (PVEs) into multisubstituted salicylaldehydes is described. The reaction is instrumentally simple, scalable, and tolerates a diverse degree of substitution at the propargylic position of the starting PVE. The generated salicylaldehyde motifs incorporate a broad range of topologies, spanning from simple aromatic monocycles to complex fused polycyclic systems. The reaction is highly regioselective and takes place under symmetry-breaking conditions. The preparative power of this reaction was demonstrated in the first total synthesis of morintrifolin B, a benzophenone metabolite isolated from the small tree Morinda citrifolia L. A DFT study of the reaction was performed with full agreement between calculated values and experimental results. The theoretically calculated values support a domino mechanism comprising a propargyl Claisen rearrangement, a [1,3]-H shift, a [1,7]-H shift (enolization), a 6π electrocyclization, and an aromatization reaction. PMID:26515241

  16. In vitro UV-A protection factor (PF-UVA) of organic and inorganic sunscreens.

    Science.gov (United States)

    Couteau, C; El-Boury, S; Paparis, E; Sébille-Rivain, V; Coiffard, L J M

    2009-01-01

    The objective of this research was to evaluate the efficacy of various sunscreen agents incorporated into an O/W emulsion. Within the scope of this study only an in vitro method was used. According to selected filter UVA, we can obtain more or less effective creams. With the seven available filters, we can cover a range of values between 2 and 12. In addition to these seven filters absorbing in UVA range, variously coated titanium dioxide and zinc oxide were tested as well. So it appears that the best organic UVA filter is anisotriazine at 10% (PF-UVA = 11.82). Its effectiveness is comparable with that of the titanium dioxide forms used at 25%. Photostability in Suntest showed that the more photostable UVA-filters are the benzophenones. PMID:19630696

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

    Science.gov (United States)

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

    2014-03-01

    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. PMID:24448461

  18. The Characteristics of Organic Matter from the Triassic Clays of nw Margin of the Holy Cross Mts (Poland) — Preliminary Report

    Science.gov (United States)

    Marynowski, Leszek; Wyszomirski, Piotr; Kurkiewicz, Sławomir

    2006-01-01

    The molecular character of organic matter in Triassic clays on the NW border of the Holy Cross Mts was determined in apolar, aromatic and polar fractions of extractable organic matter (OM) using GC-MS analysis. The contribution of terrestrial higher plants to the kerogene is revealed by the dominant presence of odd long-chain n-alkanes and by the occurrence of retene. Benzophenone, fluorenone, cyclopenta(def)phenanthrenone, antracenone and benzanthrone were among the compounds identified in polar fractions of the soluble organic matter. These commonly originate during strong oxidation of sedimentary organic matter. The aromatic fraction is characterised by the presence of phenyl derivatives (PhPAC) such as phenylnaphthalenes, terphenyls, phenyldibenzofurans and phenylphenanthrenes that are also products of the abiotic oxidation of organic matter. The oxidation processes that occurred during sedimentation and during early diagenesis resulted in a very significant decrease in the organic matter content in the clays. This decrease considerably influences their technological properties.

  19. Covalent sidewall functionalization of single-walled carbon nanotubes: a photoreduction approach.

    Science.gov (United States)

    Wei, Liangming; Zhang, Yafei

    2007-12-12

    Covalent sidewall functionalization of single-walled carbon nanotubes (SWNTs) via photoreduction of aromatic ketones by alcohols is reported for the first time. Irradiation of benzophenone, benzhydrol and SWNTs in benzene resulted in covalent attachment of benzhydrol to the sidewalls of the SWNTs. A variety of tools were used to characterize the functionalized SWNTs. Raman scattering, UV-visible and near-IR spectroscopy confirm the covalent nature of the sidewall functionalization. Attenuated total reflection (ATR) FTIR and NMR provided evidence for attachment of benzhydrol onto the sidewalls of nanotubes. Thermogravimetric analysis (TGA) showed that the degree of functionalization was about one benzhydrol in 52 sidewall carbons. A long-chain hydrocarbon marker (n-C(18)H(35)) was also grafted onto the functional groups by esterification reaction for high-resolution TEM (HRTEM) visualization. PMID:20442484

  20. Covalent sidewall functionalization of single-walled carbon nanotubes: a photoreduction approach

    International Nuclear Information System (INIS)

    Covalent sidewall functionalization of single-walled carbon nanotubes (SWNTs) via photoreduction of aromatic ketones by alcohols is reported for the first time. Irradiation of benzophenone, benzhydrol and SWNTs in benzene resulted in covalent attachment of benzhydrol to the sidewalls of the SWNTs. A variety of tools were used to characterize the functionalized SWNTs. Raman scattering, UV-visible and near-IR spectroscopy confirm the covalent nature of the sidewall functionalization. Attenuated total reflection (ATR) FTIR and NMR provided evidence for attachment of benzhydrol onto the sidewalls of nanotubes. Thermogravimetric analysis (TGA) showed that the degree of functionalization was about one benzhydrol in 52 sidewall carbons. A long-chain hydrocarbon marker (n-C18H35) was also grafted onto the functional groups by esterification reaction for high-resolution TEM (HRTEM) visualization

  1. Synthetic studies of coumarin derivatives from o-hydroxybenzophenones with phenylacetic acid and acetic anhydride

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Soon Hee; Yang, Sung Yun [Ewha Womans Univ., Seoul (Korea, Republic of)

    1999-02-01

    The 8 coumarin derivatives have been synthesized from 8 starting materials(2-hydroxy-benzophenone, 2,2'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-5-methylbenzophenone, 5-chloro-2-hydroxy-4-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-4'-dimethoxybenzophenone) with phenylacetic acid and Ac{sub 2}O/TEA in acetone at reflux temperature. The ratio of o-hydroxybenzophenone, phenylacetic acid, Ac{sub 2}O and TEA is 1:1:8:8 in acetone. Our results showed higher products yields of coumarin derivatives than Shama and Ray's method in previous papers. A new intermediate form was proposed to our mechanism of coumarin synthetic method.

  2. Process optimization of a thermoplastic polyimidesulphone

    Science.gov (United States)

    Dezern, J. F.; Young, P. R.

    1985-01-01

    The detailed characterization of an experimental thermoplastic polyimidesulfane adhesive based on 3,3 prime-diaminodiphenylsulfone and 3,3 prime,4,4 prime-benzophenone tetracarboxylic dianhydride was studied. Model compounds were also examined. Thermal cyclization of the amide-acid to the imide was studied by a variety of techniques including DSC, TGA, MS, in situ diffuse reflectance-FTIR, and flow measurement. Characterizations were continued during the processing of adhesive tapes and the fabrication, bonding, and testing of lap shear specimens. Results provide fundamental insights into the role of cure chemistry, and the effects of residual solvent and volatile produces on processing and performance. These insights and the resulting chemical models should lead to more efficient processing cycles for these and other related thermoplastic adhesive systems.

  3. Kinetic Isotope Effects in the Reduction of Methyl Iodide

    DEFF Research Database (Denmark)

    Holm, Torkil

    1999-01-01

    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...... 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...

  4. Hidrogenação eletrocatalítica de substratos orgânicos utilizando eletrodos modificados poliméricos contendo partículas de Ni/Pd e Ni/Pt Electrocatalytic hydrogenation of organic substrates on polymer modified electrodes embedding Ni/Pd and Ni/Pt particles

    Directory of Open Access Journals (Sweden)

    Fabiana L. S. Purgato

    2009-01-01

    Full Text Available Novel modified electrodes bearing dispersed Pd and Pt particles have been prepared from poly (allyl ether of the p-benzenesulfonic acid films with incorporated nickel particles making use of galvanic displacement reactions. The SEM analysis of the new modified electrodes revealed efficient deposition of Pd but weak up-take of Pt. Electrocatalytic hydrogenation of several classes of organic substrates were carried out using the MEs Ni, Ni/Pd and Ni/Pt. The Ni/Pd ME showed to be the best of them for the hydrogenation of double, triple and carbonyl bonds. The complete hydrogenation of the aromatic rings for the well-adsorbed substrates acetophenone and benzophenone is noteworthy.

  5. Photocrosslinking and click chemistry enable the specific detection of proteins interacting with phospholipids at the membrane interface.

    Science.gov (United States)

    Gubbens, Jacob; Ruijter, Eelco; de Fays, Laurence E V; Damen, J Mirjam A; de Kruijff, Ben; Slijper, Monique; Rijkers, Dirk T S; Liskamp, Rob M J; de Kroon, Anton I P M

    2009-01-30

    New lipid analogs mimicking the abundant membrane phospholipid phosphatidylcholine were developed to photocrosslink proteins interacting with phospholipid headgroups at the membrane interface. In addition to either a phenylazide or benzophenone photoactivatable moiety attached to the headgroup, the lipid analogs contained azides attached as baits to the acyl chains. After photocrosslinking in situ in the biomembrane, these baits were used for the attachment of a fluorescent tetramethylrhodamine-alkyne conjugate or a biotin-alkyne conjugate using click chemistry, allowing for the selective detection and purification of crosslink products, respectively. Proteins crosslinked to the lipid analogs in inner mitochondrial membranes from Saccharomyces cerevisiae were detected and subsequently identified by mass spectrometry. Established interaction partners of phosphatidylcholine were found, as well as known integral and peripheral inner membrane proteins, and proteins that were not previously considered mitochondrial inner membrane proteins. PMID:19171301

  6. Barbituric acid as a substituent at aryl methylium ions.

    Science.gov (United States)

    Spange, Stefan; Bauer, Mirko; Walfort, Bernhard; Lang, Heinrich

    2006-09-29

    Activation of different benzophenone derivatives with triflic anhydride for electrophilic aromatic substitution of 5-phenylbarbituric acids leads to regioselective formation of the ortho-substituted product. The resulting triphenylmethylium salt can be isolated when the Michlers ketone is used. More electrophilic cations form cyclic enol ethers such as 1-n-butyl-9,9-diaryl-1,9-dihydro-10-oxa-1,3-diazaphenanthrene-2,4-diones. Alternatively, supramolecular complex formation with 2,6-diacetamido pyridine as well as carbenium ion generation have been studied. Although in dilute acid only protonation of one of the carbonyl oxygens occurs, ring opening of the cyclic enol ether toward the carbenium ion is observed in 96% sulfuric acid. PMID:16995696

  7. Garcinol inhibits cell proliferation and promotes apoptosis in pancreatic adenocarcinoma cells.

    Science.gov (United States)

    Parasramka, Mansi A; Gupta, Smiti V

    2011-01-01

    Garcinol, or polyisoprenylated benzophenone, isolated from the rind of fruiting bodies of Garcinia indica, has been used in traditional medicine for its potential antiinflammatory and antioxidant properties. The objective of this study was to investigate the effect of garcinol on pancreatic cancer (PaCa) cell viability and proliferation. For this, 2 human PaCa cell lines, BxPC-3 and Panc-1, with wild and mutant k-ras, respectively, were treated with garcinol (0-40 μM). Garcinol significantly (P garcinol's action on PaCa cells was investigated by targeting signaling moieties involved in apoptosis (X-IAP, cIAP, caspase-3, 9, and PARP cleavage), transcription factor NF-κB, believed to contribute toward a chemoresistance phenotype in pancreatic tumors, and molecules associated with neovascularization and metastasis (MMP-9, VEGF, IL-8, and PGE(2)). Garcinol significantly (P garcinol in PaCa. Further studies are warranted, based on our findings. PMID:21462088

  8. Potential role of garcinol as an anticancer agent.

    Science.gov (United States)

    Saadat, Nadia; Gupta, Smiti V

    2012-01-01

    Garcinol, a polyisoprenylated benzophenone, is extracted from the rind of the fruit of Garcinia indica, a plant found extensively in tropical regions. Although the fruit has been consumed traditionally over centuries, its biological activities, specifically its anticancer potential is a result of recent scientific investigations. The anticarcinogenic properties of garcinol appear to be moderated via its antioxidative, anti-inflammatory, antiangiogenic, and proapoptotic activities. In addition, garcinol displays effective epigenetic influence by inhibiting histone acetyltransferases (HAT 300) and by possible posttranscriptional modulation by mi RNA profiles involved in carcinogenesis. In vitro as well as some in vivo studies have shown the potential of this compound against several cancers types including breast, colon, pancreatic, and leukemia. Although this is a promising molecule in terms of its anticancer properties, investigations in relevant animal models, and subsequent human trials are warranted in order to fully appreciate and confirm its chemopreventative and/or therapeutic potential. PMID:22745638

  9. The characteristics of organic matter from the Triassic clays of NW margin of the Holy Cross Mts (Poland — preliminary report

    Directory of Open Access Journals (Sweden)

    Leszek Marynowski

    2006-01-01

    Full Text Available The molecular character of organic matter in Triassic clays on the NW border of the Holy Cross Mts was determined in apolar, aromatic and polar fractions of extractable organic matter (OM using GC-MS analysis. The contribution of terrestrial higher plants to the kerogene is revealed by the dominant presence of odd long-chain n-alkanes and by the occurrence of retene. Benzophenone, fluorenone, cyclopenta(defphenanthrenone, antracenone and benzanthrone were among the compounds identified in polar fractions of the soluble organic matter. These commonly originate during strong oxidation of sedimentary organic matter. The aromatic fraction is characterised by the presence of phenyl derivatives (PhPAC such as phenylnaphthalenes, terphenyls, phenyldibenzofurans and phenylphenanthrenes that are also products of the abiotic oxidation of organic matter. The oxidation processes that occurred during sedimentation and during early diagenesis resulted in a very significant decrease in the organic matter content in the clays. This decrease considerably influences their technological properties.

  10. A study of factors affecting the persistence of deltamethrin applied to cotton fabric for tsetse fly control

    International Nuclear Information System (INIS)

    The effect of selected lipohilic materials on the loss of deltamethrin applied to cotton fabric and washed with water was studied. Corn oil, paraffin, linseed oil and silicone oil reduced the leaching of deltamethrin by water from the fabric. The cumulative sum of four washings of the treated cotton strips resulted in a total loss of 37.7% of deltamethrin from the cotton strip (without protectant) and 9.9% from the strip treated with deltamethrin and corn oil. The effect of the colour of fabric and a UV absorber compound on the photodegradation of deltamethrin were also studied. Photodegradation was much less on the blue or black fabric than on the white fabric, and 2, 4-dihydroxy-benzophenone reduced the photodegradation of deltamethrin applied to cotton fabric. (author). 10 refs, 4 figs, 1 tab

  11. Facile Photoimmobilization of Proteins onto Low-Binding PEG-Coated Polymer Surfaces

    DEFF Research Database (Denmark)

    Larsen, Esben Kjær Unmack; Mikkelsen, Morten Bo Lindholm; Larsen, Niels Bent

    2014-01-01

    Immobilization of proteins onto polymer surfaces usually requires specific reactive functional groups. Here, we show an easy one-step method to conjugate protein covalently onto almost any polymer surface, including low protein-binding poly(ethylene glycol) (PEG), without the requirement for the...... surface areas, showing ng/mL sensitivity to a cytokine antigen target. Moreover, spatially patterned attachment of fluorescently labeled protein onto the low-binding PEG-coated surface was achieved with a projection lithography system that enabled the creation of micrometer-sized protein features....... presence of specific functional groups. Several types of proteins, including alkaline phosphatase, bovine serum albumin, and polyclonal antibodies, were photoimmobilized onto a PEG-coated polymer surface using a water-soluble benzophenone as photosensitizer. Protein functionality after immobilization was...

  12. Solid-State and Solution Structures of Glycinimine-Derived Lithium Enolates.

    Science.gov (United States)

    Jin, Kyoung Joo; Collum, David B

    2015-11-18

    A combination of crystallographic, spectroscopic, and computational studies was applied to study the structures of lithium enolates derived from glycinimines of benzophenone and (+)-camphor. The solvents examined included toluene and toluene containing various concentrations of tetrahydrofuran, N,N,N',N'-tetramethylethylenediamine (TMEDA), (R,R)-N,N,N',N'-tetramethylcyclohexanediamine [(R,R)-TMCDA], and (S,S)-N,N,N',N'-tetramethylcyclohexanediamine [(S,S)-TMCDA]. Crystal structures show chelated monomers, symmetric disolvated dimers, S4-symmetric tetramers, and both S6- and D3d-symmetric hexamers. (6)Li NMR spectroscopic studies in conjunction with the method of continuous variations show how these species distribute in solution. Density functional theory computations offer insights into experimentally elusive details. PMID:26554898

  13. 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.

  14. 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

    2016-01-01

    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. PMID:27527194

  15. Synthesis and characterization of polymerizable one-component photoinitiator based on sesamol.

    Science.gov (United States)

    Yang, Jinliang; Tang, Ruifen; Shi, Suqing; Nie, Jun

    2013-05-01

    Migration stability and biocompatibility are the crucial features for a photoinitiator or coinitiator used in UV curable formulations, especially when the cured product is in direct contact with food or human skin. To reduce the migration issues and increase the biocompatibility, a polymerizable one-component photoinitiator, 1-(1,3-benzodioxol-5-yloxy)-3-(4-benzoylphenoxy)propan-2-yl acrylate (BDOBPAc), based on sesamol and benzophenone has been synthesized. The photopolymerization induced by BDOBPAc was monitored by real-time infrared spectroscopy. The rate of decomposition and the migration stability of photoinitiators were studied by UV-Vis spectroscopy. The results showed that BDOBPAc is an effective free radical photoinitiator with good migration stability, which has great potential to be widely used in the food packing or biomedical fields. PMID:23479096

  16. Deuterium labeling studies in the transfer hydrogenation of ketones and in the disproportionation of diphenylcarbinol over alumina

    International Nuclear Information System (INIS)

    Paper describes deuterium labeling studies which confirm the direct hydrogen transfer mechanism for the transfer hydrogenation of ketones as well as for the disproportionation and the transfer hydrogenolysis of diphenylcarbinol. Methods for the preparation of diphenylcarbinol-d and 2-propanol-2-d are described. Diphenylmethane-d and diphenylmethane-d2 were prepared as standards for product identification purposes. 2-Propanol-2-d of 92% isotopic purity was used to reduce 4-methyl-2-pentanone and cyclohexanone over 2.2% Na+/Al2O3 at 3000C. Reaction products were 4-methyl-2-pentanol and cyclohexanol. Disproportionation of diphenylcarbinol produced diphenylamine, benzophenone, and water, over pure alumina at 3000C. Reaction products were analyzed by gas chromatography, and pure samples were isolated by preparative gas chromatography. Isotopic purities were estimated by ir, NMR, and mass spectrometry. A somewhat speculative representation of the direct hybrid transfer mechanism is considered

  17. Photoclickable dendritic molecular glue: noncovalent-to-covalent photochemical transformation of protein hybrids.

    Science.gov (United States)

    Uchida, Noriyuki; Okuro, Kou; Niitani, Yamato; Ling, Xiao; Ariga, Takayuki; Tomishige, Michio; Aida, Takuzo

    2013-03-27

    A water-soluble dendron with a fluorescein isothiocyanate (FITC) fluorescent label and bearing nine pendant guanidinium ion (Gu(+))/benzophenone (BP) pairs at its periphery (Glue(BP)-FITC) serves as a "photoclickable molecular glue". By multivalent salt-bridge formation between Gu(+) ions and oxyanions, Glue(BP)-FITC temporarily adheres to a kinesin/microtubule hybrid. Upon subsequent exposure to UV light, this noncovalent binding is made permanent via a cross-linking reaction mediated by carbon radicals derived from the photoexcited BP units. This temporal-to-permanent transformation by light occurs quickly and efficiently in this preorganized state, allowing the movements of microtubules on a kinesin-coated glass plate to be photochemically controlled. A fundamental difference between such temporal and permanent bindings was visualized by the use of "optical tweezers". PMID:23477460

  18. N-(二苯基亚甲基)甘氨酸叔丁基酯的合成%Synthesis of N-(diphenylmethylene)Glycine Tert-Butyl Ester

    Institute of Scientific and Technical Information of China (English)

    聂友松; 钟敏; 李航; 贺贤然

    2015-01-01

    The N-(diphenylmethylene)glycine tert-butyl ester has been accomplished in 4 steps from phthalic anhydride and glycine with good yield. The last step in this approach is a condensation reaction of benzophenone with glycine tert-butyl ester using the Iron (III) chloride hexahydrate as a catalyst , which is a convenient synthetic method.%N-(二苯基亚甲基)甘氨酸叔丁基酯可由邻苯二甲酸酐和甘氨酸分4个步骤制得,且产率可观。此方法的最后一步是二苯甲酮与甘氨酸叔丁酯的缩合反应,以氯化铁六水合物为催化剂,该合成方法方便可行。

  19. Techniques for the Improvement of Plastics by Ultra-Violet Light

    International Nuclear Information System (INIS)

    The use of ultraviolet light for crosslinking and surface grafting of polymers is described. It is pointed out that the energy emission from a small ultra- violet lamp is at least as great as that from a large accelerating machine and that that therefore the cost of irradiation using ultraviolet light should be quite low. The polymers are sensitised by the addition of certain carbonyl compounds such as benzophenone. It is found that the crosslinking of polyethylene in the presence of sensitisers gives a material having greatly improved tensile strength at elevated temperatures. Surface grafting of polyethylene with acrylamide was also carried out. The advantages of the technique lie in cost, speed and safety although lack of penetration may limit its use to thin films. (author)

  20. Rhomboidal [Cu4] coordination cluster from self-assembly of two asymmetric phenoxido-bridged Cu2 units: Role of 1,1-azido clips

    Indian Academy of Sciences (India)

    Avijit Sarkar; Aloke Kumar Ghosh; Moumita Pait; Haridas Mandal; Tufan Singha Mahapatra; Biswajit Sharangi; Mrinal Sarkar; Debashis Ray

    2012-11-01

    The coordination cluster [Cu2(-OMe)(1,1-N3)(-bcp)(N3)]2 (1; Hbcp = 2,6-bis(2-benzoyl-4-chloro-phenylimino)-methyl)-4-methylphenol, forming a new member within the rapidly growing family of Cu4 cluster complexes, has been synthesized and structurally characterized by X-ray crystallography. The complex crystallizes in the monoclinic system, space group P21/, with unit cell parameters a = 14.620(7) Å, b = 17.923(8) Å, c = 15.008(7) Å, = 115.815(14)° and Z = 2. It is the first example of a rhomboidal [Cu4] compound formed from 1,1-azido clipping of two methoxido bridged [Cu2] complexes showing asymmetric coordination from benzophenone oxygen atoms and terminal azido groups.

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

    International Nuclear Information System (INIS)

    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 I212121, 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

  2. Photo- or EB-induced cross-linking reaction of the polymers containing pendant epoxide or vinyl ether groups from glycidyl vinyl ether

    International Nuclear Information System (INIS)

    Polymers containing pendant epoxide or vinyl ether groups were synthesized by radical copolymerization of glycidyl vinyl ether (GVE) with N-phenylmaleimide (NPM) and N-phenoxycarbonyloxymaleimide (NPCM), or by ring-opening alternating copolymerization of GVE with phthalic anhydride (PAn). In the photo-induced cross-linking reaction, the pendant vinyl ether groups in poly(GVE-PAn) showed higher reactivity than the pendant epoxide groups in poly(GVE-NPM), and poly(GVE-PAn) was readily cross-linked by various dithiols with or without benzophenone. In the electron beam (EB)-induced cross-linking reaction, the sensitivity of poly(GVE-NPCM), which has pendant epoxide and carbonate groups, was higher than that of poly(GVE-NPM) containing only pendant epoxide groups. Furthermore, the EB-sensitivity of poly(GVE-PAn) was even higher than that of poly(GVE-NPM) or poly(GVE-NPCM). (author)

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

    Directory of Open Access Journals (Sweden)

    Gilberto Silva-López,

    2012-01-01

    Full Text Available 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, docosane, triacontane, sitosterol, hexadecanoic acid, 1-eicosanol, chlorobenzene, and phosphorothioic acid trimethyl ester. Literature review showed a lack of data on the compounds´ potential effects on wildlife, although some of them could be considered harmful to the otters and their prey. The different compounds detected needs follow-up.

  4. 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

  5. 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.

  6. 具有光引发活性腰果酚衍生物的合成及其UV固化%Synthesis and UV Curing Properties of a Photo-active Cardanol Derivative

    Institute of Scientific and Technical Information of China (English)

    程传杰; 查吉伟; 刘忠彬; 申亮; 孙剑; 刘英佳

    2012-01-01

    A cardanol derivative (1) with photo-initiating activity has been synthesized in 86% yield using cardanol and 4-bromomethyl benzophenone as precursors. The photo-initiating performance of the derivative 1 is better than common benzophenone according to the results of the controlled experiments. The derivative 1 can be completely cured within 30 s under UV irradiation without the presence of any photoinitiator. Furthermore, the mixtures of the derivative 1 and cardanol with various ratios can also be cured under UV irradiation that the UV-curing time is prolonged up to dozens of minutes with the increase of cardanol content. The resulting cured films show relatively high hardness(3H-5H) , excellent solvent, acid and base resistance, which have potential application in anti-corrosion coatings.%以腰果酚与4-溴甲基二苯甲酮为原料,合成了具有光引发活性的腰果酚衍生物,收率86%.该衍生物的光引发活性优于普通的二苯甲酮.在不加其它光引发剂的情况下,UV光照30 s该液体衍生物即可固化.该衍生物与腰果酚不同比例的混合物,也可进行UV固化,腰果酚含量越高,所需固化时间越长.膜的硬度为3H-5H,且具有较好的耐溶剂与耐酸碱性能,可望用于防腐漆中.

  7. Surface modification of poly(ethylene terephthalate) fabric via photo-chemical reaction of dimethylaminopropyl methacrylamide

    International Nuclear Information System (INIS)

    Highlights: ► PET fibers were UV-grafted with dimethylaminopropyl methacrylamide (DMAPMA). ► The graft yield could be controlled by irradiation time and monomer concentration. ► The tertiary amino groups of the grafted PDMAPMA were quaternized with alkyl bromides. ► The quaternization reaction had a high yield, when bromides with shorter alkyl chain were employed. ► The antimicrobial effect was highest, when samples were quaternized with 1-bromohexane and 1-bromooctane. - Abstract: Photo-chemical reactions and surface modifications of poly(ethylene terephthalate) (PET) fabrics with the monomer dimethylaminopropyl methacrylamide (DMAPMA) and benzophenone (BP) as photo-initiator using a broad-band UV lamp source were investigated. The tertiary amino groups of the grafted poly(DMAPMA) chains were subsequently quaternized with alkyl bromides of different chain lengths to establish antibacterial activity. The surface composition, structure and morphology of modified PET fabrics were characterized by Fourier transform infrared spectroscopy (FTIR/ATR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). To evaluate the amount of quaternary and tertiary ammonium groups on the modified surface, PET was dyed with an acid dye which binds to the ammonium groups. Therefore, the color depth is a direct indicator of the amount of ammonium groups. The resulting antibacterial activity of the modified PET fabrics was tested with Escherichia coli. The results of all experiments show that a photochemical modification of PET is possible using DMAPMA, benzophenone and UV light. Also, the quaternization of tertiary amino groups as well as the increase in antibacterial activity of the modified PET by the established quaternary ammonium groups were successful.

  8. Occurrence, fate and ecotoxicological risk of personal care products in urban river-groundwater interface

    Science.gov (United States)

    Jurado, Anna; Pau Serra, Maria; Díaz-Cruz, M. Silvia; Vázquez-Suñé, Enric; Pujades, Estanislao; Barceló, Damià

    2016-04-01

    This work presents the occurrence and fate of selected personal care products (PCPs) in the urban river-groundwater interface. To this end, urban groundwater and river samples were collected in Sant Adrià del Besòs (NE of Spain) and a total of 16 PCPs were analyzed including benzophenone derivatives, camphor derivatives, p-aminobenzoic acid derivatives, triazoles and parabens in three different campaigns (from May 2010 to July 2014). These compounds reach the aquifer through the recharge of River Besòs that receives large amounts of effluents from waste water treatment plants. Results shown that most of compounds were not or barely detected (maximum concentrations around 30 ng/L) in groundwater samples during the different sampling campaigns. Only two triazoles, named as benzotriazole (BZT) and methyl benzotriazol (MeBZT) were found at high concentrations in groundwater samples (maximum concentration around 2000 ng/L). The fate of PCPs in the aquifer was assessed using mixing analysis considering the temporal variability of the River Besòs. Overall, measured groundwater concentrations were significantly much lower than those estimated by the mixing of the river water. This observation suggested that most of the PCPs are naturally removed when river water infiltrates the aquifer. However, some compounds were more persistent in the aquifer. These compounds were in descending order: the triazoles MeBZT and BZT followed by the camphor derivative 4MBC. The measured concentrations allowed us to assess the environmental risk posed by the selected UV-Fs (e.g. benzophenone derivatives) in the river-groundwater samples. Hazard Quotients (HQs) for diferent aquatic species were calculated in order to characterise the ecotoxicity potential of the studied compounds in the river-groundwater interface. HQ values will be presented and discussed in the presentation.

  9. Cross-Linking Cellulosic Fibers with Photoreactive Polymers: Visualization with Confocal Raman and Fluorescence Microscopy.

    Science.gov (United States)

    Janko, Marek; Jocher, Michael; Boehm, Alexander; Babel, Laura; Bump, Steven; Biesalski, Markus; Meckel, Tobias; Stark, Robert W

    2015-07-13

    The properties of paper sheets can be tuned by adjusting the surface or bulk chemistry using functional polymers that are applied during (online) or after (offline) papermaking processes. In particular, polymers are widely used to enhance the mechanical strength of the wet state of paper sheets. However, the mechanical strength depends not only on the chemical nature of the polymeric additives but also on the distribution of the polymer on and in the lignocellulosic paper. Here, we analyze the photochemical attachment and distribution of hydrophilic polydimethylacrylamide-co-methacrylate-benzophenone P(DMAA-co-MABP) copolymers with defined amounts of photoreactive benzophenone moieties in model paper sheets. Raman microscopy was used for the unambiguous identification of P(DMAA-co-MABP) and cellulose specific bands and thus the copolymer distribution within the cellulose matrix. Two-dimensional Raman spectral maps at the intersections of overlapping cellulose fibers document that the macromolecules only partially surround the cellulose fibers, favor to attach to the fiber surface, and connect the cellulose fibers at crossings. Moreover, the copolymer appears to accumulate preferentially in holes, vacancies, and dips on the cellulose fiber surface. Correlative brightfield, Raman, and confocal laser scanning microscopy finally reveal a reticular three-dimensional distribution of the polymer and show that the polymer is predominately deposited in regions of high capillarity (i.e., in proximity to fine cellulose fibrils). These data provide deeper insights into the effects of paper functionalization with a copolymer and aid in understanding how these agents ultimately influence the local and overall properties of paper. PMID:26101966

  10. Determining ultraviolet absorbents in sunscreen products by combining direct injection with micelle collapse on-line preconcentration capillary electrophoresis.

    Science.gov (United States)

    Hsiao, Wen-Yao; Jiang, Shiuh-Jen; Feng, Chia-Hsien; Wang, Shih-Wei; Chen, Yen-Ling

    2015-02-27

    The on-line preconcentration technique of analyte focusing by micelle collapse-micellar electrokinetic chromatography (AFMC-MEKC) was combined with direct injection without extraction to determine ultraviolet absorbents in sunscreen products. The stacking mechanism is based on the transport, release, and accumulation of analytes bound to micelle carriers that are collapsed into the micelle dilution zone. The following optimized conditions were determined: the running buffer was 10mM Tris buffer (pH 9.5) containing 60mM SDS, 7mM γ-CD and 20% ethanol; the SDS concentration was required to be slightly above the critical micelle concentration (cmc) value (7.4mM) in the sample matrix, which allowed the micelle dilution zone to form when voltage was applied; and finally, the sample was prepared in 100mM Tris buffer (pH 9.0) containing 7.5mM SDS and 20% (v/v) ethanol to provide sufficient resolution and to improve the sensitivity. Samples were injected at 0.5psi for 40s, and the separation voltage was set at 15kV for first 15min and then increased to 23kV to decrease the analysis time. The detection sensitivity for ultraviolet absorbents was enhanced by approximately 41-fold using AFMC-MEKC compared to conventional MEKC. The limit of detection (S/N=3) was 98nM for benzophenone-2 and benzophenone-4. The correlation of the regression curve was greater than 0.995. The relative error and relative standard deviation were lower than 9.94% with high precision and accuracy. The recoveries of nine ultraviolet absorbents in a homemade emulsion were between 95.08% and 104.57%. After optimization and validation, this AFMC-MEKC method combined with direct injection is considered to be established and successfully applicable to commercial sunscreen products. PMID:25637009

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

    International Nuclear Information System (INIS)

    Part I of this dissertation is a study of the magnetic isotope effect, and results are presented for the separation of 13C and 12C 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. 13C 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

  12. 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. PMID:26965011

  13. A Multimedia Fate Model to Support Chemical Management in China: A Case Study for Selected Trace Organics.

    Science.gov (United States)

    Zhu, Ying; Price, Oliver R; Kilgallon, John; Rendal, Cecilie; Tao, Shu; Jones, Kevin C; Sweetman, Andrew J

    2016-07-01

    SESAMe v3.3, a spatially explicit multimedia fate model for China, is a tool suggested to support quantitative risk assessment for national scale chemical management. The key advantage over the previous version SESAMe v3.0 is consideration of spatially varied environmental pH. We evaluate the model performance using estimates of emission from total industry usage of three UV filters (benzophenone-3, octocrylene, and octyl methoxycinnamate) and three antimicrobials (triclosan, triclocarban, and climbazole). The model generally performs well for the six case study chemicals as shown by the comparison between predictions and measurements. The importance of accounting for chemical ionization is demonstrated with the fate and partitioning of both triclosan and climbazole sensitivity to environmental pH. The model predicts ionizable chemicals (triclosan, climbazole, benzophenone-3) to primarily partition into soils at steady state, despite hypothetically only being released to freshwaters, as a result of agricultural irrigation by freshwater. However, further model calibration is needed when more field data becomes available for soils and sediments and for larger areas of water. As an example, accounting for the effect of pH in the environmental risk assessment of triclosan, limited freshwater areas (0.03% or ca. 55 km(2)) in mainland China are modeled to exceed its conservative environmental no-effect threshold. SESAMe v3.3 can be used to support the development of chemical risk assessment methodologies with the spatial aspects of the model providing a guide to the identification regions of interest in which to focus monitoring campaigns or develop a refined risk assessment. PMID:27280340

  14. 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. PMID:25008406

  15. 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)

    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.

  16. Ketoprofen removal by O3 and O3/UV processes: Kinetics, transformation products and ecotoxicity

    International Nuclear Information System (INIS)

    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. - Highlights: • Ketoprofen degradation is significantly faster using O3/UV compared to ozonation. • The presence of O3 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

  17. 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.

  18. Analysis of real-time mixture cytotoxicity data following repeated exposure using BK/TD models.

    Science.gov (United States)

    Teng, S; Tebby, C; Barcellini-Couget, S; De Sousa, G; Brochot, C; Rahmani, R; Pery, A R R

    2016-08-15

    Cosmetic products generally consist of multiple ingredients. Thus, cosmetic risk assessment has to deal with mixture toxicity on a long-term scale which means it has to be assessed in the context of repeated exposure. Given that animal testing has been banned for cosmetics risk assessment, in vitro assays allowing long-term repeated exposure and adapted for in vitro - in vivo extrapolation need to be developed. However, most in vitro tests only assess short-term effects and consider static endpoints which hinder extrapolation to realistic human exposure scenarios where concentration in target organs is varies over time. Thanks to impedance metrics, real-time cell viability monitoring for repeated exposure has become possible. We recently constructed biokinetic/toxicodynamic models (BK/TD) to analyze such data (Teng et al., 2015) for three hepatotoxic cosmetic ingredients: coumarin, isoeugenol and benzophenone-2. In the present study, we aim to apply these models to analyze the dynamics of mixture impedance data using the concepts of concentration addition and independent action. Metabolic interactions between the mixture components were investigated, characterized and implemented in the models, as they impacted the actual cellular exposure. Indeed, cellular metabolism following mixture exposure induced a quick disappearance of the compounds from the exposure system. We showed that isoeugenol substantially decreased the metabolism of benzophenone-2, reducing the disappearance of this compound and enhancing its in vitro toxicity. Apart from this metabolic interaction, no mixtures showed any interaction, and all binary mixtures were successfully modeled by at least one model based on exposure to the individual compounds. PMID:27317371

  19. 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.

  20. 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

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

    International Nuclear Information System (INIS)

    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 60Co 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 IC50 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 IC50 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 kGy is

  2. 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. PMID:24913857

  3. Antitumor Activity of Garcinol in Human Prostate Cancer Cells and Xenograft Mice.

    Science.gov (United States)

    Wang, Yu; Tsai, Mei-Ling; Chiou, Li-Yu; Ho, Chi-Tang; Pan, Min-Hsiung

    2015-10-21

    Garcinol, which is isolated from fruit rinds of Garcinia indica, is a polyisoprenylated benzophenone. It has been studied for its antitumor activity by inducing apoptosis and inhibiting autophagy in human prostate cancer cells. The Bax/Bcl-2 ratio increased when garcinol was applied to PC-3 cells indicating a presence of apoptosis. Meanwhile, procaspases-9 and -3 were suppressed with attenuating PARP and DFF-45. Autophagy was inhibited through activating p-mTOR and p-PI3 Kinase/AKT by garcinol, which as a result induced the cells to apoptosis directly. In addition, the apoptosis effect of garcinol in a xenograft mouse model was also tested, suggesting a consistent result with PC-3 cell model. The tumor size was reduced more than 80 percent after the mouse accepted the garcinol treatment. Garcinol was demonstrated to have a strong antitumor activity through inhibiting autophagy and inducing apoptosis, which was discovered for the first time. Based on these findings, our data suggests that garcinol deserves further investigation as a potent chemopreventive agent. PMID:26442822

  4. Phytochemical analysis and antioxidant potential of the leaves of Garcinia travancorica Bedd.

    Science.gov (United States)

    Aravind, A P Anu; Asha, K R T; Rameshkumar, K B

    2016-01-01

    Phytochemical analysis of the leaves of Garcinia travancorica, a hitherto uninvestigated endemic species to the Western Ghats of south India, resulted in isolation and characterisation of the polyisoprenylated benzophenones 7-epi-nemorosone (1) and garcinol (2) along with biflavonoids GB-1a (3), GB-1 (4), GB-2 (5), morelloflavone (6) and morelloflavone-7″-O-β-D-glycoside or fukugiside (7). The compounds were identified using various spectroscopic techniques, mainly through NMR and MS. The methanol extract and the biflavonoids 3, 4, 5 and 7 showed potential in vitro antioxidant activities. The IC50 value of the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activity of compound 7 was 8.34 ± 2.12 μg/mL, comparable to that of standard ascorbic acid (3.2 ± 0.50 μg/mL). In the superoxide radical scavenging assay, compound 7 gave IC50 value of 6.95 ± 1.33 μg/mL close to standard ascorbic acid with IC50 value of 5.8 ± 0.25 μg/mL. Validated HPTLC estimation revealed G. travancorica as a rich source of morelloflavone-7″-O-β-D-glycoside (7.12% dry wt. leaves). PMID:25982126

  5. Garcinol inhibits tumour cell proliferation, angiogenesis, cell cycle progression and induces apoptosis via NF-κB inhibition in oral cancer.

    Science.gov (United States)

    Aggarwal, Sadhna; Das, Satya N

    2016-06-01

    Garcinol, a polyisoprenylated benzophenone is extracted from the rind of the fruit of Garcinia indica, a plant found extensively in tropical regions. Its ability to inhibit tumour growth has been demonstrated in certain cancers. In this study, we evaluated the potential anti-tumour effects of garcinol on oral squamous cell carcinoma (OSCC) cells. Three OSCC cell lines (SCC-4, SCC-9 and SCC-25) were treated with garcinol for 48 h and its effect on growth and proliferation, clonogenic survival, cell cycle and apoptosis was studied by MTT, clonogenic assay, propidium iodide (PI) staining and annexin-V binding assay, respectively. The alteration in expression of NF-κB and COX-2 was studied by western blot analysis and that of VEGF by ELISA. Garcinol treatment significantly (p < 0.001) inhibited the growth and proliferation and colony formation of OSCC cells with a concomitant induction of apoptosis and cell cycle arrest. It did not show toxic effect on normal cells. It significantly (p < 0.05) reduced the expression of NK-κB and COX-2 expression in treated cells as compared to untreated controls besides inhibiting VEGF expression. It appears that garcinol exerts anti-proliferative, pro-apoptotic, cell-cycle regulatory and anti-angiogenic effects on oral cancer cells through inhibition of NF-κB and COX-2. Thus, garcinol may be developed as a potential chemopreventive and/or chemotherapeutic agent for treatment of oral squamous cell carcinoma. PMID:26662963

  6. 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.

  7. Structural and catalytic properties of a novel vanadium containing solid core mesoporous silica shell catalysts for gas phase oxidation reaction

    Indian Academy of Sciences (India)

    N Venkatathri; Vijayamohanan K Pillai; A Rajini; M Nooka Raju; I A K Reddy

    2013-01-01

    A novel vanadium containing solid core mesoporous silica shell catalyst was synthesized with different Si/V ratios by sol-gel method under neutral conditions. The synthesized materials were characterized by various techniques and gas phase diphenyl methane oxidation reaction. The mesoporosity combined with microporosity are formed by incorporation of octadecyltrichloro silane and triethylamine in the catalyst and it was found out from E-DAX and BET—surface area analysis. The material was found to be nanocrystalline. Vanadium is present as V4+ species in as-synthesized samples and convert to V5+ on calcination. Most of the vanadium is present in tetrahedral or square pyramidal environment. Incorporation of vanadium in silica framework was confirmed by 29Si MAS NMR analysis. Among the various vanadium containing solid core mesoporous silica shell catalysts, the Si/V =100 ratio exhibited maximum efficiency towards diphenyl methane to benzophenone gas phase reaction. The optimum condition required for maximum conversion and selectivity was found out from the catalytic studies.

  8. Gamma radiolytic eradication of methoxychlor in aqueous media. The degradation pathways using HPLC and SPME-GC-MS

    Energy Technology Data Exchange (ETDEWEB)

    Butt, S.B.; Zafar, A. [PINSTECH, Nilore, Islamabad (Pakistan). Central Analytical Facility Div.; Riaz, M. [PINSTECH, Nilore, Islamabad (Pakistan). Chemistry Div.

    2013-08-01

    The gamma radiation-induced degradation of environmental pollutant methoxychlor in water was investigated. A {sup 60}Co gamma radiation source with a dose rate of 372 Gy h{sup -1} was used for gamma irradiation of 1 mg L{sup -1} and 10 mg L{sup -1} methoxychlor in water with a varied absorbed dose of 1-5 kGy. A single step clean up and pre-concentration procedure based on solid phase micro-extraction was optimized. The extent of radiolytic degradation was monitored by reversed phase HPLC-UV and GC-ECD. The trace and ultra trace level degradation products were identified using GC-MS-SPME by comparing their mass spectra with the NIST 98 m mass spectral library. Most of the generated products for 4 kGy dose are substituted chlorophenols. The reaction pathways of these substituted chlorophenols and benzophenone formation are also proposed. However, generated chlorophenols disappeared along with methoxychlor for an absorbed dose of 5 kGy. The attained degradation of methoxychlor is {proportional_to} 95% that reflects the potential use of ionization radiation for wastewater treatment. (orig.)

  9. Pressurized liquid extraction-gas chromatography-mass spectrometry for confirming the photo-induced generation of dioxin-like derivatives and other cosmetic preservative photoproducts on artificial skin.

    Science.gov (United States)

    Alvarez-Rivera, Gerardo; Llompart, Maria; Garcia-Jares, Carmen; Lores, Marta

    2016-04-01

    The stability and photochemical transformations of cosmetic preservatives in topical applications exposed to UV-light is a serious but poorly understood problem. In this study, a high throughput extraction and selective method based on pressurized liquid extraction (PLE) coupled to gas chromatography-mass spectrometry (GC-MS) was validated and applied to investigate the photochemical transformation of the antioxidant butylated hydroxytoluene (BHT), as well as the antimicrobials triclosan (TCS) and phenyl benzoate (PhBz) in an artificial skin model. Two sets of photodegradation experiments were performed: (i) UV-Irradiation (8W, 254nm) of artificial skin directly spiked with the target preservatives, and (ii) UV-irradiation of artificial skin after the application of a cosmetic cream fortified with the target compounds. After irradiation, PLE was used to isolate the target preservatives and their transformation products. The follow-up of the photodegradation kinetics of the parent preservatives, the identification of the arising by-products, and the monitorization of their kinetic profiles was performed by GC-MS. The photochemical transformation of triclosan into 2,8-dichloro-dibenzo-p-dioxin (2,8-DCDD) and other dioxin-like photoproducts has been confirmed in this work. Furthermore, seven BHT photoproducts, and three benzophenones as PhBz by-products, have been also identified. These findings reveal the first evidences of cosmetic ingredients phototransformation into unwanted photoproducts on an artificial skin model. PMID:26948762

  10. Reaction kinetics of resveratrol with thiyl and alkoxyl radicals

    International Nuclear Information System (INIS)

    Complete text of publication follows. Plant derived resveratrol (trans-3,5,4'-trihydroxystilbene) possesses a broad spectrum of biological activities, one of them are very well known its antioxidative properties. Our work aims to provide kinetic data with regard to the reactivity of resveratrol with uninvestigated short-lived bioradicals, identified as mediators in oxidative lipid degradation processes. Radicals of our interest are alkoxyl radicals, well known propagators of the chain free radical reactions in lipids, and thiyl radicals which protect lipids from their degradation pathway, but at the same time cause the isomerization of the double bonds. In order to investigate these reactions of resveratrol laser flash photolysis was used. On the basis of competitive kinetics the rate constants were determined under pseudo-first order conditions in acetonitrile solutions at room temperature. Thiyl radicals were generated indirectly in solution containing 1-octadecanthiol and photosensitive benzophenone in acetonitrile using the light pulses at 347 nm from ruby laser. Tert-butoxyl radicals were generated directly by peroxide bond cleavage from di-tert-butyl peroxide in acetonitrile by light pulses of Nd:YAG at 355 nm, and ruby at 347 nm. Obtained rate constants for the reactions of resveratrol and radicals generated by laser flash photolysis will be summarized and compared with rare literature data for the rate constants of investigated reactions of resveratrol and other radicals generated by pulse radiolysis.

  11. 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.

  12. 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.

  13. Dendronized polyimides bearing long-chain alkyl groups and their application for vertically aligned nematic liquid crystal displays.

    Science.gov (United States)

    Tsuda, Yusuke; Min, Jae; Kuwahara, Renpei

    2009-11-01

    Polyimides having dendritic side chains were investigated. The terphenylene diamine monomer having a first-generation monodendron, 3,4,5-tris(n-dodecyloxy)-benzoate and the monomer having a second-generation monodendron, 3,4,5-tris[-3',4',5'-tri(n-dodecyloxy)benzyloxy]benzoate were successfully synthesized and the corresponding soluble dendritic polyimides were obtained by polycondensation with conventional tetracarboxylic dianhydride monomers such as benzophenone tertracarboxylic dianhydride (BTDA). The two-step polymerizations in NMP that is a general method for the synthesis of soluble polyimides is difficult; however, the expected dendritic polyimides can be obtained in aromatic polar solvents such as m-cresol and pyridine. The solubility of these dendoronized polyimides is characteristic; soluble in common organic solvents such as dichloromethane, chloroform, toluene and THF. These dendronized polyimides exhibited high glass transition temperatures and good thermal stability in both air and under nitrogen. Their application as alignment layers for LCDs was investigated, and it was found that these polyimides having dendritic side chains were applicable for the vertically aligned nematic liquid crystal displays (VAN-LCDs). PMID:20087476

  14. Dendronized Polyimides Bearing Long-Chain Alkyl Groups and Their Application for Vertically Aligned Nematic Liquid Crystal Displays

    Directory of Open Access Journals (Sweden)

    Yusuke Tsuda

    2009-11-01

    Full Text Available Polyimides having dendritic side chains were investigated. The terphenylene diamine monomer having a first-generation monodendron, 3,4,5-tris(n-dodecyloxy-benzoate and the monomer having a second-generation monodendron, 3,4,5-tris[-3’,4’,5’-tri(n-dodecyloxybenzyloxy]benzoate were successfully synthesized and the corresponding soluble dendritic polyimides were obtained by polycondensation with conventional tetracarboxylic dianhydride monomers such as benzophenone tertracarboxylic dianhydride (BTDA. The two-step polymerizations in NMP that is a general method for the synthesis of soluble polyimides is difficult; however, the expected dendritic polyimides can be obtained in aromatic polar solvents such as m-cresol and pyridine. The solubility of these dendoronized polyimides is characteristic; soluble in common organic solvents such as dichloromethane, chloroform, toluene and THF. These dendronized polyimides exhibited high glass transition temperatures and good thermal stability in both air and under nitrogen. Their application as alignment layers for LCDs was investigated, and it was found that these polyimides having dendritic side chains were applicable for the vertically aligned nematic liquid crystal displays (VAN-LCDs.

  15. 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)

  16. 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

    2016-09-01

    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. PMID:27495366

  17. 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%.

  18. Photoexcited state acceptor monomers as initiators for free radical induced polymerization

    International Nuclear Information System (INIS)

    Photoinduced alternating copolymerization can be accomplished without the presence of a conventional free radical generating photo-initiator. The structural influences in the direct photolysis of N-Alkyl and N-Arylmaleimides as well as their corresponding ground state charge transfer complexes (CTC) with suitable donors have carefully been investigated. In this paper, laser flash photolysis has been used in order to clarify and experimentally provide evidence for the mechanism of initiation. The maleimide transient intermediate generated by flash photolysis is readily quenched by typical triplet quenchers such as cyclohexadiene. Furthermore, self quenching and reduction of MI transient lifetimes as a function of increasing concentrations of typical hydrogen donors have been determined. Stern-Volmer quenching rate constants for direct versus electron transfer hydrogen abstractions are calculated and compared to benzophenone (BP). From these comparisons it is clear that the triplet state MI is more efficient in direct H-abstraction than the corresponding triplet state of BP. Finally, much higher values of the quenching rate constant for the MI/tert. amine pair versus the MI/ alcohol pair were calculated, suggesting an electron transfer process

  19. 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.

  20. Antiproliferative Constituents of Geopropolis from the Bee Melipona scutellaris.

    Science.gov (United States)

    da Cunha, Marcos Guilherme; Rosalen, Pedro Luiz; Franchin, Marcelo; de Alencar, Severino Matias; Ikegaki, Masaharu; Ransom, Tanya; Beutler, John Albert

    2016-02-01

    Fractionation of geopropolis from Melipona scutellaris, guided by antiproliferative activity against two colon cancer cell lines (COLO205 and KM12), led to the isolation of two new cinnamic acid esters, mammea-type coumarins 5,7-dihydroxy-6-(3-methyl-2-butenyl)-8-(4-cinnamoyl-3-methyl-1-oxobutyl)-4-propyl-coumarin (1) and 5,7-dihydroxy-6-(4-cinnamoyl-3-methyl-1-oxobutyl)-4-phenylcoumarin (2), along with five known coumarins, mammeigin (3), hydroxymammeigin (4), mammeisin (5), cinnamoyloxy-mammeisin (6), and mammein (7), and the prenylated benzophenone ent-nemorosone (8). Among the isolated compounds, 5 and 7 showed the highest cell growth inhibition against COLO205 (GI50 9.7 and 10.7 µM, respectively) and KM12 (GI50 12.0 and 10.9 µM, respectively). The presence of these compounds suggests that plants of Clusiaceae family, especially the genera Kielmeyera and Clusia, are likely to be major sources of geopropolis produced by M. scutellaris. PMID:26544117

  1. Weak two-photon absorption applied to the rapid prototyping of cell scaffolds.

    Science.gov (United States)

    Haq, Bibi Safia; Khan, Hidayat Ullah; Alam, Khan; Attaullah, Shahnaz; Sultan, Mamoona

    2016-01-10

    Two-photon polymerization (TPP) has been employed to generate deep structures using the biocompatible and optically transparent monomer ethoxylated bisphenol A dimethacrylate (EO=6) (EBPADMA) and 4, 4'-Bis(diethylamino)benzophenon as the photoinitiator. The two-photon absorption cross section of the initiator was measured to be 1 GM (1  GM=1×10-50  cm4 s photon-1) in EBPADMA. Here we have explored a weak absorption regime whereby deep structures (∼300  μm) can be generated in a single pass. This allows rapid fabrication of structures suitable for cell scaffolds where the length scales are small, ∼10  μm, but are required over long ranges, ∼cm. The dependence of the TPP properties on the writing power, speed, exposure time and NA, of the focusing lens were studied in detail. Diffraction calculations for the focusing optics employed show that spherical aberration plays a significant role in determining the feature sizes achieved. PMID:26835756

  2. Two-Step, One-Flask Synthesis of a Meso-Substituted Phlorin.

    Science.gov (United States)

    Kim, Dongjoon; Chun, Hao-Jung; Donnelly, Christopher C; Geier, G Richard

    2016-06-17

    A two-step, one-flask reaction of pyrrole with pentafluorobenzaldehyde and acetone was investigated to determine the potential for a streamlined synthesis of a phlorin and/or 5-isocorrole as an alternative to stepwise, dipyrromethanecarbinol routes. Analytical-scale reactions were performed examining the effect of reactant concentration, reactant ratio, acid catalyst (TFA or BF3·OEt2), concentration of acid catalyst, oxidant quantity, and reaction time on the distribution of phlorin and 5-isocorrole as well as three additional porphyrinoids (porphodimethene, porphyrin, and corrole). Phlorin was observed ubiquitously in yields up to 20-26%, whereas 5-isocorrole was not detected. Promising reaction conditions for the one-flask synthesis of the phlorin were performed on a preparative scale. The best reaction condition afforded the phlorin in an isolated yield of 20-21% (249-268 mg). Preliminary attempts to extend the methodology to the preparation of phlorins derived from other ketones resulted in a low yield of phlorin from acetophenone (5%) and no detectable phlorin from benzophenone. The discovery of reaction conditions for the two-step, one-flask synthesis of a phlorin provides easier access to this interesting compound, and provides encouragement for the further study of reactions of pyrrole with an aldehyde and a ketone. PMID:27231965

  3. 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.

  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. Developing lithium chemistry of 1,2-dihydropyridines: from kinetic intermediates to isolable characterized compounds.

    Science.gov (United States)

    Armstrong, David R; Harris, Catriona M M; Kennedy, Alan R; Liggat, John J; McLellan, Ross; Mulvey, Robert E; Urquhart, Matthew D T; Robertson, Stuart D

    2015-10-01

    Generally considered kinetic intermediates in addition reactions of alkyllithiums to pyridine, 1-lithio-2-alkyl-1,2-dihydropyridines have been rarely isolated or characterized. This study develops their "isolated" chemistry. By a unique stoichiometric (that is, 1:1, alkyllithium/pyridine ratios) synthetic approach using tridentate donors we show it is possible to stabilize and hence crystallize monomeric complexes where alkyl is tert-butyl. Theoretical calculations probing the donor-free parent tert-butyl species reveal 12 energetically similar stereoisomers in two distinct cyclotrimeric (LiN)3 conformations. NMR spectroscopy studies (including DOSY spectra) and thermal volatility analysis compare new sec-butyl and iso-butyl isomers showing the former is a hexane soluble efficient hydrolithiation agent converting benzophenone to lithium diphenylmethoxide. Emphasizing the criticalness of stoichiometry, reaction of nBuLi/Me6 TREN with two equivalents of pyridine results in non-alkylated 1-lithio-1,4-dihydropyridine⋅Me6 TREN and 2-n-butylpyridine, implying mechanistically the kinetic 1,2-n-butyl intermediate hydrolithiates the second pyridine. PMID:26333094

  6. Electron and hydrogen self-exchange of free radicals of sterically hindered tertiary aliphatic amines investigated by photo-CIDNP

    Directory of Open Access Journals (Sweden)

    Martin Goez

    2013-02-01

    Full Text Available The photoreactions of diazabicyclo[2,2,2]octane (DABCO and triisopropylamine (TIPA with the sensitizers anthraquinone (AQ and xanthone (XA or benzophenone (BP were investigated by time-resolved photo-CIDNP (photochemically induced dynamic nuclear polarization experiments. By varying the radical-pair concentration, it was ensured that these measurements respond only to self-exchange reactions of the free amine-derived radicals (radical cations DH•+ or α-amino alkyl radicals D• with the parent amine DH; the acid–base equilibrium between DH•+ and D• also plays no role. Although the sensitizer does not at all participate in the observed processes, it has a pronounced influence on the CIDNP kinetics because the reaction occurs through successive radical pairs. With AQ, the polarizations stem from the initially formed radical-ion pairs, and escaping DH•+ then undergoes electron self-exchange with DH. In the reaction sensitized with XA (or BP, the polarizations arise in a secondary pair of neutral radicals that is rapidly produced by in-cage proton transfer, and the CIDNP kinetics are due to hydrogen self-exchange between escaping D• and DH. For TIPA, the activation parameters of both self-exchange reactions were determined. Outer-sphere reorganization energies obtained with the Marcus theory gave very good agreement between experimental and calculated values of ∆G‡298.

  7. Photoprotective and toxicological activities of extracts from the Antarctic moss Sanionia uncinata

    Directory of Open Access Journals (Sweden)

    Andréia da Silva Fernandes

    2015-01-01

    Full Text Available Background: The Antarctic moss Sanionia uncinata (Hedw. Loeske has shown high ultraviolet (UV-absorbers content after exposition to high levels of UV-B radiation and can be an important source of antioxidants. Objective: The aim was to investigate photoprotection and mutagenicity by the aqueous extract (AE and hydroethanolic extract (HE from the Antarctic moss S. uncinata. Materials and Methods: Photoprotective activities were determined through survival curves of Escherichia coli strains, after UV irradiation in an aqueous solution of thymine and in vitro sun protection factor (SPF. The Salmonella/microsome assays were applied to assess the mutagenicity. Results: Both extracts induced photoprotection against UV-C radiation. The AE showed a higher protection than the hydroethanolic one against UV-induced thymine dimerization. The SPFs were low in both extracts. In association to benzophenone-3 a significant increase in the SPF was detected for the AE, and a significant decrease was induced by the HE. No mutagenicity was found in the both extracts. Furthermore, it was observed absence of cytotoxicity. Conclusion: Water-extractable compounds seem to contribute on photoprotection of this Antarctic moss.

  8. Pros and cons of analytical methods to quantify surrogate contaminants from the challenge test in recycled polyethylene terephthalate

    Energy Technology Data Exchange (ETDEWEB)

    Felix, Juliana S., E-mail: jfelix@unizar.es [Department of Analytical Chemistry, Aragon Institute of Engineering Research (I3A), CPS, University of Zaragoza, Torres Quevedo Bldg., Maria de Luna St. 3, E-50018 Zaragoza (Spain); Alfaro, Pilar, E-mail: palfarot@unizar.es [Department of Analytical Chemistry, Aragon Institute of Engineering Research (I3A), CPS, University of Zaragoza, Torres Quevedo Bldg., Maria de Luna St. 3, E-50018 Zaragoza (Spain); Nerin, Cristina, E-mail: cnerin@unizar.es [Department of Analytical Chemistry, Aragon Institute of Engineering Research (I3A), CPS, University of Zaragoza, Torres Quevedo Bldg., Maria de Luna St. 3, E-50018 Zaragoza (Spain)

    2011-02-14

    Different analytical methods were optimized and applied to quantify certain surrogate contaminants (toluene, chlorobenzene, phenol, limonene and benzophenone) in samples of contaminated and recycled flakes and virgin pellets of polyethylene terephthalate (PET) coming from the industrial challenge test. A screening analysis of the PET samples was carried out by direct solid-phase microextraction (SPME) in headspace mode (HS). The methods developed and used for quantitative analysis were a) total dissolution of PET samples in dichloroacetic acid and analysis by HS-SPME coupled to gas chromatography-mass spectrometry (GC-MS) and, b) dichloromethane extraction and analysis by GC-MS. The concentration of all surrogates in the contaminated PET flakes analyzed by HS-SPME method was lower than expected according to information provided by the supplier. Dichloroacetic acid interacted with the surrogates, resulting in a tremendous decrease of limonene concentration. The degradation compounds from limonene were identified. Dichloromethane extraction and GC-MS analysis evidenced the highest values of analytes in these PET samples. Based on the foregoing data, the efficiency of the recycling process was evaluated, whereby the removal of 99.9% of the surrogates proceeding from the contaminated flakes was confirmed.

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

    International Nuclear Information System (INIS)

    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. 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. PMID:24875873

  11. Gamma radiolytic eradication of methoxychlor in aqueous media. The degradation pathways using HPLC and SPME-GC-MS

    International Nuclear Information System (INIS)

    The gamma radiation-induced degradation of environmental pollutant methoxychlor in water was investigated. A 60Co gamma radiation source with a dose rate of 372 Gy h-1 was used for gamma irradiation of 1 mg L-1 and 10 mg L-1 methoxychlor in water with a varied absorbed dose of 1-5 kGy. A single step clean up and pre-concentration procedure based on solid phase micro-extraction was optimized. The extent of radiolytic degradation was monitored by reversed phase HPLC-UV and GC-ECD. The trace and ultra trace level degradation products were identified using GC-MS-SPME by comparing their mass spectra with the NIST 98 m mass spectral library. Most of the generated products for 4 kGy dose are substituted chlorophenols. The reaction pathways of these substituted chlorophenols and benzophenone formation are also proposed. However, generated chlorophenols disappeared along with methoxychlor for an absorbed dose of 5 kGy. The attained degradation of methoxychlor is ∝ 95% that reflects the potential use of ionization radiation for wastewater treatment. (orig.)

  12. Serine-324 of myosin's heavy chain is photoaffinity-labeled by 3'(2')-O-(4-benzoylbenzoyl)adenosine triphosphate

    International Nuclear Information System (INIS)

    A portion of the active site of rabbit skeletal myosin near the ribose ring of ATP can be labeled by the photoaffinity analogue 3'(2')-O-(4-benzoylbenzoyl)adenosine triphosphate (Bz2ATP). The specificity of the photolabeling was assured by first trapping [14C]Bz2ATP at the active site by use of thiol cross-linking agents. Five radioactive peptides were isolated by high-performance liquid chromatography after extensive trypsin and subtilisin digestion of photolabeled myosin subfragment 1. Four of these peptides were sequenced by Edman techniques, and all originated from a region with the sequence Gly-Glu-Ile-Thr-Val-Pro-Ser-Ile-Asp-Asp-Gln, which corresponds to rabbit myosin heavy chain residues 312-328. The fifth labeled peptide had an amino acid composition appropriate for residues 312-328. Amino acid composition, radiochemical analysis, and sequence data indicate that Ser-324 is the major amino acid residue photolabeled by Bz2ATP. Spectrophotometric evidence indicates that the benzophenone carbonyl group has inserted into a C-H bond from either the α- or β-carbon of serine. These results place Ser-324 at a distance of 6-7 angstrom from the 3'(2') ribose oxygens of ATP bound at the active site of myosin

  13. Coextruded, aligned, and gradient-modified poly(ε-caprolactone) fibers as platforms for neural growth.

    Science.gov (United States)

    Kim, Si-Eun; Harker, Emily C; De Leon, Al C; Advincula, Rigoberto C; Pokorski, Jonathan K

    2015-03-01

    Polymeric fibers are of increasing interest to regenerative medicine, as materials made from these fibers are porous, allowing for cell infiltration, influx of nutrients, and efflux of waste products. Recently, multilayered coextrusion has emerged as a scalable and rapid fabrication method to yield microscale to submicron fibers. In this report, we describe the multilayered coextrusion of aligned poly(ε-caprolactone) (PCL) fibers, followed by a simple photochemical patterning to create surface-immobilized gradients onto the polymer fibers. PCL fibers were photochemically decorated with a linear gradient of propargyl benzophenone using a gradient photomask to control light source intensity. The pendant alkynes were then able to undergo the copper-catalyzed azide-alkyne cycloaddition reaction with an azide-modified IKVAV peptide to further functionalize the surface. Gradient-modified IKVAV fibers were evaluated for neural cell adhesion and neural differentiation, using PC-12 cells cultured onto the fibers. The aligned gradient fibers provided directional cues for neurite outgrowth and alignment of neural cells, as observed by cellular elongation, neurite differentiation, and orientation. The work presented herein describes a scalable fiber system combined with simple chemical patterning to generate aligned fibers with controlled surface gradients as cell-seeding scaffolds. PMID:25715836

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

    International Nuclear Information System (INIS)

    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. The use of natural rubber-based material for the preparation of radiation-curable resin. I. The reaction of epoxidised natural rubbers of low molecular weight with acrylic acid

    International Nuclear Information System (INIS)

    A synthesis method for the preparation of a new radiation-curable resin based on natural rubber has been established. The method was based on the reaction between epoxidised natural rubbers (ENR) of low molecular weight, i.e. Mn 0f 5,800 to 82,000, with acrylic acid in the presence of a catalyst and an inhibitor. Two grades of ENR namely ENR-25 and ENR-50 corresponding to 25 and 50 mole % epoxidation levels, respectively were used. The acrylation was carried out at temperatures between 95-105 degree C and was monitored by the measurements of the acid value of the reaction mixture as the reaction proceeded. It was confirmed by IR spectroscopic technique that the reaction occurred through the ring opening of the epoxide group of ENR. As a result, the new resin contains radiation-curable acrylate groups as well as hydroxyl groups on its main chain. When formulated with benzophenone, it solidified upon with UV light

  16. Food contact materials, flavouring substances and smoke flavourings

    Directory of Open Access Journals (Sweden)

    Engel K-H

    2012-10-01

    Full Text Available

    The EFSA Panel on Food Additives, Flavourings, Processing Aids and Materials in Contact with Food (AFC Panel and the subsequent Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids (CEF Panel have undertaken evaluations of the safety of flavourings (both chemically defined substances and mixtures such as smoke flavourings and food contact materials (FCM, as well as assessments on other substances used in food. The major progress in methodologies for the evaluation of the safety of these substances is highlighted in this article. By December 2011, scientific opinions had been adopted for 247 substances for food contact materials, mainly plastics. Adoption of a series of opinions on active and/or intelligent packaging substances and on recycling processes of plastics is planned between July 2012 and December 2013. Panel opinions, EFSA statements/reports and guidance documents were published on specific issues and on substances for which there was an urgent request for safety evaluation (for example isopropylthioxanthone (ITX, bisphenol A (BPA, phthalates, epoxidised soybean oil (ESBO, benzophenone and 4-methylbenzophenone. By 2009, the AFC and CEF Panels had completed the safety review of 2 067 flavourings substances used in the EU. Additional data, which were requested for 404 substances, are currently under evaluation or have been generated. Eleven smoke flavourings have been evaluated, and the CEF Panel has prepared a guidance document on the future data required for the evaluation of flavourings.

  17. Pestalone, a new antibiotic produced by a marine fungus in response to bacterial challenge.

    Science.gov (United States)

    Cueto, M; Jensen, P R; Kauffman, C; Fenical, W; Lobkovsky, E; Clardy, J

    2001-11-01

    The isolation and structure determination of a new chlorinated benzophenone antibiotic, pestalone (1), is described. The new compound was produced by a cultured marine fungus only when a unicellular marine bacterium, strain CNJ-328, was co-cultured in the fungal fermentation. The fungus, isolated from the surface of the brown alga Rosenvingea sp. collected in the Bahamas Islands, was identified as an undescribed member of the genus Pestalotia. The structure of 1, initially assigned with only modest confidence by combined spectral and chemical data, was confirmed by single-crystal X-ray analysis. Pestalone (1) exhibits moderate in vitro cytotoxicity in the National Cancer Institute's 60 human tumor cell line screen (mean GI(50) = 6.0 microM). More importantly, pestalone shows potent antibiotic activity against methicillin-resistant Staphylococcus aureus (MIC = 37 ng/mL) and vancomycin-resistant Enterococcus faecium (MIC = 78 ng/mL), indicating that pestalone should be evaluated in advanced models of infectious disease. PMID:11720529

  18. Preparation of Polypropylene Spin Tips Filled with Immobilized Titanium(IV) Ion Monolithic Adsorbent for Robust Phosphoproteome Analysis.

    Science.gov (United States)

    Liu, Fangjie; Wan, Hao; Liu, Zhongshan; Wang, Hongwei; Mao, Jiawei; Ye, Mingliang; Zou, Hanfa

    2016-05-17

    In this study, we developed a Ti(IV) monolithic spin tip for phosphoproteome analysis of a minute amount of biological sample for the first time. The surface of polypropylene pipet tip was activated by the photoinitiator benzophenone under UV light radiation followed by polymerization of ethylene glycol methacrylate phosphate and bis-acrylamide in the tip to form a porous monolith with reactive phosphate groups. The as-prepared tips grafted with monolithic adsorbent were then chelated with titanium(IV) ion for phosphopeptide enrichment. It was found that the tips enabled fast and efficient capture of phosphopeptides from microscale complex samples. The monolithic tip was demonstrated to have a detection limit as low as 5 fmol β-casein tryptic digest, along with an exceptionally high specificity to capture phosphopeptides from complex tryptic digest mixed with an unphosphorylated protein and a phosphorylated protein at a molar ratio up to 1000:1. When the tip was applied to enrich phosphopeptides from 5 μg of tryptic digest of complex HeLa cell proteins, 1185 high confidence of phosphorylated sites were successfully identified with the specificity as high as 92.5%. So far, this is the most sensitive phosphoproteomics analysis using a standard liquid chromatography-tandem mass spectrometry (LC-MS/MS) system for proteome-wide phosphorylation analysis in mammalian cells. PMID:27101427

  19. Polyphenols with Antiulcerogenic Action from Aqueous Decoction of Mango Leaves (Mangifera indica L.

    Directory of Open Access Journals (Sweden)

    Juliana Aparecida Severi

    2009-03-01

    Full Text Available This study was designed to determine the gastroprotective effect of a Mangifera indica leaf decoction (AD, on different experimental models in rodents. The administration of AD up to a dose of 5 g/kg (p.o. did not produce any signs or symptoms of toxicity in the treated animals, while significantly decreasing the severity of gastric damage induced by several gastroprotective models. Oral pre-treatment with AD (250, 500 or 1000 mg/kg in mice and rats with gastric lesions induced by HCl/ethanol, absolute ethanol, non-steroidal anti-inflammatory drug (NSAID or stress-induced gastric lesions resulted in a significant decrease of said lesions. Phytochemical analyses of AD composition demonstrated the presence of bioactive phenolic compounds that represent 57.3% of total phenolic content in this extract. Two main phenolic compounds were isolated, specifically mangiferin (C-glucopyranoside of 1,3,6,7-tetrahydroxyxanthone and C-glucosyl-benzophenone (3-C-β-D-glucopyranosyl-4’,2,4,6-tetrahydroxybenzophenone. These findings indicate the potential gastroprotective properties of aqueous decoction from M. indica leaves.

  20. A highly reactive photobase catalytic system for sol–gel polymerization

    International Nuclear Information System (INIS)

    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

  1. Radiation sterilization of ketoprofen

    International Nuclear Information System (INIS)

    Radiation sterilization of ketoprofen (KP) dry powder was investigated by selected physico-chemical methods. High-performance liquid chromatography, ultraviolet spectrophotometry, infrared spectrophotometry, differential scanning calorimetry, X-ray diffraction and electron spin resonance spectroscopy did not show any significant degradation at sterilization dose 25 kGy. To determine the nature, extent and direction of radiation-induced changes, KP was irradiated to extremely high doses, much higher than necessary to achieve sterility. The irradiated KP did not show any difference of XRD patterns up to 200 kGy; with DSC and IR some changes were detected only above 1000 and 2000 kGy, respectively; HPLC has shown about 5% destruction at 2000 kGy. Acetyl benzophenon (AcBph) was generated by irradiation with G(AcBph)=(1.6±0.1)x10-8 mol J-1. Ames test has shown no mutagenicity of KP irradiated with 3000 kGy or of the oily mixture of radiolytic products isolated from it. Solid KP has proven to be very stable on irradiation, and irradiation has been found to be a suitable method for its sterilization

  2. Radiation sterilization of ketoprofen

    Energy Technology Data Exchange (ETDEWEB)

    Katusin-Razem, Branka [Ruder Boskovic Institute, P.O.B 180, Zagreb 10000 (Croatia)]. E-mail: brazem@irb.hr; Hamitouche, Katia [Centre de Recherche et Developpement Saidal, El Harrach (Algeria); Maltar-Strmecki, Nadica [Faculty of Veterinary Medicine, University of Zagreb, Zagreb 10000 (Croatia); Kos, Karmen [Belupo Pharmaceutical Works, Koprivnica 48000 (Croatia); Pucic, Irina [Ruder Boskovic Institute, P.O.B 180, Zagreb 10000 (Croatia); Britvic-Budicin, Smiljana [Ruder Boskovic Institute, P.O.B 180, Zagreb 10000 (Croatia); Razem, Dusan [Ruder Boskovic Institute, P.O.B 180, Zagreb 10000 (Croatia)

    2005-06-01

    Radiation sterilization of ketoprofen (KP) dry powder was investigated by selected physico-chemical methods. High-performance liquid chromatography, ultraviolet spectrophotometry, infrared spectrophotometry, differential scanning calorimetry, X-ray diffraction and electron spin resonance spectroscopy did not show any significant degradation at sterilization dose 25 kGy. To determine the nature, extent and direction of radiation-induced changes, KP was irradiated to extremely high doses, much higher than necessary to achieve sterility. The irradiated KP did not show any difference of XRD patterns up to 200 kGy; with DSC and IR some changes were detected only above 1000 and 2000 kGy, respectively; HPLC has shown about 5% destruction at 2000 kGy. Acetyl benzophenon (AcBph) was generated by irradiation with G(AcBph)=(1.6{+-}0.1)x10{sup -8} mol J{sup -1}. Ames test has shown no mutagenicity of KP irradiated with 3000 kGy or of the oily mixture of radiolytic products isolated from it. Solid KP has proven to be very stable on irradiation, and irradiation has been found to be a suitable method for its sterilization.

  3. Radiation sterilization of ketoprofen

    Science.gov (United States)

    Katušin-Ražem, Branka; Hamitouche, Katia; Maltar-Strmečki, Nadica; Kos, Karmen; Pucić, Irina; Britvić-Budicin, Smiljana; Ražem, Dušan

    2005-06-01

    Radiation sterilization of ketoprofen (KP) dry powder was investigated by selected physico-chemical methods. High-performance liquid chromatography, ultraviolet spectrophotometry, infrared spectrophotometry, differential scanning calorimetry, X-ray diffraction and electron spin resonance spectroscopy did not show any significant degradation at sterilization dose 25 kGy. To determine the nature, extent and direction of radiation-induced changes, KP was irradiated to extremely high doses, much higher than necessary to achieve sterility. The irradiated KP did not show any difference of XRD patterns up to 200 kGy; with DSC and IR some changes were detected only above 1000 and 2000 kGy, respectively; HPLC has shown about 5% destruction at 2000 kGy. Acetyl benzophenon (AcBph) was generated by irradiation with G(AcBph)=(1.6±0.1)×10 -8 mol J -1. Ames test has shown no mutagenicity of KP irradiated with 3000 kGy or of the oily mixure of radiolytic products isolated from it. Solid KP has proven to be very stable on irradiation, and irradiation has been found to be a suitable method for its sterilization.

  4. Measurement, analysis and prediction of topical UV filter bioavailability.

    Science.gov (United States)

    Roussel, L; Gilbert, E; Salmon, D; Serre, C; Gabard, B; Haftek, M; Maibach, H I; Pirot, F

    2015-01-30

    The aim of the present study was to objectively quantify and predict bioavailability of three sunscreen agents (i.e., benzophenone-3, 2-ethylhexylsalicylate, and 2 ethylhexyl-4-methoxycinnamate) in epidermis treated by petrolatum and emulsion-based formulations for 7 and 30min on four human volunteers. Profiles of sunscreen agents through stratum corneum (SC), derived from the assessment of chemical amounts in SC layers collected by successive adhesive tape-stripping, were successfully fitted to Fick's second law of diffusion. Therefore, permeability coefficients of sunscreen agents were found lower with petrolatum than with emulsion based formulations confirming the crucial role of vehicle in topical delivery. Furthermore, the robustness of that methodology was confirmed by the linear relationship between the chemical absorption measured after 30min and that predicted from the 7-min exposure experiment. Interestingly, in this dermatopharmacokinetic method, the deconvolution of permeability coefficients in their respective partition coefficients and absorption constants allowed a better understanding of vehicle effects upon topical bioavailability mechanisms and bioequivalence of skin products. PMID:25526673

  5. Simultaneous determination of cosmetics ingredients in nail products by fast gas chromatography with tandem mass spectrometry.

    Science.gov (United States)

    Zhou, Wanlong; Wang, Perry G; Wittenberg, James B; Rua, Diego; Krynitsky, Alexander J

    2016-05-13

    A rapid and sensitive gas chromatography with tandem mass spectrometry (GC-MS/MS) method has been developed and validated to quantitatively determine cosmetic ingredients, such as toluene, N-methylpyrrolidone, 2,4-dihydroxybenzophenone (benzophenone-1, BP-1), and diethylene glycol dimethacrylate, in nail products. In this procedure, test portions were extracted with acetone, followed by vortexing, sonication, centrifugation, and filtration. During the extraction procedure, BP-1 was derivatized making it amenable to GC-MS analysis, using N,O-​bis(trimethylsilyl)​trifluoroacetamide. The four ingredients were quantified by GC-MS/MS in an electron ionization mode. Four corresponding stable isotopically labeled analogues were selected as internal standards, which were added at the beginning of the sample preparation to correct for recoveries and matrix effects. The validated method was used to screen 34 commercial nail products for these four cosmetic ingredients. The most common ingredients detected in the nail products were toluene and BP-1. Toluene was detected in 26 products and ranged from 1.36 to 173,000μg/g. BP-1 ranged from 18.3 to 2,370μg/g in 10 products. PMID:27083261

  6. Protective effects of garcinol in mice with lipopolysaccharide/D-galactosamine-induced apoptotic liver injury.

    Science.gov (United States)

    Jing, Yuping; Ai, Qing; Lin, Ling; Dai, Jie; Jia, Mengying; Zhou, Dan; Che, Qian; Wan, Jingyuan; Jiang, Rong; Zhang, Li

    2014-04-01

    Garcinol is a polyisoprenylated benzophenone derivative of Garcinia indica. Recent researches have revealed the antioxidant, anticancer and anti-inflammatory properties of garcinol. In the present study, the pharmacological effects of garcinol in lipopolysaccharide (LPS)-induced hepatic injury in D-galactosamine (D-Gal)-sensitized mice were investigated. We found that treatment with garcinol significantly decreased serum ALT and AST levels in LPS/D-Gal-exposed mice. These were accomplished with improved histological alterations in liver sections and reduced malondialdehyde (MDA) content in liver homogenates. Garcinol significantly reduced the acetylation level of NF-κB, but it had no obvious effects on the elevation of TNF-α or IL-6 in plasma or liver tissue. Garcinol significantly attenuated LPS/D-Gal-induced hepatic apoptosis as evidenced by reduced number of TUNEL-positive cells in liver sections. Our experiments also showed that garcinol markedly suppressed the cleavage of caspase-3 and significantly decreased the activities of caspase-3, -8, and -9 in liver tissues. In addition, garcinol obviously reduced the induction of Bax but did not alter the level of Bcl-2. These results indicated that garcinol might provide protective benefits in LPS/D-Gal-induced liver injury through suppressing apoptosis. PMID:24560905

  7. Chemoprevention of 7,12-dimethylbenz[a]anthracene (DMBA)-induced hamster cheek pouch carcinogenesis by a 5-lipoxygenase inhibitor, garcinol.

    Science.gov (United States)

    Chen, Xin; Zhang, Xinyan; Lu, Ye; Shim, Joong-Youn; Sang, Shengmin; Sun, Zheng; Chen, Xiaoxin

    2012-01-01

    Our previous studies have shown that aberrant arachidonic acid metabolism, especially the 5-lipoxygenase (5-Lox) pathway, is involved in oral carcinogenesis and can be targeted for cancer prevention. To develop potent topical agents for oral cancer chemoprevention, 5 known 5-Lox inhibitors from dietary and synthetic sources (Zileuton, ABT-761, licofelone, curcumin, and garcinol) were evaluated in silico for their potential efficacy. Garcinol, a polyisoprenylated benzophenone from the fruit rind of Garcinia spp., was found to be a promising agent based on the calculation of a theoretical activity index. Computer modeling showed that garcinol well fit the active site of 5-Lox, and potentially inhibited enzyme activity through interactions between the phenolic hydroxyl groups and the non-heme catalytic iron. In a short-term study on 7,12-dimethylbenz[a]anthracene (DMBA)-treated hamster cheek pouch, topical garcinol suppressed leukotriene B4 (LTB4) biosynthesis and inhibited inflammation and cell proliferation in the oral epithelium. In a long-term carcinogenesis study, topical garcinol significantly reduced the size of visible tumors, the number of cancer lesions, cell proliferation, and LTB4 biosynthesis. These results demonstrated that topical application of a 5-Lox inhibitor, garcinol, had chemopreventive effect on DMBA-induced hamster cheek pouch carcinogenesis. PMID:23137051

  8. Protective effects of garcinol on dimethylnitrosamine-induced liver fibrosis in rats.

    Science.gov (United States)

    Hung, Wei-Lun; Tsai, Mei-Ling; Sun, Pei-Pei; Tsai, Chen-Yu; Yang, Chin-Chou; Ho, Chi-Tang; Cheng, An-Chin; Pan, Min-Hsiung

    2014-11-01

    Garcinol, a polyisoprenylated benzophenone derivative, mainly isolated from Garcinia indica fruit rind, has been suggested to exhibit many biological benefits including antioxidative, anti-inflammatory, and anti-tumor activities. The aim of this study is to evaluate the protective effects of garcinol on dimethylnitrosamine (DMN)-induced liver fibrosis in rats. The administration of DMN for six consecutive weeks resulted in the decrease of body weights, the elevation of serum aminotransferases, as well as histological lesions in livers. However, oral administration of garcinol remarkably inhibited the elevation of aspartate transaminase (AST) and relieved liver damage induced by DMN. Furthermore, our results revealed that garcinol not only effectively reduced the accumulation of extracellular matrix (ECM) components but also inhibited the expression of α-smooth muscle actin (α-SMA) in livers. The expression of transforming growth factor-β1 (TGF-β1) and the phosphorylation of Smad 2 and Smad 3 were also suppressed by garcinol supplementation. In conclusion, our current study suggested that garcinol exerted hepatoprotective and anti-fibrotic effects against DMN-induced liver injury in rats. PMID:25183344

  9. 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.

  10. 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.

  11. 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.

  12. A model assessment of the ability of lake water in Terra Nova Bay, Antarctica, to induce the photochemical degradation of emerging contaminants.

    Science.gov (United States)

    Minella, Marco; Maurino, Valter; Minero, Claudio; Vione, Davide

    2016-11-01

    The shallow lakes located in Terra Nova Bay, Antarctica, are free from ice for only up to a couple of months (mid December to early/mid February) during the austral summer. In the rest of the year, the ice cover shields the light and inhibits the photochemical processes in the water columns. Previous work has shown that chromophoric dissolved organic matter (CDOM) in these lakes is very reactive photochemically. A model assessment is here provided of lake-water photoreactivity in field conditions, based on experimental data of lake water absorption spectra, chemistry and photochemistry obtained previously, taking into account the water depth and the irradiation conditions of the Antarctic summer. The chosen sample contaminants were the solar filter benzophenone-3 and the antimicrobial agent triclosan, which have very well known photoreactivity and have been found in a variety of environmental matrices in the Antarctic continent. The two compounds would have a half-life time of just a few days or less in the lake water during the Antarctic summertime, largely due to reaction with CDOM triplet states ((3)CDOM*). In general, pollutants that occur in the ice and could be released to lake water upon ice melting (around or soon after the December solstice) would be quickly photodegraded if they undergo fast reaction with (3)CDOM*. With some compounds, the important (3)CDOM* reactions might favour the production of harmful secondary pollutants, such as 2,8-dichlorodibenzodioxin from the basic (anionic) form of triclosan. PMID:27487093

  13. Protective effects of 2,4-dihydroxybenzophenone against acetaminophen-induced hepatotoxicity in mice

    Institute of Scientific and Technical Information of China (English)

    Yue-Ying He; Bao-Xu Zhang; Feng-Lan Jia

    2011-01-01

    AIM: To examine the effects of 2,4-dihydroxybenzophenone (BP-1), a benzophenone derivative used as an ultraviolet light absorbent, on acetaminophen (APAP)- induced hepatotoxicity in C57BL/6J mice. METHODS: Mice were administered orally with BP-1 at doses of 200, 400 and 800 mg/kg body weight respectively every morning for 4 d before a hepatotoxic dose of APAP (350 mg/kg body weight) was given subcutaneously. Twenty four hours after APAP intoxication, the serum enzyme including serum alaine aminotransferase (ALT), aspartate aminotransferase (AST), lactate dehydrogenase (LDH) were measured and liver histopathologic changes were examined. RESULTS: BP-1 administration dramatically reduced serum ALT, AST and LDH levels. Liver histopathological examination showed that BP-1 administration antagonized APAP-induced liver pathological damage in a dose-dependent manner. Further tests showed that APAP-induced hepatic lipid peroxidation was reduced significantly by BP-1 pretreatment, and glutathione depletion was ameliorated obviously. CONCLUSION: BP-1 can effectively protect C57BL/6J mice from APAP-induced hepatotoxicity, and reduction of oxidative stress might be part of the protection mechanism.

  14. Garcinielliptone FC: antiparasitic activity without cytotoxicity to mammalian cells.

    Science.gov (United States)

    Silva, Ana P; Silva, Marcos P; Oliveira, Cristiano G; Monteiro, Daniela C; Pinto, Pedro L; Mendonça, Ronaldo Z; Costa Júnior, Joaquim S; Freitas, Rivelilson M; de Moraes, Josué

    2015-06-01

    Garcinielliptone FC (GFC) is a natural prenylated benzophenone found in the seeds of Platonia insignis Mart. (Clusiaceae), a native Brazilian plant. It has been chemically characterized and it is known that GFC has several biological activities such as antioxidant and vasorelaxant properties. In this study, we report the in vitro effect of GFC against the blood fluke Schistosoma mansoni, the parasite responsible for schistosomiasis mansoni. The anti-S. mansoni activity and cytotoxicity toward mammalian cells were determined for the compound. GFC⩾6.25 μM showed antischistosomal activity and confocal laser scanning microscopy analysis demonstrated several morphological alterations on the tegument of worms, and a correlation between viability and tegumental damage was observed. In addition, at sub-lethal concentrations of GFC (⩽3.125 μM), the number of S. mansoni eggs was reduced. More importantly, GFC exhibited no activity toward mammalian cells and, therefore, there is an appreciable selectivity of this compound against the helminths. In conclusion, these findings indicate the potential of GFC as an antiparasitic agent. PMID:25553916

  15. Garcinol sensitizes human head and neck carcinoma to cisplatin in a xenograft mouse model despite downregulation of proliferative biomarkers.

    Science.gov (United States)

    Li, Feng; Shanmugam, Muthu K; Siveen, Kodappully Sivaraman; Wang, Fan; Ong, Tina H; Loo, Ser Yue; Swamy, Mahadeva M M; Mandal, Somnath; Kumar, Alan Prem; Goh, Boon Cher; Kundu, Tapas; Ahn, Kwang Seok; Wang, Ling Zhi; Hui, Kam Man; Sethi, Gautam

    2015-03-10

    Platinum compounds such as cisplatin and carboplatin are frequently used as the first-line chemotherapy for the treatment of the head and neck squamous cell carcinoma (HNSCC). In the present study, we investigated whether garcinol, a polyisoprenylated benzophenone can chemosensitize HNSCC to cisplatin. We found that garcinol inhibited the viability of a panel of diverse HNSCC cell lines, enhanced the apoptotic effect of cisplatin, suppressed constitutive as well as cisplatin-induced NF-κB activation, and downregulated the expression of various oncogenic gene products (cyclin D1, Bcl-2, survivin and VEGF). In vivo study showed that administration of garcinol alone (0.5 mg/kg body weight, i.p. five times/week) significantly suppressed the growth of the tumor, and this effect was further increased by cisplatin. Both the markers of proliferation index (Ki-67) and microvessel density (CD31) were downregulated in tumor tissues by the combination of cisplatin and garcinol. The pharmacokinetic results of garcinol indicated that good systemic exposure was achievable after i.p. administration of garcinol at 0.5 mg/kg and 2 mg/kg with mean peak concentration (Cmax) of 1825.4 and 6635.7 nM in the mouse serum, respectively. Overall, our results suggest that garcinol can indeed potentiate the effects of cisplatin by negative regulation of various inflammatory and proliferative biomarkers. PMID:25762616

  16. Synthesis and properties of new polyimide/clay nanocomposite films

    Indian Academy of Sciences (India)

    Yagoub Mansoori; Somayeh Shah Sanaei; Mohammad-Reza Zamanloo; Gholamhassan Imanzadeh; Seyed Vahid Atghia

    2013-10-01

    A series of polymer–clay nanocomposite (PCN) materials consisting of polyimide and typical clay were prepared by solution dispersion. Quaternary alkylammonium modified montmorillonite, Cloisite 20A, was used as organoclay. Poly(amic acid) solution was prepared fromthe reaction of benzophenone-4,4′,3,3′-tetracarboxylic dianhydride and 2-(5-(3,5-diaminophenyl)-1,3,4-oxadiazole-2-yl) pyridine in dimethylacetamide. Thermal imidization was performed on poly(amic acid)/organoclay dispersion in a regular temperature-programmed circulation oven. The study of interlayer -spacing with X-ray diffraction pattern indicates that an exfoliated structure may be present in the nanocomposite 1%. Intercalated structures were obtained at higher organoclay loadings. Nanocomposites were studied using thermogravimertic analysis and differential scanning calorimetry. Nanocomposites exhibit higher glass transition temperature and improved thermal properties compared to neat polyimide due to the interaction between polymer matrix and organoclay particles. The results are also compared with data of a similar work. Morphology study with scanning electron microscopy showed that the surface roughness in nanocomposite 1%increased with respect to pristine polyimide. Solvent uptake measurements were also carried out for the prepared materials. Maximum solvent adsorption was observed for dimethyl sulfoxide (DMSO). It was found that the solvent uptake capacity decreased with increasing clay content.

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

    International Nuclear Information System (INIS)

    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

  18. Biomimetic phosphorylcholine polymer grafting from polydimethylsiloxane surface using photo-induced polymerization.

    Science.gov (United States)

    Goda, Tatsuro; Konno, Tomohiro; Takai, Madoka; Moro, Toru; Ishihara, Kazuhiko

    2006-10-01

    The biomimetic synthetic phospholipid polymer containing a phosphorylcholine group, 2-methacryloyloxyethyl phosphorylcholine (MPC), has improved the surface property of biomaterials. Both hydrophilic and anti-biofouling surfaces were prepared on polydimethylsiloxane (PDMS) with MPC grafted by surface-initiated photo-induced radical polymerization. Benzophenone was used as the photoinitiator. The quantity of the adsorbed initiator on PDMS was determined by UV absorption and ellipsometry. The poly(MPC)-grafted PDMS surfaces were characterized by XPS, ATR-FTIR and static water contact angle (SCA) measurements. The SCA on PDMS decreased from 115 degrees to 25 degrees after the poly(MPC) grafting. The in vitro single protein adsorption on the poly(MPC)-grafted PDMS decreased 50-75% compared to the unmodified PDMS. The surface friction of the poly(MPC)-grafted PDMS was lower than the unmodified PDMS under wet conditions. The oxygen permeability of the poly(MPC)-grafted PDMS was as high as the unmodified PDMS. The tensile property of PDMS was maintained at about 90% of the ultimate stress and strain after the poly(MPC) grafting. The surface-modified PDMS is expected to be a novel medical elastomer which possesses an excellent surface hydrophilicity, anti-biofouling property, oxygen permeability and tensile property. PMID:16797692

  19. Effect of photografting 2-hydroxyethyl acrylate on the hemocompatibility of electrospun poly(ethylene-co-vinyl alcohol) fibroporous mats.

    Science.gov (United States)

    Mayuri, P V; Bhatt, Anugya; Joseph, Roy; Ramesh, P

    2016-03-01

    Poly(ethylene-co-vinyl alcohol) (EVAL) has been recommended as a material suitable for blood contacting applications. Effect of ethylene content and associated hydrophobicity of EVAL on the blood-material interactions have been documented in the literature. In this work, surface chemistry of EVAL substrate was altered by photografting a hydrophilic monomer, 2-hydroxyethyl acrylate (HEA) with the aid of a photoinitiator, benzophenone (BP), and the effect of surface modification on the blood-material interactions was investigated. Since the modified material was intended to be used as leukodepletion filters, a solution containing EVAL, HEA and BP was electrospun into fibroporous mats and UV treated to induce grafting. Degree of grafting, bonding between fibers and fiber diameter increased with increase in UV exposure time whereas mechanical properties showed a decreasing trend. Decreased water contact angle indicated improved wetting characteristics. In vitro hemocompatibility tests revealed that the modified EVAL surface exhibited significantly lower hemolytic activity, protein adsorption and platelet adhesion than neat EVAL. The modification did not have any substantial effect on the activation of the complement system and coagulation parameters. Photografting led to significant reduction in the adhesion of red blood cells (RBC) whereas white blood cell (WBC) consumption remained above 90%. The results implied that photografting HEA on EVAL substantially improves hemocompatibility of EVAL and when it is used as a filter, it selectively removes leukocytes and allows easy passage of other blood components. PMID:26706502

  20. A novel photosynthesis of carboxymethyl starch-stabilized silver nanoparticles.

    Science.gov (United States)

    El-Sheikh, M A

    2014-01-01

    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. PMID:24672325

  1. 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.

  2. Ultravilolet-radiation-induced graft polymerization of acrylamide onto the melt-blown polypropylene filter element by dynamic method

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    By dynamic method under UV irradiation, commercial melt-blown polypropylene (PPMB) filter element was modified with acrylamide (AAm) using benzophenone (BP) as initiator. Attenuated total reflection-Fourier transform infrared spectroscopy and scanning electron microscope verified that polyacrylamide chain was grafted on the fiber surface of PPMB filter element. Elemental content analysis with energy dispersive X-ray of fibers revealed that the polymerization content in the inner part of filter element was relatively higher than that in the outer. Degree of grafting changed with initiator concentration, monomer concentration, reaction temperature and reached 2.6% at the reaction condition: CBP=0.06 mol/L, CAAm=2.0 mol/L, irradiation time: 80 min, 60℃. Relative water flux altered with the hydrophilicity and pore size of filter element. In the antifouling test, the modified filter gave greater flux recovery (approximately 70%) after filtration of the water extract of Liuweidihuang, suggesting that the fouling layer was more easily reversible due to the hydrophilic nature of the modified filter.

  3. 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.

  4. Modified low temperature Czochralski growth of xylenol orange doped benzopheone single crystal for fabricating dual band patch antenna

    Science.gov (United States)

    Yadav, Harsh; Sinha, Nidhi; Kumar, Binay

    2016-09-01

    Organic non-linear optical pure and xylenol orange (XO) doped benzophenone (BP) single crystals have been grown by a modified Czochralski technique. A low cost CZ system was designed and fabricated that is suitable for the growth of single crystals of low melting point organic materials. Structural analysis was performed by powder and single crystal XRD. LC-HRMS spectra reveal that the dye molecules are present in the doped crystal. The linear optical characterization was carried out by UV-vis spectroscopy. In the case of the XO doped BP crystal, two absorption peaks were found at 504 nm and 620 nm. The enhancement of photoluminescence intensity of blue emission was observed in the dye doped crystal. Dielectric studies reveal that the XO doped BP has shown improved a dielectric constant with low dielectric loss. A dual band compact circular patch antenna was simulated and fabricated using the XO doped crystal. Resonant frequencies of the dual bands at 4.80 GHz and 9.22 GHz were achieved by introducing a defect ground state in the circular patch antenna. The piezoelectric coefficient (d33) value was increased from 1 to 4 pC/N by XO dye doping, which opens up the possibilities of simultaneous transducer applications.

  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. PMID:25792520

  6. High-Dielectric Constant Inorganic-Organic Hybrid Materials Prepared with Sol-Gel-Derived Crystalline BaTiO3

    Science.gov (United States)

    Pramanik, Nimai Chand; Seok, Sang Il

    2008-01-01

    The preparation of ceramic/polymer composites (BaTiO3-polymer in particular) has received much current interest for various electronic applications, because of the possibility of combining the effect of the processability of the organic components with that of the desired electrical properties of the ceramics. The synthesis of polyimide-based inorganic-organic hybrid thin films containing crystalline BaTiO3 nanoparticles and their dielectric properties are discussed. The precursor for the polyimide was prepared from benzophenone-3,3',4,4'-tetracarboxylic dianhydride (BTDA) and 4,4'-diamino-3,3'-dimethyl diphenyl methane (DADMDPM) and used as an organic matrix for a ceramic/polymer hybrid and that of the crystalline BaTiO3 nanoparticles was prepared by the wet-chemical decomposition of the [Ti(acac)3]+ complex with Ba(OH)2. The BaTiO3, prepared by the decomposition of the Ti-acac complex showed good crystallinity (average particle size = 90 nm) with better dispersibility in an organic medium (NMP). Crack-free thin films of 3.5-4.5 µm thickness were obtained by a single spin coating operation after curing the air-dried films at 150 °C. The polyimide/BaTiO3 hybrids exhibited a wide range of relative permittivity values (ɛ= 3.81-31.57) at room temperature.

  7. 3-Hydroxybenzoate:coenzyme A ligase from cell cultures of Centaurium erythraea: isolation and characterization.

    Science.gov (United States)

    Barillas, W; Beerhues, L

    2000-02-01

    In xanthone biosynthesis, 3-hydroxybenzoate:coenzyme A ligase (3HBL) supplies the starter substrate for the formation of an intermediate benzophenone. 3HBL from cell cultures of the medicinal plant Centaurium erythraea was purified to apparent homogeneity using a seven-step-procedure. The enzyme was an AMP-forming CoA ligase with a Km = 14.7 microM for 3-hydroxybenzoic acid, 8.5 microM for coenzyme A and 229 microM for ATP. The pH and temperature optima were 7.5 and 35 degrees C, respectively. In SDS-PAGE, two polypeptides of Mr 41,500 and 40,500 were detected. Both proteins were structurally related to each other as shown by tryptic digestion. Their N-termini were blocked. The difference in their apparent molecular masses could not be attributed to glycosylation. 3HBL had a native Mr of approx. 50,000 and is thus active as a monomer. PMID:10746747

  8. Functionalized polymer film surfaces via surface-initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    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

  9. Studies on the kinetics of gel formation in polyurethane acrylate cured by UV-radiation

    International Nuclear Information System (INIS)

    In this paper, the kinetics of gel formation in polyurethane acrylate initiated by UV-radiation was investigated with the help of IR spectra, in which benzophenone/benzoic ethyl ether was a mixed photo sensitizer. The reaction degrees of double-bonds changing at 1408 cm-1 of acrylates in IR were detected in the different UV exposure time. The relationship between reaction degree Pc-c = 0.325 t0.135. After a critical geloint, the reaction degrees of double-bonds existed: Pc=c (gel) > Pc=c > Pc=c(sol) and besides there was a distributional relation between gel and sol fractions in the whole processing. The critical gel point was obtained with the extrapolation method, and its experimental gel point and the theoretical modeling one were quite close to each other. The experimental curves of Pc=c, Pc=c(gel) and Pc=c(sol) functions related to gel fractions were in fairly good agreement with their theoretical modeling ones in both shape and tendency

  10. Transfer hydrogenation with abnormal dicarbene rhodium(iii) complexes containing ancillary and modular poly-pyridine ligands.

    Science.gov (United States)

    Farrell, Kevin; Melle, Philipp; Gossage, Robert A; Müller-Bunz, Helge; Albrecht, Martin

    2016-03-21

    Treatment of an abnormal dicarbene ligated rhodium(iii) dimer with 2,2'-bipyridine (bipy), 1,10-phenanthroline (phen) or 2,2':6',2''-terpyridine (terpy) results in coordination of the N-donor ligands and concomitant cleavage of the dimeric structure. Depending on the denticity of the pyridyl ligand, this situation retains one (L = terpy) or two (L = bipy, phen) flexible sites for substrate coordination. In the case of the bipy complexes, modification of the electron density at Rh, without directly affecting the steric environment about the metal centre, was achieved by the incorporation of electron-donating or electron-withdrawing substituents on the bipy backbone. The dicarbene pyridyl complexes were active in transfer hydrogenation catalysis of benzophenone at 0.15 mol% catalyst loading in a iPrOH/KOH mixture. The catalysts displayed a strong characteristic colour change (yellow to purple) after activation which allowed for visual monitoring of the status of the reaction. The colour probe and the robustness of the active catalysts proved useful for catalyst recycling. The catalytic activity sustained over five consecutive substrate batch additions and gave a maximum overall turnover number of 3100. PMID:26842739

  11. Photochemically modified ATO NPs as conductive support of Pt electrocatalysts for proton exchange membrane fuel cells

    International Nuclear Information System (INIS)

    Antimony-doped tin oxide (ATO) nanoparticles (NPs) were covalently modified with a benzophenone-silicate photoreactive organic molecule to enable the UV-mediated photoreduction of Pt(IV) on the surface of the ATO NPs to give Pt(0) NPs. The successfully synthesized Pt/ATO nanocomposites (NCs) that were based on these novel hybrid photoreactive ATO NPs showed a much better Pt dispersion than Pt/ATO NCs prepared by traditional methods. The size of the Pt NPs was below 2.8 nm for all the NCs. The prepared NCs were studied with respect to their properties as durable and active electrocatalysts for proton exchange membrane fuel cells. They were subjected to fuel-cell-relevant electrochemical characterization by rotating disc electrode cyclic voltammetry. The electrochemically active surface area was found to be significantly lower for the novel NCs than for the standard Pt/C catalyst, while on the other hand, their specific electrocatalytic activity towards the oxygen reduction reaction (ORR) was found to exceed that of the reference Pt/C by several times. The ORR activity in terms of the mass of Pt was comparable to, or greater than, that of the Pt/C. The stability towards electrochemical ageing was greatly improved for Pt/ATO NCs relative to Pt/C

  12. Development of microbial and chemical MST tools to identify the origin of the faecal pollution in bathing and shellfish harvesting waters in France.

    Science.gov (United States)

    Gourmelon, M; Caprais, M P; Mieszkin, S; Marti, R; Wéry, N; Jardé, E; Derrien, M; Jadas-Hécart, A; Communal, P Y; Jaffrezic, A; Pourcher, A M

    2010-09-01

    The microbiological quality of coastal or river waters can be affected by faecal pollution from human or animal sources. An efficient MST (Microbial Source Tracking) toolbox consisting of several host-specific markers would therefore be valuable for identifying the origin of the faecal pollution in the environment and thus for effective resource management and remediation. In this multidisciplinary study, after having tested some MST markers on faecal samples, we compared a selection of 17 parameters corresponding to chemical (steroid ratios, caffeine, and synthetic compounds), bacterial (host-specific Bacteroidales, Lactobacillus amylovorus and Bifidobacterium adolescentis) and viral (genotypes I-IV of F-specific bacteriophages, FRNAPH) markers on environmental water samples (n = 33; wastewater, runoff and river waters) with variable Escherichia coli concentrations. Eleven microbial and chemical parameters were finally chosen for our MST toolbox, based on their specificity for particular pollution sources represented by our samples and their detection in river waters impacted by human or animal pollution; these were: the human-specific chemical compounds caffeine, TCEP (tri(2-chloroethyl)phosphate) and benzophenone; the ratios of sitostanol/coprostanol and coprostanol/(coprostanol+24-ethylcopstanol); real-time PCR (Polymerase Chain Reaction) human-specific (HF183 and B. adolescentis), pig-specific (Pig-2-Bac and L. amylovorus) and ruminant-specific (Rum-2-Bac) markers; and human FRNAPH genogroup II. PMID:20709349

  13. Multi function Finishing and Pigment Printing of UV Cured Cotton/Polyester Fabrics Coated with Plasticized Epoxy Resin/ZnO Formulation

    International Nuclear Information System (INIS)

    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%.

  14. Bent CNN bond of diazo compounds, RR'(Cdbnd N+dbnd N-)

    Science.gov (United States)

    Akita, Motoko; Takahashi, Mai; Kobayashi, Keiji; Hayashi, Naoto; Tukada, Hideyuki

    2013-02-01

    The reaction of ninhydrin with benzophenone hydrazone afforded 2-diazo-3-diphenylmethylenehydrazono-1-indanone 1 and 2-diazo-1,3-bis(diphenylmethylenehydrazono)indan 2. X-ray crystal structure analyses of these products showed that the diazo functional group Cdbnd N+dbnd N- of 1 is bent by 172.9°, while that of 2 has a linear geometry. The crystal structure data of diazo compounds have been retrieved from the Cambridge Structural Database (CSD), which hit 177 entries to indicate that the angle of 172.9° in 1 lies in one of the most bent structures. The CSD search also indicated that diazo compounds consisting of a distorted diazo carbon tend to bend the Cdbnd N+dbnd N- bond. On the basis of DFT calculations (B3LYP/6-311++G(d,p)) of model compounds, it was revealed that the bending of the CNN bond is principally induced by steric factors and that the neighboring carbonyl group also plays a role in bending toward the carbonyl side owing to an electrostatic attractive interaction. The potential surface along the path of Cdbnd N+dbnd N- bending in 2-diazopropane shows a significantly shallow profile with only 4 kcal/mol needed to bend the Cdbnd N+dbnd N- bond from 180° to 160°. Thus, the bending of the diazo group in 1 is reasonable as it is provided with all of the factors for facile bending disclosed in this investigation.

  15. 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.

  16. Pros and cons of analytical methods to quantify surrogate contaminants from the challenge test in recycled polyethylene terephthalate

    International Nuclear Information System (INIS)

    Different analytical methods were optimized and applied to quantify certain surrogate contaminants (toluene, chlorobenzene, phenol, limonene and benzophenone) in samples of contaminated and recycled flakes and virgin pellets of polyethylene terephthalate (PET) coming from the industrial challenge test. A screening analysis of the PET samples was carried out by direct solid-phase microextraction (SPME) in headspace mode (HS). The methods developed and used for quantitative analysis were a) total dissolution of PET samples in dichloroacetic acid and analysis by HS-SPME coupled to gas chromatography-mass spectrometry (GC-MS) and, b) dichloromethane extraction and analysis by GC-MS. The concentration of all surrogates in the contaminated PET flakes analyzed by HS-SPME method was lower than expected according to information provided by the supplier. Dichloroacetic acid interacted with the surrogates, resulting in a tremendous decrease of limonene concentration. The degradation compounds from limonene were identified. Dichloromethane extraction and GC-MS analysis evidenced the highest values of analytes in these PET samples. Based on the foregoing data, the efficiency of the recycling process was evaluated, whereby the removal of 99.9% of the surrogates proceeding from the contaminated flakes was confirmed.

  17. 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. PMID:25827406

  18. [Skin tanning and light protection-theory, agents and analytic aspects. 1. Skin tanning and skin tanning agents].

    Science.gov (United States)

    Matissek, R

    1984-10-01

    The different approaches to achieving skin tanning with emphasis on natural tanning, due to UV radiation of the sun or solaria, and artificial tanning through tannings agents are described. In contrast to the artificial tan the natural tan is a protection against UV radiation and is caused by pigmentation (melanin formation). The artificial tanning is based on a chemical reaction usually by means of dihydroxy acetone (melanoidin formation). Reaction mechanisms by both agents are reported. The determination of dihydroxy acetone in cosmetic tanning preparations by TLC, GC, HPLC, enzymatic tests and by a new method for capillary GC including sample preparation is described. When exceeding the natural protection mechanisms the skin should be protected by physico-chemical measures. The active principles in sunscreens are the UV filtering substances. UV filters permitted in the EG are listed. 2-Hydroxy benzophenone is used as an example to explain the mechanism of UV filtering substances. Analysis of UV filtering substances in cosmetic sunscreens by TLC, GC, HPLC is described as well as a fast and simple method for separation of lipophilic UV filters followed by capillary GC determination. PMID:6506884

  19. The oxidation of PET track-etched membranes by hydrogen peroxide as an effective method to increase efficiency of UV-induced graft polymerization

    Directory of Open Access Journals (Sweden)

    Il'ya Korolkov

    2015-12-01

    Full Text Available In this article, we report on functionalization of track-etched membrane based on poly(ethylene terephthalate (PET TeMs oxidized by advanced oxidation systems and by grafting of acrylic acid using photochemical initiation technique for the purpose of increasing functionality thus expanding its practical application. Among advanced oxidation processes (H2O2/UV system had been chosen to introduce maximum concentration of carboxylic acid groups. Benzophenone (BP photo-initiator was first immobilized on the surfaces of cylindrical pores which were later filled with aq. acrylic acid solution. UV-irradiation from both sides of PET TeMs has led to the formation of grafted poly(acrylic acid (PAA chains inside the membrane nanochannels. Effect of oxygen-rich surface of PET TeMs on BP adsorption and subsequent process of photo-induced graft polymerization of acrylic acid (AA were studied by ESR. The surface of oxidized and AA grafted PET TeMs was characterized by UV-vis, ATR-FTIR, XPS spectroscopies and by SEM.

  20. UV-induced graft polymerization of acrylic acid in the sub-micronchannels of oxidized PET track-etched membrane

    Science.gov (United States)

    Korolkov, Ilya V.; Mashentseva, Anastassiya A.; Güven, Olgun; Taltenov, Abzal A.

    2015-12-01

    In this article, we report on functionalization of track-etched membrane based on poly(ethylene terephthalate) (PET TeMs) oxidized by advanced oxidation systems and by grafting of acrylic acid using photochemical initiation technique for the purpose of increasing functionality thus expanding its practical application. Among advanced oxidation processes (H2O2/UV) system had been chosen to introduce maximum concentration of carboxylic acid groups. Benzophenone (BP) photo-initiator was first immobilized on the surfaces of cylindrical pores which were later filled with aq. acrylic acid solution. UV-irradiation from both sides of PET TeMs has led to the formation of grafted poly(acrylic acid) (PAA) chains inside the membrane sub-micronchannels. Effect of oxygen-rich surface of PET TeMs on BP adsorption and subsequent process of photo-induced graft polymerization of acrylic acid (AA) were studied by ESR. The surface of oxidized and AA grafted PET TeMs was characterized by UV-vis, ATR-FTIR, XPS spectroscopies and by SEM.

  1. 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.

  2. Catalytic Transfer Hydogenation Reactions for Undergraduate Practical Programs

    Science.gov (United States)

    Hanson, R. W.

    1997-04-01

    A brief review of catalytic transfer hydrogenation (CTH) reactions is given. Attention is drawn, particularly, to the utility of ammonium formate as the hydrogen donor in this type of reaction. The reduction of aryl carbonyl compounds to the corresponding methylene derivatives by ammonium formate in the presence of 10% Pd/C at 110°C is compared to their reductive ammonation which occurs at higher temperatures in the absence of the catalyst (the Leuckart reaction). It is suggested that the low cost and simplicity of CTH reactions using ammonium formate as the hydrogen donor, together with the high yields obtained in many cases, make them excellent candidates for inclusion in undergraduate practical programmes. Laboratory instructions are given for the reduction of nitrobenzene to aniline (isolated as benzanilide), benzophenone to diphenylmethanol and fluorenone to fluorene, in all cases using ammonium formate as the hydrogen donor and 10% Pd/C as the catalyst. Thin layer chromatography shows that in each case the product is homogeneous; the yields are essentially quantitative.

  3. Luminescent single-ion magnets from Lanthanoid(III) complexes with monodentate ketone ligands

    International Nuclear Information System (INIS)

    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

  4. Nuclear energy gradients for internally contracted complete active space second-order perturbation theory: Multistate extensions

    CERN Document Server

    Vlaisavljevich, Bess

    2016-01-01

    We report the development of the theory and computer program for analytical nuclear energy gradients for (extended) multi-state 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. 142, 051103 (2015)]; in this extension, the so-called {\\lambda} equation is solved to account for the variation of the multi-state 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 c...

  5. Identification of selective enzyme inhibitors by fragment library screening.

    Science.gov (United States)

    Gao, Geng; Liu, Xuying; Pavlovsky, Alexander; Viola, Ronald E

    2010-10-01

    The microbial threat to human health is growing due to the dramatic increase in the number of multidrug-resistant organisms. The decline in effective antibiotics available to treat these growing threats has provided greater urgency to the search for new antibiotics. Clearly, new approaches must be developed against novel targets to control these resistant infectious organisms. The screening of low molecular weight compounds against new protein targets provides an opportunity to identify novel inhibitors as starting points for the development of new antibiotics. Custom fragment libraries have been assembled and screened against 3 representative forms of a key enzyme in an essential microbial biosynthetic pathway. Although each of these aspartate semialdehyde dehydrogenases (ASADHs) catalyzes the same reaction and each shares identical active site functional groups, subtle differences in enzyme structures have led to different binding selectivity among the initial hits from these fragment libraries. Amino acid analogues have been identified that show selectivity for either the gram-negative or gram-positive bacterial enzyme forms. A series of benzophenone analogues selectively inhibit the gram-negative ASADH, whereas some haloacids and substituted aromatic acids have been found to inhibit only the fungal form of ASADH. Each of these low molecular weight compounds possesses high ligand binding efficiency for their target enzyme forms. These results support the goal of designing lead compounds that will selectively target ASADHs from different microbial species. PMID:20855558

  6. Food Ingredient Extracts of Cyclopia subternata (Honeybush: Variation in Phenolic Composition and Antioxidant Capacity

    Directory of Open Access Journals (Sweden)

    Maria A. Stander

    2012-12-01

    Full Text Available Cyclopia subternata plants are traditionally used for the production of the South African herbal tea, honeybush, and recently as aqueous extracts for the food industry. A C. subternata aqueous extract and mangiferin (a major constituent are known to have anti-diabetic properties. Variation in phenolic composition and antioxidant capacity is expected due to cultivation largely from seedlings, having implications for extract standardization and quality control. Aqueous extracts from 64 seedlings of the same age, cultivated under the same environmental conditions, were analyzed for individual compound content, total polyphenol (TP content and total antioxidant capacity (TAC in a number of assays. An HPLC method was developed and validated to allow quantification of xanthones (mangiferin, isomangiferin, flavanones (hesperidin, eriocitrin, a flavone (scolymoside, a benzophenone (iriflophenone-3-C-β-glucoside and dihydrochalcones (phloretin-3',5'-di-C-β-glucoside, 3-hydroxyphloretin-3',5'-di-C-hexoside. Additional compounds were tentatively identified using mass spectrometric detection, with the presence of the 3-hydroxyphloretin-glycoside, an iriflophenone-di-O,C-hexoside, an eriodictyol-di-C-hexoside and vicenin-2 being demonstrated for the first time. Variability of the individual phenolic compound contents was generally higher than that of the TP content and TAC values. Among the phenolic compounds, scolymoside, hesperidin and iriflophenone-3-C-β-glucoside contents were the most variable. A combination of the measured parameters could be useful in product standardization by providing a basis for specifying minimum levels.

  7. 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.

  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. Photochemically modified ATO NPs as conductive support of Pt electrocatalysts for proton exchange membrane fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Ostrovsky, Stella [Bar-Ilan University, Department of Chemistry, Nanomaterials Research Center, Institute of Nanotechnology and Advanced Materials (Israel); Larsen, Mikkel Juul, E-mail: mjl@ird.dk [IRD Fuel Cells A/S (Denmark); Peled, Anna; Lellouche, Jean-Paul, E-mail: lellouj@mail.biu.ac.il [Bar-Ilan University, Department of Chemistry, Nanomaterials Research Center, Institute of Nanotechnology and Advanced Materials (Israel)

    2015-06-15

    Antimony-doped tin oxide (ATO) nanoparticles (NPs) were covalently modified with a benzophenone-silicate photoreactive organic molecule to enable the UV-mediated photoreduction of Pt(IV) on the surface of the ATO NPs to give Pt(0) NPs. The successfully synthesized Pt/ATO nanocomposites (NCs) that were based on these novel hybrid photoreactive ATO NPs showed a much better Pt dispersion than Pt/ATO NCs prepared by traditional methods. The size of the Pt NPs was below 2.8 nm for all the NCs. The prepared NCs were studied with respect to their properties as durable and active electrocatalysts for proton exchange membrane fuel cells. They were subjected to fuel-cell-relevant electrochemical characterization by rotating disc electrode cyclic voltammetry. The electrochemically active surface area was found to be significantly lower for the novel NCs than for the standard Pt/C catalyst, while on the other hand, their specific electrocatalytic activity towards the oxygen reduction reaction (ORR) was found to exceed that of the reference Pt/C by several times. The ORR activity in terms of the mass of Pt was comparable to, or greater than, that of the Pt/C. The stability towards electrochemical ageing was greatly improved for Pt/ATO NCs relative to Pt/C.

  10. Analytical procedure for quantifying five compounds suspected as possible contaminants in recycled paper/paperboard for food packaging.

    Science.gov (United States)

    Song, Y S; Park, H J; Komolprasert, V

    2000-12-01

    Because contaminants in recycled paper intended for food packaging could be a risk to public health, analytical methods are needed to identify and quantify residues of concern in paper/paperboard. The U. S. Food and Drug Administration is considering development of a guidance document for testing levels of contaminants that might be retained through paper recycling processes. An analytical procedure was developed using paper spiked with suspected contaminants at concentrations of 1-50 ppm in the paper. Benzophenone, dimethyl phthalate, anthracene, methyl stearate, and pentachlorophenol were introduced by soaking the paper in a solution in acetone at 25 degrees C for 24 h; the paper was removed and dried by evaporating the solvent with nitrogen. The model contaminant residues were extracted from the paper using ultrasonication and quantified by GC with flame ionization and electron capture detectors. Recoveries from the spiked paper were 80-109% with a repeatability of +/-4%. The method was also used to analyze commercial recycled paperboard to validate its applicability. PMID:11141258

  11. Synthesis and testing of ZnO nanoparticles for photo-initiation: experimental observation of two different non-migration initiators for bulk polymerization

    Science.gov (United States)

    Schmitt, M.

    2015-05-01

    The migration and transport of polymerization initiators are problematic for commercially used polymerization procedures. For example, UV printing of packaging generates products with potentially harmful components that come in contact with food. Enlarging the size of the initiator is the only way to prevent contamination, e.g., by gas phase transport. In this manuscript, the synthesis and advanced and full analyses of novel nanoparticle-based types of non-migration, fragmenting and non-fragmenting photo-initiators will be presented in detail. This study introduces non-fragmenting/``Norrish type II'' and fragmenting/``Norrish type I'' ZnO nanoparticle-based initiators and compares them with two commercial products, a ``Norrish type I'' initiator and a ``Norrish type II'' initiator. Therefore, inter alia, the recently developed analysis involves examining the solidification by UV-vis and the double bond content by Raman. Irradiation is performed using absolute and spectrally calibrated xenon flash lights. A novel procedure for absolute and spectral calibration of such light sources is also presented. The non-optimized ``Norrish type II'' particle-based initiator is already many times faster than benzophenone, which is a molecular initiator of the same non-fragmenting type. This experimentally observed difference in reactive particle-based systems without co-initiators is unexpected. Co-initiators are normally an additional molecular species, which leads to migration problems. The discovery of significant initiation potential resulting in a very well-dispersed organic-inorganic hybrid material suggests a new field of research opportunities at the interface of physical chemistry, polymer chemistry and engineering science, with enormous value for human health.The migration and transport of polymerization initiators are problematic for commercially used polymerization procedures. For example, UV printing of packaging generates products with potentially harmful

  12. Improvement of polymer stability by radiation grafting

    International Nuclear Information System (INIS)

    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)

  13. Reactions of ketones with uranium tetraborohydride, mechanism and stereoselectivity, synthesis and structure of uranium (IV) tetrahydroborato alkoxide complexes

    International Nuclear Information System (INIS)

    The mono- and bisalkoxide uranium complexes U(BH4)3(OCHR1R2)(THF)2 1 and U(BH4)2(OCHR1R2)2(THF)2 2 were prepared successively in tetrahydrofuran (THF) by treatment of U(BH4)4 with the corresponding ketone R1R2C = O (acetone, benzophenone, cyclohexanone, 2-methylcyclohexanone, 4-tert-butylcyclohexanone, and norcamphor). The borane BH3.THF was liberated during the formation of 1 and 2, and reacted with the ketone to give the alkoxyborane species B(OCHR1R2)nH3-n. Formation of 1 also resulted from: a) reaction of U-BH4)4 with the alkoxyborane species; b) reaction of U(BH4)4 with 2; and c) reaction of 2 with BH3.THF. The alkoxide groups of 1 and 2 rapidly exchange with those of the alkoxyborane species. The uranium complexes 1 and alkoxyborane species resulting from the reaction of U(BH4)4 with the substituted cyclohexanones or norcamphor have been separated and their hydrolysis afforded the corresponding epimeric alcohols in different proportions. The monoalkoxide compounds 1 were alternatively prepared by reaction of the ketones R1R2C = O with UCl4 in the presence of LiBH4 or by treatment of U(BH4)4 with the alcohols R1R2CHOH. The octahedral crystal structures of U(BH4)3(OCHPh2)(THF)2 1b and U(BH4)2(OCHPh2)2(THF)2 2b show that in 1b, the two equatorial THF ligands (and the two equatorial BH4 groups) are in relative cis positions whereas they are trans in 2b

  14. Offline solid-phase extraction for preconcentration of pharmaceuticals and personal care products in environmental water and their simultaneous determination using the reversed phase high-performance liquid chromatography method.

    Science.gov (United States)

    G Archana; Dhodapkar, Rita; Kumar, Anupama

    2016-09-01

    The present study reports a precise and simple offline solid-phase extraction (SPE) coupled with reversed-phase high-performance liquid chromatography (RP-HPLC) method for the simultaneous determination of five representative and commonly present pharmaceuticals and personal care products (PPCPs), a new class of emerging pollutants in the aquatic environment. The target list of analytes including ciprofloxacin, acetaminophen, caffeine benzophenone and irgasan were separated by a simple HPLC method. The column used was a reversed-phase C18 column, and the mobile phase was 1 % acetic acid and methanol (20:80 v/v) under isocratic conditions, at a flow rate of 1 mL min(-1). The analytes were separated and detected within 15 min using the photodiode array detector (PDA). The linearity of the calibration curves were obtained with correlation coefficients 0.98-0.99.The limit of detection (LOD), limit of quantification (LOQ), precision, accuracy and ruggedness demonstrated the reproducibility, specificity and sensitivity of the developed method. Prior to the analysis, the SPE was performed using a C18 cartridge to preconcentrate the targeted analytes from the environmental water samples. The developed method was applied to evaluate and fingerprint PPCPs in sewage collected from a residential engineering college campus, polluted water bodies such as Nag river and Pili river and the influent and effluent samples from a sewage treatment plant (STP) situated at Nagpur city, in the peak summer season. This method is useful for estimation of pollutants present in microquantities in the surface water bodies and treated sewage as compared to nanolevel pollutants detected by mass spectrometry (MS) detectors. PMID:27502523

  15. 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. PMID:25247795

  16. A novel photo-grafting of acrylamide onto carboxymethyl starch. 1. Utilization of CMS-g-PAAm in easy care finishing of cotton fabrics.

    Science.gov (United States)

    El-Sheikh, Manal A

    2016-11-01

    The photosensitized grafting of vinyl monomers onto a range of polymeric substrates has been the subject of particular interest in the recent past. Carboxymethyl starch (CMS)-poly acrylamide (PAAm) graft copolymer (CMS-g-PAAm) with high graft yield was successfully prepared by grafting of acrylamide onto CMS using UV irradiation in the presence of the water soluble 4-(trimethyl ammoniummethyl) benzophenone chloride photoinitiator. CMS-g-PAAm with nitrogen content of 8.3% and grafting efficiency up to 98.9% was obtained using 100% AAm, a material: liquor ratio of 1:14 and 1% photinitiator at 30°C for 1h of UV irradiation. The synthesis of CMS-g-PAAm was confirmed by FTIR and Nitrogen content (%). Surface morphology of CMS and surface morphological changes of CMS after grafting with AAm were studied using SEM. Thermal properties of both CMS and CMS-g-PAAm were studied using TGA and DSC. To impart easy care finishing to cotton fabrics, aqueous formulations of: CMS-g-PAAm, dimethylol dihydroxy ethylene urea (DMDHEU), CMS-g-PAAm-DMDHEU mixture or methylolated CMS-g-PAAm were used. Cotton fabrics were padded in these formulations, squeezed to a wet pick up 100%, dried at 100°C for 5min, cured at 150°C for 5min, washed at 50°C for 10min and air-dried. CRA (crease recovery angle) of untreated fabrics and fabrics finished with a mixture of 2% CMS-g-PAAm and 10% DMDHEU or methylolated CMS-g-PAAm (10% formaldehyde) were: 136°, 190°, 288° respectively. Increasing the number of washing cycles up to five cycles results in an insignificant decrease in the CRA and a significant decrease in RF (releasable formaldehyde) of finished fabric samples. The morphologies of the finished and unfinished cotton fabrics were performed by SEM. PMID:27516255

  17. 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

  18. Polydopamine-coated magnetic nanoparticles for isolation and enrichment of estrogenic compounds from surface water samples followed by liquid chromatography-tandem mass spectrometry determination.

    Science.gov (United States)

    Capriotti, Anna Laura; Cavaliere, Chiara; La Barbera, Giorgia; Piovesana, Susy; Samperi, Roberto; Zenezini Chiozzi, Riccardo; Laganà, Aldo

    2016-06-01

    Estrogens, phytoestrogens, and mycoestrogens may enter into the surface waters from different sources, such as effluents of municipal wastewater treatment plants, industrial plants, and animal farms and runoff from agricultural areas. In this work, a multiresidue analytical method for the determination of 17 natural estrogenic compounds, including four steroid estrogens, six mycoestrogens, and seven phytoestrogens, in river water samples has been developed. (Fe3O4)-based magnetic nanoparticles coated by polydopamine (Fe3O4@pDA) were used for dispersive solid-phase extraction, and the final extract was analyzed by ultra-high performance liquid chromatography coupled with tandem mass spectrometry. The Fe3O4 magnetic nanoparticles were prepared by a co-precipitation procedure, coated by pDA, and characterized by scanning electron microscopy, infrared spectroscopy, and elemental analysis. The sample preparation method was optimized in terms of extraction recovery, matrix effect, selectivity, trueness, precision, method limits of detection, and method limits of quantification (MLOQs). For all the 17 analytes, recoveries were >70 % and matrix effects were below 30 % when 25 mL of river water sample was treated with 90 mg of Fe3O4@pDA nanoparticles. Selectivity was tested by spiking river water samples with 50 other compounds (mycotoxins, antibacterials, conjugated hormones, UV filters, alkylphenols, etc.), and only aflatoxins and some benzophenones showed recoveries >60 %. This method proved to be simple and robust and allowed the determination of natural estrogenic compounds belonging to different classes in surface waters with MLOQs ranging between 0.003 and 0.1 μg L(-1). Graphical Abstract Determination of natural estrogenic compounds in water by magnetic solid phase extraction followed by liquid chromatography-tandem mass spectrometry analysis. PMID:27032407

  19. Synthesis and biochemical evaluation of benzoylbenzophenone thiosemicarbazone analogues as potent and selective inhibitors of cathepsin L.

    Science.gov (United States)

    Parker, Erica N; Song, Jiangli; Kishore Kumar, G D; Odutola, Samuel O; Chavarria, Gustavo E; Charlton-Sevcik, Amanda K; Strecker, Tracy E; Barnes, Ashleigh L; Sudhan, Dhivya R; Wittenborn, Thomas R; Siemann, Dietmar W; Horsman, Michael R; Chaplin, David J; Trawick, Mary Lynn; Pinney, Kevin G

    2015-11-01

    Upregulation of cathepsin L in a variety of tumors and its ability to promote cancer cell invasion and migration through degradation of the extracellular matrix suggest that cathepsin L is a promising biological target for the development of anti-metastatic agents. Based on encouraging results from studies on benzophenone thiosemicarbazone cathepsin inhibitors, a series of fourteen benzoylbenzophenone thiosemicarbazone analogues were designed, synthesized, and evaluated for their inhibitory activity against cathepsins L and B. Thiosemicarbazone inhibitors 3-benzoylbenzophenone thiosemicarbazone 1, 1,3-bis(4-fluorobenzoyl)benzene thiosemicarbazone 8, and 1,3-bis(2-fluorobenzoyl)-5-bromobenzene thiosemicarbazone 32 displayed the greatest potency against cathepsin L with low IC50 values of 9.9 nM, 14.4 nM, and 8.1 nM, respectively. The benzoylbenzophenone thiosemicarbazone analogues evaluated were selective in their inhibition of cathepsin L compared to cathepsin B. Thiosemicarbazone analogue 32 inhibited invasion through Matrigel of MDA-MB-231 breast cancer cells by 70% at 10 μM. Thiosemicarbazone analogue 8 significantly inhibited the invasive potential of PC-3ML prostate cancer cells by 92% at 5 μM. The most active cathepsin L inhibitors from this benzoylbenzophenone thiosemicarbazone series (1, 8, and 32) displayed low cytotoxicity toward normal primary cells [in this case human umbilical vein endothelial cells (HUVECs)]. In an initial in vivo study, 3-benzoylbenzophenone thiosemicarbazone (1) was well-tolerated in a CDF1 mouse model bearing an implanted C3H mammary carcinoma, and showed efficacy in tumor growth delay. Low cytotoxicity, inhibition of cell invasion, and in vivo tolerability are desirable characteristics for anti-metastatic agents functioning through an inhibition of cathepsin L. Active members of this structurally diverse group of benzoylbenzophenone thiosemicarbazone cathepsin L inhibitors show promise as potential anti-metastatic, pre

  20. Combined effects of pharmaceuticals, personal care products, biocides and organic contaminants on the growth of Skeletonema pseudocostatum.

    Science.gov (United States)

    Petersen, Karina; Heiaas, Harald Hasle; Tollefsen, Knut Erik

    2014-05-01

    Organisms in the environment are exposed to a number of pollutants from different compound groups. In addition to the classic pollutants like the polychlorinated biphenyls, polyaromatic hydrocarbons (PAHs), alkylphenols, biocides, etc. other compound groups of concern are constantly emerging. Pharmaceuticals and personal care products (PPCPs) can be expected to co-occur with other organic contaminants like biocides, PAHs and alkylphenols in areas affected by wastewater, industrial effluents and intensive recreational activity. In this study, representatives from these four different compound groups were tested individually and in mixtures in a growth inhibition assay with the marine algae Skeletonema pseudocostatum (formerly Skeletonema costatum) to determine whether the combined effects could be predicted by models for additive effects; the concentration addition (CA) and independent action (IA) prediction model. The eleven tested compounds reduced the growth of S. pseudocostatum in the microplate test in a concentration-dependent manner. The order of toxicity of these chemicals were irgarol>fluoxetine>diuron>benzo(a)pyrene>thioguanine>triclosan>propranolol>benzophenone 3>cetrimonium bromide>4-tert-octylphenol>endosulfan. Several binary mixtures and a mixture of eight compounds from the four different compound groups were tested. All tested mixtures were additive as model deviation ratios, the deviation between experimental and predicted effect concentrations, were within a factor of 2 from one or both prediction models (e.g. CA and IA). Interestingly, a concentration dependent shift from IA to CA, potentially due to activation of similar toxicity pathways at higher concentrations, was observed for the mixture of eight compounds. The combined effects of the multi-compound mixture were clearly additive and it should therefore be expected that PPCPs, biocides, PAHs and alkylphenols will collectively contribute to the risk in areas contaminated by such complex

  1. 液晶显示器用聚酰亚胺取向膜的合成与性能研究Ⅱ.主链含柔性基团的聚酰亚胺液晶取向膜的合成与性能研究%Synthesis and Characterization of polyimide alignment films for LCDⅡ.Synthesis and charactenization of polyimide alignment film containting flexible linkage in the backbones

    Institute of Scientific and Technical Information of China (English)

    刘金刚; 王强; 朱普坤; 李佐邦; 杨士勇

    2000-01-01

      在以前的工作中,对液晶显示器(LCD)用聚酰亚胺取向膜进行了分子设计,并在此基础上合成了一类双醚二胺单体。本文采用所合成的两种双醚二胺单体:4,4'-双(氨基苯氧基)二苯甲酮(BAPB)与单醚二酐:3,3',4,4'-二苯醚四羧酸二酐(ODPA)合成了一种主链含柔性基团(—O—)的有机可溶性聚酰亚胺(PI)。对其进行了热性能、电性能、电光性能等表征,证明所合成的PI对液晶分子具有较好的取向效果,具有一定的应用前景。%  The molecular structure of polyimide alignment layer for Liquid Crystal Display(LCD) was designed in our previous work. In this research, according to the result of the design, a kind of polyimide alignment layer was synthesized by using the synthesized double-ether diamine monomers: 4,4'-bis(aminophenoxy)benzophenone(BAPB), 4,4'-bis(aminophenoxy)propane(BAPP) and a single-ether dianhydride monomer: 3,3',4,4'-oxydiphthalic dianhydride(ODPA). Because of the ether bonds in the molecular chain, the synthesized polyimide could be solved in organic solvents. The thermal properties, electrical properties, electro-optical properties were characterized at the same time.

  2. Biodegradation of crystal violet by Agrobacterium radiobacter.

    Science.gov (United States)

    Parshetti, G K; Parshetti, S G; Telke, A A; Kalyani, D C; Doong, R A; Govindwar, S P

    2011-01-01

    Agrobacterium radiobacter MTCC 8161 completely decolorized the Crystal Violet with 8 hr (10 mg/L) at static anoxic conditions. The decreased decolorization capability by A. radiobacter was observed, when the Crystal Violet concentration was increased from 10 to 100 mg/L. Semi-synthetic medium containing 1% yeast extract and 0.1% NH4C1 has shown 100% decolorization of Crystal Violet within 5 hr. A complete degradation of Crystal Violet by A. radiobacter was observed up to 7 cycles of repeated addition (10 mg/L). When the effect of increasing inoculum concentration on decolorization of Crystal Violet (100 mg/L) was studied, maximum decolorization was observed with 15% inoculum concentration. A significant increase in the activities of laccase (184%) and aminopyrine N-demethylase (300%) in cells obtained after decolorization indicated the involvement of these enzymes in decolorization process. The intermediates formed during the degradation of Crystal Violet were analyzed by gas chromatography and mass spectroscopy (GC/MS). It was detected the presence of N,N,N',N"-tetramethylpararosaniline, [N, N-dimethylaminophenyl] [N-methylaminophenyl] benzophenone, N, N-dimethylaminobenzaldehyde, 4-methyl amino phenol and phenol. We proposed the hypothetical metabolic pathway of Crystal Violet biodegradation by A. radiobacter. Phytotoxicity and microbial toxicity study showed that Crystal Violet biodegradation metabolites were less toxic to bacteria (A. radiobacter, P. aurugenosa and A. vinelandii) contributing to soil fertility and for four kinds of plants (Sorghum bicolor Vigna radiata, Lens culinaris and Triticum aestivum) which are most sensitive, fast growing and commonly used in Indian agriculture. PMID:22128547

  3. Bioassay guided purification of the antimicrobial fraction of a Brazilian propolis from Bahia state

    Directory of Open Access Journals (Sweden)

    de Alencar Severino

    2009-07-01

    Full Text Available Abstract Background Brazilian propolis type 6 (Atlantic forest, Bahia is distinct from the other types of propolis especially due to absence of flavonoids and presence of other non-polar, long chain compounds, but presenting good in vitro and in vivo antimicrobial activity. Several authors have suggested that fatty acids found in this propolis might be responsible for its antimicrobial activity; however, so far no evidence concerning this finding has been reported in the literature. The goals of this study were to evaluate the antibacterial activity of the main pure fatty acids in the ethanolic extract and fractions and elucidate the chemical nature of the bioactive compounds isolated from Brazilian propolis type 6. Methods Brazilian propolis type 6 ethanolic extract (EEP, hexane fraction (H-Fr, major fatty acids, and isolated sub-fractions were analyzed using high performance liquid chromatography (HPLC, high resolution gas chromatography with flame ionization detection (HRGC-FID, and gas chromatography-mass spectrometry (GC-MS. Three sub-fractions of H-Fr were obtained through preparative HPLC. Antimicrobial activity of EEP, H-Fr, sub-fractions, and fatty acids were tested against Staphyloccus aureus ATCC 25923 and Streptococcus mutans Ingbritt 1600 using minimum inhibitory concentration (MIC and minimum bactericidal concentration (MBC. Results EEP and H-Fr inhibited the growth of the microorganisms tested; nevertheless, no antimicrobial activity was found for the major fatty acids. The three sub-fractions (1, 2, and 3 were isolated from H-Fr by preparative HPLC and only sub-fraction 1 showed antimicrobial activity. Conclusion a The major fatty acids tested were not responsible for the antimicrobial activity of propolis type 6; b Sub-fraction 1, belonging to the benzophenone class, was responsible for the antimicrobial activity observed in the present study. The identification of the bioactive compound will improve the development of more

  4. Endocrine disrupting chemicals and other substances of concern in food contact materials: an updated review of exposure, effect and risk assessment.

    Science.gov (United States)

    Muncke, Jane

    2011-10-01

    Food contact materials (FCM) are an underestimated source of chemical food contaminants and a potentially relevant route of human exposure to endocrine disrupting chemicals (EDCs). Quantifying the exposure of the general population to substances from FCM relies on estimates of food consumption and leaching into food. Recent studies using polycarbonate plastics show that food simulants do not always predict worst-case leaching of bisphenol A, a common FCM substance. Also, exposure of children to FCM substances is not always realistically predicted using the common conventions and thus possibly misjudged. Further, the exposure of the whole population to substances leaching into dry foods is underestimated. Consumers are exposed to low levels of substances from FCM across their entire lives. Effects of these compounds currently are assessed with a focus on mutagenicity and genotoxicity. This approach however neglects integrating recent new toxicological findings, like endocrine disruption, mixture toxicity, and developmental toxicity. According to these new toxicology paradigms women of childbearing age and during pregnancy are a new sensitive population group requiring more attention. Furthermore, in overweight and obese persons a change in the metabolism of xenobiotics is observed, possibly implying that this group of consumers is insufficiently protected by current risk assessment practice. Innovations in FCM risk assessment should therefore include routine testing for EDCs and an assessment of the whole migrate toxicity of a food packaging, taking into account all sensitive population groups. In this article I focus on recent issues of interest concerning either exposure to or effects of FCM-related substances. Further, I review the use of benzophenones and organotins, two groups of known or suspected EDCs, in FCM authorized in the US and EU. PMID:21073950

  5. Observation of Emerging Photoinitiator Additives in Household Environment and Sewage Sludge in China.

    Science.gov (United States)

    Liu, Runzeng; Lin, Yongfeng; Hu, Fanbao; Liu, Ruirui; Ruan, Ting; Jiang, Guibin

    2016-01-01

    Photoinitiators (PIs) are widely used additives in industrial polymerization process, the contamination of which through migration into foodstuffs has been subjected to increasing public scrutiny. Nevertheless, little attention has been paid to the PI residue levels and potential exposure pathways from other environmental compartments. In the present study, the occurrence of PI additives with discrete molecular structures, that is, nine benzophenones (BZPs), four thioxanthones (TXs), and eight amine co-initiators (ACIs), was investigated in commercial products, indoor dust and sewage sludge samples. Nine PI compounds were positively detected in ultraviolet curable resins with concentrations of ∑PIs (sum of the detected PIs) up to 2.51 × 10(4) ng/g, and 20 PIs can be found in food contact materials with concentrations of ∑PIs varying from 65.9 to 6.93 × 10(3) ng/g. The wide usage of PIs in commercial products led to the occurrence of 19 PIs in indoor dust, with concentrations of ∑PIs in the range of 245-5.68 × 10(3) ng/g. Meanwhile, all 21 targeted PIs could be identified in the sewage sludge, with concentrations from 67.6 to 2.03 × 10(3) ng/g. Distinct PI composition profiles were observed in different investigated compartments, and BZPs were the dominant homologues in all samples. Most of the target PIs were further identified as class III chemicals by toxic hazard estimation algorithm (Toxtree), which indicates the compounds might be of significant toxicity or have reactive functional groups. PMID:26649800

  6. UV filters bioaccumulation in fish from Iberian river basins

    International Nuclear Information System (INIS)

    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

  7. The frequency and causes of photoallergic contact dermatitis among dermatology outpatients.

    Science.gov (United States)

    Spiewak, Radoslaw

    2013-01-01

    Too many patients with photoallergy remain undiagnosed due to unsatisfactory knowledge among doctors and limited access to photopatch testing. The objectives of this study were to analyze the frequency of patients requiring diagnostic work-up for photoallergic contact dermatitis among dermatology patients, and to identify the causative photosensitizers. This prospective study involved 1000 consecutive, first-referred dermatology outpatients. All patients with a history of dermatitis induced or aggravated by exposure to light were qualified for photopatch testing. In the study group, 36 (3.6%; 95%CI: 2.4-4.8%) persons required photopatch testing based on their clinical symptoms. As the total number of patients requiring patch tests of any kind amounted to 205, the percentage of photopatch tested patients among all patch-tested patients was 17.5% (95%CI: 12.2-22.8%). Photoallergic contact dermatitis was ultimately confirmed in 15 (1.5%; 0.7-2.3%) persons: 7 females and 8 males aged 6-60 (median 33) years. Nine patients turned out photoallergic to at least one nonsteroidal antiinflammatory drug, with ketoprofen photoallergy being most frequent (5 patients, in each case clinically relevant), followed by etofenamate (4 non-relevant reactions) and diclofenac (1 relevant reaction). Five patients were positive to at least one organic sunscreen, most frequently to benzophenone-3 (2 patients). "Classical" contact allergy to tested photohaptens was found in 15 persons, including 7 with coexisting photoallergy. In conclusion, patients requiring diagnostic work-up for photoallergy constitute a relevant group among dermatology patients, therefore, it seems advisable that all second-level dermatology referral centers be capable of photopatch testing. Due attention should also be paid to photoallergy in dermatology training. PMID:24476609

  8. The anti-cancer agent guttiferone-A permeabilizes mitochondrial membrane: Ensuing energetic and oxidative stress implications

    International Nuclear Information System (INIS)

    Guttiferone-A (GA) is a natural occurring polyisoprenylated benzophenone with cytotoxic action in vitro and anti-tumor action in rodent models. We addressed a potential involvement of mitochondria in GA toxicity (1-25 μM) toward cancer cells by employing both hepatic carcinoma (HepG2) cells and succinate-energized mitochondria, isolated from rat liver. In HepG2 cells GA decreased viability, dissipated mitochondrial membrane potential, depleted ATP and increased reactive oxygen species (ROS) levels. In isolated rat-liver mitochondria GA promoted membrane fluidity increase, cyclosporine A/EGTA-insensitive membrane permeabilization, uncoupling (membrane potential dissipation/state 4 respiration rate increase), Ca2+ efflux, ATP depletion, NAD(P)H depletion/oxidation and ROS levels increase. All effects in cells, except mitochondrial membrane potential dissipation, as well as NADPH depletion/oxidation and permeabilization in isolated mitochondria, were partly prevented by the a NAD(P)H regenerating substrate isocitrate. The results suggest the following sequence of events: 1) GA interaction with mitochondrial membrane promoting its permeabilization; 2) mitochondrial membrane potential dissipation; 3) NAD(P)H oxidation/depletion due to inability of membrane potential-sensitive NADP+ transhydrogenase of sustaining its reduced state; 4) ROS accumulation inside mitochondria and cells; 5) additional mitochondrial membrane permeabilization due to ROS; and 6) ATP depletion. These GA actions are potentially implicated in the well-documented anti-cancer property of GA/structure related compounds. - Graphical abstract: Guttiferone-A permeabilizes mitochondrial membrane and induces cancer cell death Display Omitted Highlights: → We addressed the involvement of mitochondria in guttiferone (GA) toxicity toward cancer cells. → GA promoted membrane permeabilization, membrane potential dissipation, NAD(P)H depletion, ROS accumulation and ATP depletion. → These actions could be

  9. 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 Leachate from landfills in areas receiving greater amounts of precipitation had greater frequencies of CEC detections and concentrations in leachate than landfills receiving less precipitation.

  10. Photodegradation of (-)-epigallocatechin-3-gallate in topical cream formulations and its photostabilization.

    Science.gov (United States)

    Bianchi, Anna; Marchetti, Nicola; Scalia, Santo

    2011-12-01

    The aim of the study was to examine the photostability of the major catechin of green tea, (-)-epigallocatechin-3-gallate (EGCG), which possesses important antioxidant and skin photoprotective properties. In order to simulate realistic conditions of use of topical preparations, the photolysis studies were performed in model creams (oil-in-water emulsions) containing 1% (w/w) EGCG and exposed to a solar simulator at an irradiance corresponding to natural sunlight. The extent of photodegradation was measured by HPLC-UV and HPLC-ESI-MS. EGCG was found to decompose by 68.9±2.3%, after 1h irradiation. Addition of the coantioxidants, vitamin E or butylated hydroxytoluene to the emulsion formulation, significantly enhanced the photolability of the catechin, the EGCG loss reached 85.7±1.3% and 80.5±1.4%, respectively. On the other hand, inclusion of the UVB (290-320nm) filter, ethylhexyl methoxycinnamate in the cream produced a small but significant reduction of EGCG photodegradation to 61.0±2.9%, while the UVA (320-400nm) filter, butyl methoxydibenzoylmethane was ineffective (EGCG degradation, 67.8±1.5%). A more marked decrease in the light-induced decomposition of EGCG to 51.6±2.7% was achieved, under the same conditions, using the water-soluble UVB filter, benzophenone-4 (BP-4). This effect was concentration dependent, maximal EGCG photostabilization (catechin loss, 29.4±2.2%) was attained in the presence of 2.1% (w/w) BP-4. Therefore, BP-4 represents a useful additive to improve the light stability of EGCG in topical formulations for skin photoprotection. PMID:21807473

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

    Science.gov (United States)

    Janzen, Niklas; Banzhaf, Stefan; Scheytt, Traugott; Bester, Kai

    2009-11-01

    A technical scale activated soil filter has been used to study the elimination rates of diverse environmentally relevant micro pollutants from storm and waste water. The filter was made of layers of peat, sand and gravel. The upper (organic) layer was planted with reed (phragmites australis) 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), 2,6-di-tert-butyl-1,4-benzoquinone (2,6-DTB-1,4-BQ), 1,1-biphenyl-3,3-dimethyl (1,1-BP-3,3-DM) and dibenzyl (DB) have been included in this study. The chemical characteristics of these compounds ranged from the hydrophilic (pK(OW) 2.6) to the lipophilic (pK(OW) 5) properties. For the elimination studies, synthetic waste water spiked to 3000 ng L(-1) with the selected compounds was used. Elimination rates with low hydraulic load (61 L m(-2)d(-1), water retention time: 2d) were higher than 96%. During a storm water simulation experiment (hydraulic load: 255 L m(-2), water retention time: <1h), the elimination rates of the most analytes decreased to 79-96%. The elimination performance of the hydrophilic compound NBBS declined to 21%. Balancing studies including the soil of the filter system revealed that degradation or transformation were both relevant elimination mechanism. PMID:19828173

  12. 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. PMID:26018285

  13. Development and application of a HPLC method for eight sunscreen agents in suncare products.

    Science.gov (United States)

    Peruchi, L M; Rath, S

    2012-06-01

    This work describes the development, validation and application of a simple and fast high-performance liquid chromatography-with diode array dectection (HPLC-DAD) method for the determination of eight sunscreen agents: benzophenone-3, octocrylene, ethylhexyl methoxycinnamate, ethylhexyl salicylate, homosalate (used in two isomeric forms), butyl methoxydibenzoylmethane, 4-methylbenzylidene camphor and ethylhexyl dimethyl PABA in sunscreen formulations. The separation of the eight sunscreen compounds was achieved using an ACE C18 column (250 × 4.6 mm, 5 μm), with a column temperature 20°C, and a mobile phase of 88 : 12 (v/v) methanol-water with isocratic elution. Column temperature strongly influences the retention time and resolution of the compounds. The flow rate was 1.0 mL min(-1) and quantitation was performed by external calibration at the maximum wavelength of each compound. The sample preparation was simple and consisted basically of sample dilution with methanol, centrifugation and filtration in syringe filters before quantitation. Total run time was 18 min. The method was validated according to the parameters: linear range, linearity, selectivity, intra-day and inter-day precision and accuracy. Ten samples of sunscreen emulsions commercially available in Brazil (SPF 30) from different manufacturers were analysed using the proposed method. The number of the sunscreen agents varied between one and five in a single sample. The concentrations of all compounds were in the range of 0.9-10% (w/w) and were in accordance with the current Brazilian legislation. PMID:22214440

  14. Skin absorption and human exposure estimation of three widely discussed UV filters in sunscreens--In vitro study mimicking real-life consumer habits.

    Science.gov (United States)

    Klimová, Z; Hojerová, J; Beránková, M

    2015-09-01

    Due to health concerns about safety, three UV-filters (Benzophenone-3, BP3, 10%; Ethylhexyl Methoxycinnamate, EHMC, 10%; Butyl Methoxydibenzoylmethane, BMDBM; 5%) were examined in vitro for absorption on full-thickness pig-ear skin, mimicking human in-use conditions. Kinetic profiles confirmed the rapid permeation of BP3; after the first hour of skin (frozen-stored) exposure to 2 mg/cm(2) (W/O sunscreen; recommended but unrealistic amount), about 0.5% of the applied dose passed into the receptor fluid. The absorption rate of filters was higher from W/O than from O/W emulsions. The fresh/frozen-stored skin permeability coefficient (0.83-0.54) for each UV filter was taken into account. Systemic Exposure Dosage of BP3, EHMC, BMDBM for humans as a consequence of (i) whole-body and (ii) face treatment with 0.5 mg/cm(2) of W/O sunscreen for 6-h skin exposure followed by washing and subsequent 18-h permeation (a realistic scenario) were estimated to be (i) 4744, 1032 and 1036 μg/kg-bw/day, and (ii) 153, 33 and 34 μg/kg-bw/day, respectively. From Margin of Safety for BP3, EHMC and BMDBM (i) 42, 485 and 192 as well as (ii) 1307; 15,151 and 5882, respectively, only the value of 42 (<100) for BP3 indicated a possible health risk. Escalation of a phobia towards all organic UV filters is undesirable. PMID:26151237

  15. Development of palm oil-based UV-curable epoxy acrylate and urethane acrylate resins for wood coating application

    International Nuclear Information System (INIS)

    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)

  16. Development of palm oil-based UV-curable epoxy acrylate and urethane acrylate resins for wood coating application

    International Nuclear Information System (INIS)

    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

  17. On the mechanism of the Di-π-methane rearrangement of bicyclo[3.2.1]octa-2,6-diene: Deuterium labeling and generation of diradical intermediates via photolysis and thermolysis of appropriate azoalkanes

    International Nuclear Information System (INIS)

    The direct (254 nm) and acetone-sensitized (300 nm) photolyses of 2,4,4-trideuteriobicyclo[3.2.1]octa-2,6-diene (D-1) gave exclusively 3,5,5-trideuteriotricyclo[4.2.0.0]oct-3-ene (D-7) and 2,6,6-trideuteriotricyclo[3.2.1.0]oct-3-ene (D-8) but no rearranged diene, namely, 2,8,8-trideuteriobicyclo[3.2.1]octa-2,6-diene (D-1'). Pyrolysis (400 degree C) and direct (334 nm) and benzophenone-sensitized (364 nm) photolyses of the azoalkane 3,5,5-trideuterio-9,10-diazatricyclo[4.4.0.0]deca-3,9-diene (D-9) afforded a mixture of tricyclooctenes D-7 (major product) and D-8 and bicyclooctadiene D-1, but no rearranged diene D-1'. These three modes of denitrogenation of the azoalkane 2,2,7-trideuterio-4,5-diazatricyclo[4.3.1.0]deca-4,8-diene (D-10) led only to the tricyclooctene D-8 (major product) and equal amounts of the bicyclooctadienes D-1 and D-1'. Distinct temperature profiles were observed in the product fingerprints of the direct photolysis (334 nm) of the azoalkanes 9 and 10. For both azoalkanes 9 and 10 the quantum yields of denitrogenation increased with rising temperature. In none of these transformations could bicyclo[3.3.0]octa-2,7-diene (2) be detected. These results imply that the di-π-methane rearrangement of the bicyclooctadienes 1 (D-1) and the denitrogenations of the azoalkanes 9 (D-9) and 10 (D-10) are disjoint chemical events. The intervention of diazenyl diradicals (one-bond cleavage of the azoalkanes) is postulated to be responsible for this disparity. The intervention of cyclopropyldicarbinyl diradical 3 as bona fide reaction intermediate in the di-π-methane rearrangement of bicyclooctadiene 1 is questioned

  18. Garcinol promotes neurogenesis in rat cortical progenitor cells through the duration of extracellular signal-regulated kinase signaling.

    Science.gov (United States)

    Weng, Meng-Shih; Liao, Chiung-Ho; Yu, Sheng-Yung; Lin, Jen-Kun

    2011-02-01

    Garcinol is a polyisoprenylated benzophenone derivative found in Garcinia indica fruit rind and other species. The potential antioxidative and neuroprotective effects of garcinol in rat cortical astrocyte were demonstrated in our laboratory recently. Here, the effects of garcinol on the neuritogenesis process in cultured cortical progenitor cells were investigated to understand the roles of garcinol in neuronal survival and differentiation. These cells, derived from embryonic day 17 rats, differentiated into EGF-responsive neural precursor cells, would further form neurospheres. Our data exhibited garcinol induced neurite outgrowth in early developing EGF-treated neurospheres and significantly enhanced the expression of neuronal proteins, microtubule-associated protein 2 (MAP-2), and glial fibrillary acidic protein (GFAP). Furthermore, the neuronal marker, high-molecular-weight subunit of neurofilaments (NFH), was highly expressed after 5 μM garcinol treatment in neural precursor cells for 20 days. To identify the extracellular mechanism, rat cortical progenitor cells were treated garcinol and accordingly mediated the sustained activation of extracellular signal-regulated kinase (ERK) for different periods up to 20 h. In this regard, NMDA receptor-mediated calcium influx led to excitotoxic death and activated tyrosine phosphatase which limited the duration of ERK in cultured neurons. MK801, the NMDA receptor antagonist, treatment also induced the sustained phosphorylation of ERK and therefore enhanced neuronal survival. In our observation, garcinol treatment reduced growth factor deprivation-mediated cell death and nuclear import of C/EBPβ levels. Noteworthy, garcinol could promote neurite outgrowth in EGF-responsive neural precursor cells and modulate the ERK pathway in the enhancement of neuronal survival. PMID:21214247

  19. 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. PMID:26517997

  20. 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.

  1. 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.

  2. Occurrence, fate and risk assessment of personal care products in river-groundwater interface.

    Science.gov (United States)

    Serra-Roig, Maria Pau; Jurado, Anna; Díaz-Cruz, M Silvia; Vázquez-Suñé, Enric; Pujades, Estanislao; Barceló, Damià

    2016-10-15

    This work presents the occurrence and fate of selected personal care products (PCPs) in the urban river-groundwater interface. To this end, urban river and groundwater samples were collected in Sant Adrià del Besòs (NE of Spain) and a total of 16 PCPs were analyzed including benzophenone derivatives, camphor derivatives, p-aminobenzoic acid derivatives, triazoles and parabens in three different campaigns (from May 2010 to July 2014). These compounds reach the aquifer through the recharge of Besòs River that receives large amounts of effluents from waste water treatment plants. Results have shown that most of the compounds were not or barely detected (maximum concentrations around 200ng/L) in groundwater samples during the different sampling campaigns. Only two triazoles, namely benzotriazole (BZT) and methyl benzotriazol (MeBZT) were found at high concentrations in groundwater samples (maximum concentration around 2000ng/L). The fate of PCPs in the aquifer was assessed using mixing analysis considering the seasonal variability of the Besòs River. Overall, measured groundwater concentrations were significantly much lower than those estimated by the mixing of the river water. This observation suggested that most of the PCPs are naturally removed when river water infiltrates the aquifer. However, some compounds were more persistent in the aquifer. These compounds were in descending order: the triazoles BZT and MeBZT followed by the camphor derivative 4MBC and the paraben MePB. The measured concentrations allowed us to assess the environmental risk posed by the selected UV-filters and parabens in the river and groundwater samples. Hazard Quotients (HQs) for different aquatic species were calculated in order to characterize the ecotoxicity potential of the studied compounds in the river-groundwater interface. HQ values were always below 1 indicating that at the concentrations observed in the surface or aquifer water of Besòs River these compounds pose no risk to

  3. The effects of binary UV filter mixtures on the midge Chironomus riparius.

    Science.gov (United States)

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

    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 0.1mg/L 4MBC but returned to normal levels after exposure to mixtures of 4MBC with 0.1, 1, and 10mg/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. PMID:26971216

  4. 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. PMID:27315091

  5. 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.

  6. 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. PMID:27089421

  7. Synthesis and characterization of heat-resistant and highly adherent copolyimide%高耐热高附着力共聚型聚酰亚胺的合成与表征

    Institute of Scientific and Technical Information of China (English)

    廖海星

    2011-01-01

    以自制的二胺-二(3-胺基苯)-3,5-二(三氟甲基)苯基氧化膦(mDA6FPPO),4,4’-(1,3-苯二醚)二胺( PDODA)和二酐二苯酮四酸二酐(BTDA)进行共聚制得了高耐热高附着力的难溶性聚酰亚胺.测定了其特性粘度为0.414 dL/g;在氮气氛中5%的热分解温度(Td)高达580℃,10%热分解温度(Td)达607℃;附着力实验表明氧膦的引入提高了聚酰亚胺的附着力.%Heat-resistant and highly adherent copolyimide was prepared by using bis(3-aminophenyl)-3,5-bis(trifluoromethyl)phenyl phosphine oxide(mDA6FPP0) , 4,4'-(1,3-phenyle-nedioxy) dianiline(PDODA) and 3,3' , 4,4'-benzophenone tetracarboxylic dianhydride (BTDA). It was found that the solubility was poor in organic solvents. The intrinsic viscosity of the polymer was tested to be 0. 414 dL/g. The thermal decomposition temperature (Td) of 5% loss in N2 was observed to be 580℃ and 10% loss to be 607℃. Adhesiveness test proved that adhesiveness was improved when phosphine oxide was introduced.

  8. Endocrine activity and developmental toxicity of cosmetic UV filters--an update

    International Nuclear Information System (INIS)

    UV filters represent a new class of endocrine active chemicals. In vitro, 8/9 chemicals showed estrogenic (MCF-7 cells), and 2/9 antiandrogenic activity (MDA-kb2 cells). Six/nine filters (benzophenone (Bp)-1, Bp-2, Bp-3, 3-benzylidene camphor (3-BC), 4-methylbenzylidene camphor (4-MBC), octyl-methoxycinnamate (OMC)) increased uterine weight in immature rats. 3-Benzylidene camphor and 4-MBC displaced 16α125I-estradiol from human estrogen receptor (ER)β , not ERα. Developmental toxicity of 4-MBC (0.7-47 mg/kg body weight/day) and 3-BC (0.24-7 mg/kg), administered in chow was investigated in Long Evans (LE) rats. Weight gain of pregnant rats was reduced only by 3-BC, early postnatal survival rate and thymus weight by both compounds at higher doses. 4-Methylbenzylidene camphor and 3-BC delayed male puberty, and dose-dependently affected reproductive organ weights of adult male and female F1 offspring, with partly different effect patterns. Thyroid weight was increased by higher 4-MBC doses. Tissue-specific changes in mRNA levels of estrogen-regulated genes in prostate, uterus and brain regions, determined by real-time PCR, and in their response to acute estradiol challenge in adult gonadectomized offspring were observed. Lowest effective doses were 0.24 mg/kg/day for 3-BC and 7 mg/kg/day for 4-MBC. Fat tissue levels at 7 mg/kg 4-MBC (GC-MS) approached the range of UV filters in fish (Nagtegaal et al., 1997; Balmer et al., 2004)

  9. Composite polymer electrolytes using fumed silica fillers: synthesis, rheology and electrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Khan, Saad A.; Fedkiw, Peter S.; Baker, Gregory L.

    1999-06-28

    The goal of the synthesis research was to devise routes to PEG/fumed silica/lithium salt composites that can be processed and then photochemically cross-linked to form mechanically stable electrolytes. An essential feature of the system is that the ionic conductivity and the mechanical properties must be de-coupled from each other, i.e., cross-linking of the fumed silica matrix must not cause a significant deterioration of the conductivity of the composite. As shown in Figure 2, we prepared a range of surface-modified fumed silicas and investigated their ability to form mechanically stable composite electrolytes. The groups used to modify the surface properties of the silica ranged from simple linear alkyls that render the silica hydrophobia to polyethers that promote compatibility with the electrolyte. From these materials we developed a cross-linkable system that satisfies the criteria of processibility and high-conductivity. The key material needed for the cross-linking reaction are silicas that bear surface-attached monomers. As shown schematically in Figure 3a, we prepared fumed silicas with a combination of surface groups, for example, an octyl chain with different coverages of tethered methacrylates. The length of the tether was varied, and we found that both C{sub 3} and C{sub 8} tethers gave useful composites. The functionalized silicas were combined with PEG-DM, AIBN or benzophenone (free radical initiators), LiClO{sub 4} or Li imide, and either methyl, butyl, or octyl, methacrylate to form stable clear gels. Upon irradiation with UV light, polymerization of both the tethered methacrylate and the added methacrylate took place, yielding a cross-linked rubbery composite material. Ionic conductivity measurements before and after cross-linking showed only a slight decrease (see Figure 9 later), thereby offering strong experimental evidence that the mechanical properties conferred by the silica matrix are de-coupled from the ionic conductivity of the PEG

  10. 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

  11. Evaluation of the L5178Y mouse lymphoma cell mutagenesis assay: intralaboratory results for sixty-three coded chemicals tested at Litton Bionetics, Inc.

    Science.gov (United States)

    Myhr, B C; Caspary, W J

    1988-01-01

    The reliability of the L5178Y TK+/- forward mutation assay as a rapid screen for genotoxicity was evaluated by testing 63 coded chemicals. Replicate treatments were used, and at least two independent experiments were performed for each test condition. The test conditions consisted of no exogenous activation, activation by Aroclor 1254-induced Fischer 344 rat liver S9 homogenate, and in some cases activation by noninduced Fischer 344 rat liver S9. The results were organized into tables that show the mutant colony counts, mutant frequency, and toxicity for each test chemical treatment, positive control treatment, and solvent negative control cultures. The repeat experiments were highly consistent and yielded contradictory evaluations for only a few of the chemicals studied. Fifty-one of the chemicals (81%) were evaluated as mutagenic under one or both of the test conditions. A range in minimum effective concentrations of almost 10(6)-fold (0.008 to 5,000 micrograms/ml) was observed among the mutagenic chemicals. Nine chemicals (14%) were considered to be nonmutagenic. Three chemicals (progesterone, p-rosaniline HCl, and 1,1,1-trichloroethane) gave responses that were not easily evaluated under any test condition: evidence for mutagenesis was obtained in some experiments but not for all repeat studies. Under nonactivation conditions, specifically, the mutagenic activities of 4,4'-bis(dimethylamino)benzophenone, progesterone, and p-rosaniline HCl remained uncertain. With S9 activation, uncertain evidence for mutagenesis was obtained for 2-naphthylamine, progesterone, and 1,1,1-trichloroethane. In some cases, changes in the treatment conditions could lead to different evaluations of the mutagenic activity, and these possibilities are discussed in the descriptive evaluations of each chemical. Comparisons of the observed responses with published results were possible for 29 of the compounds and yielded highly confirmatory evaluations. PMID:3416838

  12. 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.

  13. Assessment of Extraction Parameters on Antioxidant Capacity, Polyphenol Content, Epigallocatechin Gallate (EGCG, Epicatechin Gallate (ECG and Iriflophenone 3-C-β-Glucoside of Agarwood (Aquilaria crassna Young Leaves

    Directory of Open Access Journals (Sweden)

    Pei Yin Tay

    2014-08-01

    Full Text Available The effects of ethanol concentration (0%–100%, v/v, solid-to-solvent ratio (1:10–1:60, w/v and extraction time (30–180 min on the extraction of polyphenols from agarwood (Aquilaria crassna were examined. Total phenolic content (TPC, total flavonoid content (TFC and total flavanol (TF assays and HPLC-DAD were used for the determination and quantification of polyphenols, flavanol gallates (epigallocatechin gallate—EGCG and epicatechin gallate—ECG and a benzophenone (iriflophenone 3-C-β-glucoside from the crude polyphenol extract (CPE of A. crassna. 2,2'-Diphenyl-1-picrylhydrazyl (DPPH radical scavenging activity was used to evaluate the antioxidant capacity of the CPE. Experimental results concluded that ethanol concentration and solid-to-solvent ratio had significant effects (p < 0.05 on the yields of polyphenol and antioxidant capacity. Extraction time had an insignificant influence on the recovery of EGCG, ECG and iriflophenone 3-C-β-glucoside, as well as radical scavenging capacity from the CPE. The extraction parameters that exhibited maximum yields were 40% (v/v ethanol, 1:60 (w/v for 30 min where the TPC, TFC, TF, DPPH, EGCG, ECG and iriflophenone 3-C-β-glucoside levels achieved were 183.5 mg GAE/g DW, 249.0 mg QE/g DW, 4.9 mg CE/g DW, 93.7%, 29.1 mg EGCG/g DW, 44.3 mg ECG/g DW and 39.9 mg iriflophenone 3-C-β-glucoside/g DW respectively. The IC50 of the CPE was 24.6 mg/L.

  14. A novel and simplified procedure for patterning hydrophobic and hydrophilic SAMs for microfluidic devices by using UV photolithography.

    Science.gov (United States)

    Besson, Eric; Gue, Anne-Marie; Sudor, Jan; Korri-Youssoufi, Hafsa; Jaffrezic, Nicole; Tardy, Jacques

    2006-09-26

    This work describes how selective patterning of hydrophobic and hydrophilic areas inside microchannels of microfluidic devices can be achieved by combining well-known chemical protocols and standard photolithography equipment (365 nm). Two techniques have been performed and compared. The first technique is based on the preparation of self-assembled monolayers of photocleavable organosilane and the second one on photoassisted grafting (365 nm) of self-assembled monolayers (SAMs) on a silicon or glass substrate. In the first case, we begin with monolayers carrying an o-nitrobenzyl function (hydrophobic area) that is photochemically cleaved, revealing a carboxylic acid group (hydrophilic area). The problem is that the energy necessary to cleave this monolayer is too high and the reaction time is more than 1 h with 50 mW/cm(2) irradiation flux. To overcome this practical disadvantage, we propose another approach that is based on the thiol-ene reaction with benzophenone as photoinitiator. In this approach, a monolayer of mercaptopropyltrimethoxysilane (MPTS) is prepared first. Subsequently, a hydrocarbon chain is photografted locally onto the thiol layer, forming a hydrophobic surface while the reminding unmodified thiol surface is oxidized into sulfonic acid (hydrophilic area). We demonstrated the feasibility of this approach and synthesized high-quality self-assembled monolayers by UV grafting with an irradiation time of 30 s at 365 nm (50 mW/cm(2)). The modified surfaces have been characterized by contact angle measurements, X-ray photoelectron spectroscopy (XPS), AFM, and multiple internal reflection infrared spectroscopy (MIR-FTIR). The difference in the contact angles on the hydrophilic and hydrophobic surfaces reached a remarkable 77 degrees. We have also demonstrated that this method is compatible with selective surface grafting inside microfluidic channels. PMID:16981747

  15. Estimating Margin of Exposure to Thyroid Peroxidase Inhibitors Using High-Throughput in vitro Data, High-Throughput Exposure Modeling, and Physiologically Based Pharmacokinetic/Pharmacodynamic Modeling.

    Science.gov (United States)

    Leonard, Jeremy A; Tan, Yu-Mei; Gilbert, Mary; Isaacs, Kristin; El-Masri, Hisham

    2016-05-01

    Some pharmaceuticals and environmental chemicals bind the thyroid peroxidase (TPO) enzyme and disrupt thyroid hormone production. The potential for TPO inhibition is a function of both the binding affinity and concentration of the chemical within the thyroid gland. The former can be determined through in vitro assays, and the latter is influenced by pharmacokinetic properties, along with environmental exposure levels. In this study, a physiologically based pharmacokinetic (PBPK) model was integrated with a pharmacodynamic (PD) model to establish internal doses capable of inhibiting TPO in relation to external exposure levels predicted through exposure modeling. The PBPK/PD model was evaluated using published serum or thyroid gland chemical concentrations or circulating thyroxine (T4) and triiodothyronine (T3) hormone levels measured in rats and humans. After evaluation, the model was used to estimate human equivalent intake doses resulting in reduction of T4 and T3 levels by 10% (ED10) for 6 chemicals of varying TPO-inhibiting potencies. These chemicals were methimazole, 6-propylthiouracil, resorcinol, benzophenone-2, 2-mercaptobenzothiazole, and triclosan. Margin of exposure values were estimated for these chemicals using the ED10 and predicted population exposure levels for females of child-bearing age. The modeling approach presented here revealed that examining hazard or exposure alone when prioritizing chemicals for risk assessment may be insufficient, and that consideration of pharmacokinetic properties is warranted. This approach also provides a mechanism for integrating in vitro data, pharmacokinetic properties, and exposure levels predicted through high-throughput means when interpreting adverse outcome pathways based on biological responses. PMID:26865668

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

    Science.gov (United States)

    Frederiksen, Hanne; Aksglaede, Lise; Sorensen, Kaspar; Nielsen, Ole; Main, Katharina M; Skakkebaek, Niels E; Juul, Anders; Andersson, Anna-Maria

    2013-11-01

    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 suspected endocrine disrupters. In this study the urinary excretion of eight phenols in Danish children recruited from the general population were investigated. One 24h urine and two consecutive first morning samples were collected from each of 129 healthy Danish children and adolescents (6-21 years). The concentrations of urinary phenols were analyzed by a new on-line TurboFlow-liquid chromatography-tandem mass spectrometry (LC-MS/MS) method. Most of the analyzed phenols were detectable in more than 80% of the 24h urine samples and the median concentration of BPA, TCS, BP-3, 2,4-dichorophenol and 2,5-dichorophenol (analyzed as ∑DCP), 2-phenylphenol and 4-phenylphenol were 1.37, 1.45, 1.41, 0.65, 0.36 and 0.53ng/mL, respectively. The ranges of the excreted TCS and BP-3 were wide; from below limit of detection to maximum levels of 955ng/mL and 162ng/mL, respectively, while the other phenols were excreted in a more narrow range with maximum levels below 25ng/mL. Concentrations in first morning urine were in general higher than in 24h urine and comprised 30-47% of the absolute amount excreted during 24h. The youngest children aged 6-10 years had a significantly higher urinary BPA concentration (ng/mL) and also a relatively higher daily BPA excretion (ng/kg bw/24h) than the older children and adolescents. The opposite pattern was observed for TCS, BP-3 and ∑DCP for which urinary levels increased significantly with age. No gender difference or associations to pubertal development were observed. In conclusion, our study showed that Danish children were exposed to multiple phenols simultaneously. Small children were relatively more exposed to BPA than older children, while higher

  17. Ultrathin films of functional polyelectrolytes on flat surfaces and colloidal particles using the layer-by-layer deposition technique

    Science.gov (United States)

    Park, Mi-Kyoung

    Layer-by-layer (LbL) self-assembly techniques have been used to prepare ultrathin polymer films with controlled thicknesses and compositions. The technique is based on the alternate adsorption of oppositely charged polyelectrolyte layers on substrates. This dissertation details the investigation of ultrathin films with functional polyelectrolytes coated on flat substrates and colloidal particles. Several systems were investigated including: liquid crystal (LC) photoalignment layers, photo-crosslinkable permselective membranes, luminescent hollow-shell particles, and conducting polymer colloidal particles. The multilayer films of an azo-polymer and a polycation were utilized to control azimuthal alignment of liquid crystals. Irradiation of a hybrid LC cell with linearly polarized light resulted in in-plane homogeneous LC alignment, which is dependent on the thickness, and irradiation time. The director of the LC molecules was found to be perpendicular to the polarization plane and can be reoriented. The photocross-linkable multilayer membranes comprising poly(acrylic acid) and poly(allyamine hydrochloride) modified with benzophenone groups have been prepared. It was demonstrated that the permeability of the multilayer films can be controlled by the number of layers as well as the UV irradiation time. Furthermore, a "smart" pH-switchable membrane was produced by adjusting the pH of the dipping solution while maintaining stability throughout the cross-linked structure. The membrane showed pH-sensitive permselectivity, that is, the film was permeable to the cationic molecules, but impermeable to the anionic molecules at pH 10 and vise versa at pH 3. Luminescent core-shell particles and hollow capsules were prepared by the LbL deposition of polystyrenesulfonate (PSS) and a water-soluble ionene precursor polymer containing fluorene units (PI) onto spherical colloid particles. Subsequent cross-linking of the PI in the multilayer shell formed luminescent conjugated oligo

  18. A new NMR approach for structure determination of thermally unstable biflavanones and application to phytochemicals from Garcinia buchananii.

    Science.gov (United States)

    Stark, Timo D; Lösch, Sofie; Salger, Mathias; Balemba, Onesmo B; Wakamatsu, Junichiro; Frank, Oliver; Hofmann, Thomas

    2015-10-01

    Previous activity-guided phytochemical studies on Garcinia buchananii stem bark, which is traditionally used in Africa to treat various gastrointestinal and metabolic illnesses, revealed xanthones, polyisoprenylated benzophenones, flavanone-C-glycosides, biflavonoids, and/or biflavanones as bioactive key molecules. Unequivocal structure elucidation of biflavonoids and biflavanones by means of NMR spectroscopy is often complicated by the hindered rotation of the monomers around the C-C axis (atropisomerism), resulting in a high spectral complexity. In order to facilitate an unrestricted rotation, NMR spectra are usually recorded at elevated temperatures, commonly over 80 °C, which effects in a single set of resonance signals. However, under these conditions, one of the target compounds of this investigation, (2R,3S,2″R,3″R)-manniflavanone (1), undergoes degradation. Therefore, we demonstrated in the present study that the 1,1-ADEQUATE could be successfully used as a powerful alternative approach to confirm the C-C connectivities in 1, avoiding detrimental conditions. However, a moderate increase in temperature up to 50 °C was sufficient to deliver sharp signals in the proton NMR experiment of (2R,3S,2″R,3″R)-isomanniflavanone (2) and (2″R,3″R)-preussianone (3). In addition, two new compounds could be isolated, namely (2R,3S,2″R,3″R)-GB-2 7″-O-β-D-glucopyranoside (4) and (2R,3S,2″R,3″R)-manniflavanone-7″-O-β-D-glucopyranoside (5), and whose structures were elucidated by spectroscopic analysis including 1D and 2D NMR and mass spectrometry methods. The absolute configurations were determined by a combination of NMR and electronic circular dichroism (ECD) spectroscopy. The aforementioned compounds exhibited high anti-oxidative capacity in the H2O2 scavenging, hydrophilic Trolox equivalent antioxidant capacity (H-TEAC) and hydrophilic oxygen radical absorbance capacity (H-ORAC) assays. PMID:26195084

  19. Photocurable surgical tissue adhesive glues composed of photoreactive gelatin and poly(ethylene glycol) diacrylate.

    Science.gov (United States)

    Nakayama, Y; Matsuda, T

    1999-01-01

    This article presents a novel photochemically driven surgical tissue adhesive technology using photoreactive gelatins and a water-soluble difunctional macromer (poly(ethylene glycol) diacrylate: PEGDA).The gelatins were partially derivatized with photoreactive groups, such as ultraviolet light (UV)-reactive benzophenone and visible light-reactive xanthene dye (e.g., fluorescein sodium salt, eosin Y, and rose bengal). A series of the prepared photocurable tissue adhesive glues, consisting of the photoreactive gelatin, PEGDA, and a saline solution with or without ascorbic acid as a reducing agent, were viscous solutions under warming, and their effectiveness was evaluated as hemostasis- and anastomosis-aid in cardiovascular surgery. Regardless of the type of photoreactive groups, the irradiation of the photocurable tissue adhesive glues by UV or visible light within 1 min produced water-swollen gels, which had a high adhesive strength to wet collagen film. These were due to the synergistic action of photoreactive group-initiated photo-cross-linking and photograft polymerization. An increase in the irradiation time resulted in increased gel yield and reduced water swellability. A decrease in the molecular weight of PEGDA and an increase in concentration of both gelatin and PEGDA resulted in reduced water swellability and increased tensile and burst strengths of the resultant gels. In rats whose livers were injured with a trephine in laparotomy, the bleeding spots were coated with the photocurable adhesive glue and irradiated through an optical fiber. The coated solution was immediately converted to a swollen gel. The gel was tightly adhered to the liver tissue presumably by interpenetration, and concomitantly hemostasis was completed. The anastomosis treatment with the photocurable glue in the canine abdominal or thoracic aortas incised with a knife resulted in little bleeding under pulsatile flow after declamping. Histological examination showed that the glues

  20. [Determination of the migration of seven photoinitiators in food packaging materials into aqueous solvent].

    Science.gov (United States)

    Liu, Pengyan; Huang, Enjie; Chen, Yanjie

    2012-12-01

    The quantity of photoinitiators (PIs) migrated into hydrosoluble foods from packaging materials is usually very small. It is hardly detectable by using the current methods. For this reason, the article describes a new effective method for detecting the migration of PIs. In this method, the migration experiment was done in aqueous food simulation. After the PIs in printing inks used in food contact materials were extracted from the solution via solid-phase microextraction (SPME) using 65 microm polydimethylsiloxane/divinylbenzene (PDMS-DVB)-coated fiber, their migration amounts were determined by gas chromatography-mass spectrometry (GC-MS) in the selected ion monitoring mode (SIM). The PIs determined by SPME/GC-MS were benzophenone (BP), 1-hydroxycyclohexyl-phenylketone (CPK), ethyl-4-dimethyl-aminobenzoate (EDMAB), 4-methylbenzophenone (4-MBP), 2, 2-dimethoxy-2-phenylacetophenone (2,2-DMPA), methyl 2-benzoylbenzoate (OMBB) and 2-ethylhexyl-4-dimethyl-aminobenzoate (EHDAB). The limits of detection (S/N = 3) were between 0.0012 and 0.0069 microg/L. The linearity ranged from 0.03 to 1.0 microg/L (r2 > 0.9909). The recoveries were in the range from 70.8% to 112.0% (n = 3) with the relative standard deviations no more than 14.0%. Twenty samples were tested by using this developed method. The analytical results showed that BP was detected in all samples, and the migration amounts of BP were from 0.002 to 0.074 microg/dm2; 4-MBP was detected in ten samples, and the migration amounts of 4-MBP were from 0.006 to 0.019 microg/dm2; CPK was detected in three samples, and its amounts were 0.005, 0.005, 0.007 microg/dm2; 2,2-DMPA was detected as 0.009 microg/dm2 in one sample. The determination of real samples showed this method is feasible. The method is sensitive, simple and free from organic solvents. It could make reference to migrating determination of PIs in printing inks on food packaging surface. PMID:23593879

  1. Ionic Liquids: Radiation Chemistry, Solvation Dynamics and Reactivity Patterns

    Energy Technology Data Exchange (ETDEWEB)

    Wishart, J.F.

    2011-06-12

    , 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.

  2. Do pharmaceuticals, pathogens, and other organic waste water compounds persist when waste water is used for recharge?

    Science.gov (United States)

    Cordy, Gail E.; Duran, Norma L.; Bouwer, Herman; Rice, Robert C.; Furlong, Edward T.; Zaugg, Steven D.; Meyer, Michael T.; Barber, Larry B.; Kolpin, Dana W.

    2004-01-01

    A proof-of-concept experiment was devised to determine if pharmaceuticals and other organic waste water compounds (OWCs), as well as pathogens, found in treated effluent could be transported through a 2.4 m soil column and, thus, potentially reach ground water under recharge conditions similar to those in arid or semiarid climates. Treated effluent was applied at the top of the 2.4 m long, 32.5 cm diameter soil column over 23 days, Samples of the column inflow were collected from the effluent storage tank at the beginning (Tbegin) and end (Tend) of the experiment, and a sample of the soil column drainage at the base of the column (Bend) was collected at the end of the experiment. Samples were analyzed for 131 OWCs including veterinary and human antibiotics, other prescription and nonprescription drugs, widely used household and industrial chemicals, and steroids and reproductive hormones, as well as the pathogens Salmonella and Legionella. Analytical results for the two effluent samples taken at the beginning (Tbegin) and end (Tend) of the experiment indicate that the number of OWCs detected in the column inflow decreased by 25% (eight compounds) and the total concentration of OWCs decreased by 46% while the effluent was in the storage tank during the 23-day experiment. After percolating through the soil column, an additional 18 compounds detected in Tend (67% of OWCs) were no longer detected in the effluent (Bend) and the total concentration of OWCs decreased by more than 70%. These compounds may have been subject to transformation (biotic and abiotic), adsorption, and (or) volatilization in the storage tank and during travel through the soil column. Eight compounds—carbamazapine; sulfamethoxazole; benzophenone; 5-methyl-1H-benzotriazole; N,N-diethyltoluamide; tributylphosphate; tri(2-chloroethyl) phosphate; and cholesterol—were detected in all three samples indicating they have the potential to reach ground water under recharge conditions similar to those in

  3. 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

  4. 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. PMID:20428853

  5. 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

  6. 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

  7. Study on modified polypropylene membrane induced by UV-irradiation grafting%紫外光接枝改性聚丙烯薄膜的研究

    Institute of Scientific and Technical Information of China (English)

    王翱; 魏俊富; 赵孔银; 李绍宁; 王晓磊; 王磊

    2012-01-01

    A new kind of hydrophilic membrane was prepared through grafting polymerization of acrylic acid(AA) and methacrylic acid (MAA) onto the surface of polypropylene (PP) membrane initiated by ultraviolet (UV), using benzophenone as photosensitizer. The factors influenceing the grafting degree were discussed, such as the concentration of photosensitizer, irradiation time and solvent type. Attenuated total reflection-fou-rier transform infrared spectroscopy (ATR-FT-IR) and scanning electron microscopy (SEM) were used to char- acterize the chemical and morphological changes of the original and grafted PP membrane, the results indicated that acrylic acid was grafted onto the surface of PP membrane. Static contact angle measurements and water ab-sorption ratio were used to characterize the hydrophilic changes of the polypropylene membrane surface. In ad- dition, the grafting degree of AA was commonly higher than MAA under the same grafting conditons, further- more, the grafting degree of AA in water was obviously higher than that in organic solvent. The contact angle of grafted PP membrane decreased from 95° to 35° over a critical grafting degree of 11.8%, the hydrophilic ofPP membranes improved dramatically.%以二苯甲酮为光敏剂,通过紫外光辐照引发,将亲水性单体丙烯酸(AA)和甲基丙烯酸(MAA)接枝在聚丙烯薄膜表面。考察了光敏剂浓度、辐照时间以及溶剂类型对接枝率的影响。利用衰减全反射红外光谱和扫描电子显微镜对接枝薄膜的表面化学组成和形貌结构进行表征,通过水接触角和吸水率研究了接枝后薄膜的亲水性。结果表明,在相同条件下,AA的接枝率高于MAA;相比于有机溶剂,在水溶剂中AA的接枝率明显提高;当接枝率达到11.8%时,薄膜表面水接触角由原膜的95°降低到35°,亲水性显著提高。

  8. Garcinol, an acetyltransferase inhibitor, suppresses proliferation of breast cancer cell line MCF-7 promoted by 17β-estradiol.

    Science.gov (United States)

    Ye, Xia; Yuan, Lei; Zhang, Li; Zhao, Jing; Zhang, Chun-Mei; Deng, Hua-Yu

    2014-01-01

    The acetyltransferase inhibitor garcinol, a polyisoprenylated benzophenone, is extracted from the rind of the fruit of Garcinia indica, a plant found extensively in tropical regions. Anti-cancer activity has been suggested but there is no report on its action via inhibiting acetylation against cell proliferation, cell cycle progression, and apoptosis-inhibtion induced by estradiol (E2) in human breast cancer MCF-7 cells. The main purposes of this study were to investigate the effects of the acetyltransferase inhibitor garcinol on cell proliferation, cell cycle progression and apoptosis inhibition in human breast cancer MCF-7 cells treated with estrogen, and to explore the significance of changes in acetylation levels in this process. We used a variety of techniques such as CCK-8 analysis of cell proliferation, FCM analysis of cell cycling and apoptosis, immunofluorescence analysis of NF-κB/ p65 localization, and RT-PCR and Western blotting analysis of ac-H3, ac-H4, ac-p65, cyclin D1, Bcl-2 and Bcl- xl. We found that on treatment with garcinol in MCF-7 cells, E2-induced proliferation was inhibited, cell cycle progression was arrested at G0/G1 phase, and the cell apoptosis rate was increased. Expression of ac-H3, ac-H4 and NF-κB/ac-p65 proteins in E2-treated MCF-7 cells was increased, this being inhibited by garcinol but not ac- H4.The nuclear translocation of NF-κB/p65 in E2-treated MCF-7 cells was also inhibited, along with cyclin D1, Bcl-2 and Bcl-xl in mRNA and protein expression levels. These results suggest that the effect of E2 on promoting proliferation and inhibiting apoptosis is linked to hyperacetylation levels of histones and nonhistone NF-κB/ p65 in MCF-7 cells. The acetyltransferase inhibitor garcinol plays an inhibitive role in MCF-7 cell proliferation promoted by E2. Mechanisms are probably associated with decreasing ac-p65 protein expression level in the NF-κB pathway, thus down-regulating the expression of cyclin D1, Bcl-2 and Bcl-xl. PMID

  9. Induction of p21(Waf1/Cip1) by garcinol via downregulation of p38-MAPK signaling in p53-independent H1299 lung cancer.

    Science.gov (United States)

    Yu, Sheng-Yung; Liao, Chiung-Ho; Chien, Ming-Hsien; Tsai, Tsung-Yu; Lin, Jen-Kun; Weng, Meng-Shih

    2014-03-01

    Garcinol, a polyisoprenylated benzophenone, from Garcinia indica fruit rind has possessed anti-inflammatory, antioxidant, antiproliferation, and anticancer activities. However, the anticancer mechanisms of garcinol in lung cancer were still unclear. Therefore, we examine the effects of garcinol on antiproliferation in human lung cancer cells. Treatments with garcinol for 24 h exhibited morphological changes and inhibited the proliferation of H460 (p53-wild type) and H1299 (p53-null) cells in dose- and time-dependent manners. Furthermore, a significant G1 cell cycle arrest was observed in a dose-dependent treatment after H1299 cells were exposed in garcinol, whereas garcinol induced apoptosis rather than cell cycle arrest in H460 cells. Moreover, cyclin-dependent kinase 2 (CDK2), cyclin-dependent kinase 4 (CDK4), cyclin D1, and cyclin D3 were decreased, although cyclin E and cyclin-dependent kinase 6 (CDK6) were increased in garcinol-treated H1299 cells. Meanwhile, the protein levels of CDK inhibitors p21(Waf1/Cip1) and p27(KIP1) also exhibited upregulation after garcinol treatments. The enhanced protein-associated level between p21(Waf1/Cip1) and CDK4/2 rather than p27(KIP1) and CDK4/2 was demonstrated in garcinol-treated cells. Additionally, knock-down p21(Waf1/Cip1) by specific siRNA competently prevented garcinol-induced G1 arrest. Besides, garcinol also inhibited ERK and p38-MAPK activations in time-dependent mode. The pretreatment with p38-MAPK inhibitor but not ERK inhibitor raised garcinol-induced G1 population cells. Co-treatment with p38-MAPK inhibitor and garcinol synergistically elevated cyclin E, p21(Waf1/Cip1), and p27(Kip1) expressions. Meanwhile, overexpression dominant negative p38-MAPK also enhanced garcinol-induced p21(Waf1/Cip1) expression in H1299 cells. Accordingly, our data suggested that garcinol induced G1 cell cycle arrest and apoptosis in lung cancer cells under different p53 statuses. The p53-independent G1 cell cycle arrest induced by

  10. The Preparation and Characterization of Hyper-Branched Polyimides Based on Polyetheramine%以聚醚胺为单体的超支化聚酰亚胺的制备与表征

    Institute of Scientific and Technical Information of China (English)

    陈川; 黄明富; 颜善银; 徐祖顺; 易昌凤

    2012-01-01

    以聚醚胺(T-403)、4,4′-二氨基二苯醚(ODA)和3,3′,4,4′-二苯甲酮二酐(BTDA)为单体,采用A2+B3法通过热亚胺化和化学亚胺化得到一系列超支化聚酰亚胺(HBPIs)。通过红外光谱测试(FT-IR)、热重分析测试(TGA)、溶解性测试和X射线衍射分析(XRD)对聚合物进行了结构表征和性能测试。FT-IR表明生成了预期的聚合物;TGA表明合成的超支化共聚PI随着共聚体系中芳香二胺的比例增大,其在N2中5%和10%的热失重温度也随之升高;溶解性测试表明合成的超支化聚酰胺酸具有较好的溶解性,化学亚胺化合成的HBPI溶解性良好;X射线衍射分析(XRD)表明聚合物的结晶度较低。%A series of hyper-branched polyimides were synthesized via A2+B3 approach using 3,3′,4,4′-benzophenone tetracarboxylic dianhydride(BTDA) and 4,4′-diaminodiphenyl ether(ODA) and poly(oxyalkylene) triamine(T-403) as materials.The structure and properties of the products were characterized by Fourier transform infrared spectroscopy(FT-IR),thermal gravimetric analysis(TGA),X-ray diffraction(XRD) and solubility test.The chemical structure of hyper-branched copolyimides was confirmed by FT-IR spectra.The thermogravimetric curve indicates that PI′s 5% or 10% thermal decomposition temperature in N2 increases as the proportion of ODA increases;the solubility test shows that the obtained hyper-branched poly(amic acid)s and the polyimide obtained by chemical imidization are soluble in several polar aprotic solvents.XRD spectrum demonstrates that the polymers have low-order aggregation structure.

  11. 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

  12. Enhancing the Value of Free Metals in the Synthesis of Lanthanoid Formamidinates: Is a Co-oxidant Needed?

    Science.gov (United States)

    Deacon, Glen B; Junk, Peter C; Werner, Daniel

    2016-01-01

    Treatment of N,N'-bis(aryl)formamidines (ArFormH), N,N'-bis(2,6-difluorophenyl)formamidine (DFFormH) or N,N'-bis(2,6-diisopropylphenyl)formamidine (DippFormH), with europium metal in CH3 CN is an efficient synthesis of the divalent complexes: [{Eu(DFForm)2 (CH3 CN)2 }2 ] (Eu1) or [Eu(DippForm)2 (CH3 CN)4 ] (Eu2). The synthetic method was extended to ytterbium, but the metal required activation by addition of Hg(0) . With DFFormH in CH3 CN, [{Yb(DFForm)2 (CH3 CN)}2 ] (Yb1) was obtained in good yield, and [Yb(DFForm)2 (thf)3 ] (Yb3) was obtained from a synthesis in CH3 CN/THF. Thus, this synthetic method completely circumvents the use of either salt metathesis, or redox transmetallation/protolysis (RTP) protocols to prepare divalent rare-earth formamidinates. Heating Yb1 in PhMe/C6 D6 resulted in decomposition to trivalent products, including one from a CH3 CN activation process. For a synthetic comparison, divalent ytterbium DFForm and DippForm complexes were synthesised by RTP reactions between Yb(0) , Hg(R)2 (R=Ph, C6 F5 ), and ArFormH in THF, leading to the isolation of either [Yb(DFForm)2 (thf)3 ] (Yb3), or the first five coordinate rare-earth formamidinate complex [Yb(DippForm)2 (thf)] (Yb4 b), and, from adjustment of the stoichiometry, trivalent [Yb(DFForm)3 (thf)] (Yb6). Oxidation of Yb3 with benzophenone (bp), or halogenating agents (TiCl4 (thf)2 , Ph3 CCl, C2 Cl6 ) gave [Yb(DFForm)3 (bp)] or [Yb(DFForm)2 Cl(thf)2 ], respectively. Furthermore, the structural chemistry of divalent ArForm complexes has been substantially broadened. Not only have the highest and lowest coordination numbers for divalent rare-earth ArForm complexes been achieved in Eu2 and Yb4 b, respectively, but also dimeric Eu1 and Yb1 have highly unusual ArForm bridging coordination modes, either perpendicular μ-1κ(N:N'):2κ(N:N') in Eu1, or the twisted μ-1κ(N:N'):2κ(N':F') DFForm coordination in Yb1, both unprecedented in divalent rare-earth ArForm chemistry and in the wider

  13. Synthesis of a mononuclear, non-square-planar chromium(ii) bis(alkoxide) complex and its reactivity toward organic carbonyls and CO2.

    Science.gov (United States)

    Yousif, Maryam; Cabelof, Alyssa C; Martin, Philip D; Lord, Richard L; Groysman, Stanislav

    2016-06-14

    In this paper, we report the synthesis and reactivity of a rare mononuclear chromium(ii) bis(alkoxide) complex, Cr(OR')2(THF)2, that is supported by a new bulky alkoxide ligand (OR' = di-t-butyl-(3,5-diphenylphenyl)methoxide). The complex is prepared by protonolysis of square-planar Cr(N(SiMe3)2)2(THF)2 with HOR'. X-ray structure determination disclosed that Cr(OR')2(THF)2 features a distorted seesaw geometry, in contrast to nearly all other tetra-coordinate Cr(ii) complexes, which are square-planar. The reactivity of Cr(OR')2(THF)2 with aldehydes, ketones, and carbon dioxide was investigated. Treatment of Cr(OR')2(THF)2 with two equivalents of aromatic aldehydes ArCHO (ArCHO = benzaldehyde, 4-anisaldehyde, 4-trifluorbenzaldehyde, and 2,4,6-trimethylbenzaldehyde) leads cleanly to the formation of Cr(iv) diolate complexes Cr(OR')2(O2C2H2Ar2) that were characterized by UV-vis and IR spectroscopies and elemental analysis; the representative complex Cr(OR')2(O2C2H2Ph2) was characterized by X-ray crystallography. In contrast, no reductive coupling was observed for ketones: treatment of Cr(OR')2(THF)2 with one or two equivalents of benzophenone forms invariably a single ketone adduct Cr(OR')2(OCPh2) which does not react further. QM/MM calculations suggest the steric demands prevent ketone coupling, and demonstrate that a mononuclear Cr(iii) bis-aldehyde complex with partially reduced aldehydes is sufficient for C-C bond formation. The reaction of Cr(OR')2(THF)2 with CO2 leads to the insertion of CO2 into a Cr-OR' bond, followed by complex rearrangement to form a diamagnetic dinuclear paddlewheel complex Cr2(O2COR')4(THF)2, that was characterized by NMR, UV-vis, and IR spectroscopy, and X-ray crystallography. PMID:27073074

  14. A method for the amplification of chemically induced transformation in C3H/10T1/2 clone 8 cells: its use as a potential screening assay.

    Science.gov (United States)

    Schechtman, L M; Kiss, E; McCarvill, J; Nims, R; Kouri, R E; Lubet, R A

    1987-09-01

    A method has been developed by which to amplify expression of phenotypic transformation of C3H/10T1/2 clone 8 mouse embryo cells not otherwise observed in the standard transformation assay. The expression of transformed foci was amplified by subcultivating chemically treated target cells after they had reached confluence and replating them at subconfluent cell densities. Conditions leading to the expression of the highest numbers of transformed foci include a) a cell seeding density for chemical treatment of 1 X 10(4) cells/dish, b) subculture 4 weeks after treatment, and c) replating cells at a density of 2 X 10(5) cells/-dish. Agents capable of inducing transformation in the standard assay (e.g., 4,4'-bis(dimethylamino)benzophenone, benzo[a]pyrene, 7,12-dimethylbenz[a]anthracene, and others) also yielded transformation in the replating assay. The more marginal transforming activities of chemicals such as ethyl methanesulfonate, 7-(bromomethyl)-12-methylbenz[a]anthracene, and N-methyl-N'-nitro-N-nitrosoguanidine were enhanced by the amplification procedure. Compounds that failed to elicit focal transformation in the standard assay (e.g., dibenz[a,h]anthracene, Tris(2,3-dibromopropyl) phosphate, lead acetate, benzidine, propyleneimine, N-hydroxy-2-fluorenylacetamide, and numerous other compounds of various chemical classes) induced significant levels of phenotypic transformation upon amplification. Noncarcinogens (e.g., phenanthrene, anthracene, 2-aminobiphenyl, cycloheximide, and others) failed to cause significant phenotypic transformation even when cells were replated. To further enhance the applicability of this new replating system, an exogenous source of metabolic activation was added: a 9,000 X g supernatant from Aroclor 1254-induced rat hepatic S-9. This activation system was found a) to be only minimally cytotoxic by itself and b) to be able to mediate NADPH-dependent, dose-dependent toxicity, and transformation by activating the procarcinogens

  15. Bespoke contrast-matched diblock copolymer nanoparticles enable the rational design of highly transparent Pickering double emulsions

    Science.gov (United States)

    Rymaruk, Matthew J.; Thompson, Kate L.; Derry, Matthew J.; Warren, Nicholas J.; Ratcliffe, Liam P. D.; Williams, Clive N.; Brown, Steven L.; Armes, Steven P.

    2016-07-01

    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 substantial spectral

  16. Alkylphenols, Other Endocrine-Active Chemicals, and Fish Responses in Three Streams in Minnesota - Study Design and Data, February-September 2007

    Science.gov (United States)

    Lee, Kathy E.; Schoenfuss, Heiko L.; Jahns, Nathan D.; Brown, Greg K.; Barber, Larry B.

    2008-01-01

    included the presence and concentration of vitellogenin in plasma, gonadosomatic indices, and histological characterizations of liver and testes tissue. Hydrologic, chemical and biological characteristics were different among sites. The percentage of streamflow contributed by WWTP effluent (ranging from less than 1 to 79 percent) was greatest at the South Fork Crow River and least at the Grindstone River. WWTP effluent generally contributed the greatest percentage of streamflow during winter and late summer when streamflows were low. A wide variety of chemicals were detected. More chemicals were detected in WWTP effluent samples than in stream samples during most time periods. The most commonly detected chemicals in samples collected monthly and analyzed at the USGS National Research Program Laboratory were 2,6-di-tert-butyl-1,4-benzoquinone, 2,6-di-tert-butyl-4-methylphenol, 3-beta-coprostanol, 4-methylphenol, 4-nonylphenol (NP), 4-tert-octylphenol, bisphenol A, cholesterol, ethylenediaminetetraacetic acid, and triclosan. The chemicals 4-nonylphenolmonoethoxycarboxylate (NP1EC), 4-nonylphenoldiethoxycarboxylate (NP2EC), and 4-nonylphenoltriethoxycarboxylate (NP3EC) also were detected. Excluding nondetections, the sum of NP1EC through NP3EC concentrations ranged from 5.1 to 260 ug/L among all samples. NP was detected in upstream, effluent, and downstream samples in each stream during at least one time period. NP was detected in 49 percent of environmental samples. Excluding nondetections, concentrations of NP ranged from 100 to 880 nanograms per liter among all samples. NP was also detected in more than one-half of the bed-sediment samples. The most commonly detected wastewater indicator chemicals in samples analyzed by schedule 4433 at the USGS National Water Quality Laboratory were 3,4-dichlorophenyl isocyanate, acetyl-hexamethyl-tetrahydronaphthalene, benzophenone, cholesterol, hexahydrohexamethyl-cyclopenta-benzopyran, N,N-diethyl-meta-toluamide, and

  17. 大叶藤黄茎皮化学成分研究%Studies on the chemical constituents of the barks of Garcinia xanthochymus

    Institute of Scientific and Technical Information of China (English)

    季丰; 李占林; 牛生吏; 华会明

    2012-01-01

    目的 研究大叶藤黄(Garcinia xanthochymus)茎皮95%(体积分数)乙醇提取物的化学成分.方法 利用制备薄层色谱、反复硅胶柱色谱、Sephadex LH-20柱色谱、开放ODS柱色谱等方法进行分离纯化;根据理化性质及波谱分析鉴定化合物的结构.结果 分离得到10个已知化合物,分别鉴定为1,2,5-三羟基咄酮(1)、1,4,5-三羟基(口山)酮(2)、1,6-二羟基-4,5-二甲氧基=酮(3)、1,5-二羟基-3-甲氧基(口山)酮(4)、1,4-二羟基-5-甲氧基-6,6′-二甲基吡喃(2′,3′:6,7)(口山)酮(5)、木犀草素(6)、槲皮素(7)、山柰酚(8)、tirucallane-7,24-dien-3-ol (9)、morolic acid acetate(10).结论 化合物6、9、10为首次从该植物中分离得到.%Garcinia xanthochymus is a traditional Dai medicine native to the south and southwest of Yunnan Province of China. The medicinal plants of the genus Garcinia are well-known as rich sources of xanthones, benzophenones. These phenolic constituents have been reported to possess a wide range of biological and pharmacological properties, such as antibacterial, antimalarial, and cytotoxic activities. In the course of our search for anticaner agents from the genus Garcinia,we investigated the chemical constituents of the 95% EtOH extract of the barks of Garcinia xanthochymus. Ten compounds were isolated by various kinds of column chromatography on silica gel,Sephadex LH-20 and ODS. Their structures were identified as 1,2,5-tri-hydroxyxanthone(1),1,4,5-trihydroxyxanthone(2), 1,6-dihydroxy-4,5-dimethoxyxanthone(3),1,5-di-hydroxy-3-rnethoxyxanthone(4) ,1,4-dihydroxy-5-methoxy-6,6'-dimethylpyrano(2',3':6,7)xanthone(5), luteolin(6) ,quercetin(7) ,kaempferol(8) ,tirucallane-7 ,24-dien-3-ol(9) and morolic acid acetate(10) .respectively. Compounds 6,9,10 are isolated from Garcinia xanthochymus for the first time.

  18. Simultaneous Determination of Eleven Ulta-violet Absorbents in Cosmetics by High Performance Liquid Chromatography%高效液相色谱法同时测定化妆品中的11种紫外吸收剂

    Institute of Scientific and Technical Information of China (English)

    黄雄风; 刘绿叶; 许群; 庄国顺; 杜军伟

    2014-01-01

    An accurate, fast and sensitive method based on high performance liquid chromatography was established for the simultaneous determination of eleven ultra-violet absorbents in cosmetics. Eleven ultra-violet absorbents were baseline separated on an Acclaim C18 column within 11. 5 min using acetonitrile-0. 1%formic acid in water ( V/V) mobile phase, and detected at 361 nm with UV detection. Under the optimized conditions, the relative standard derivations ( RSDs) of the eleven ultra-violet absorbents were all less than 0. 1% for retention time, and less than 1. 2% for peak area; good linearity was obtained from 5 to and 500 mg/L with the correlation coefficients of above 0 . 9990 for these analytes; the recoveries spiked in a cosmetic sample were in the range of 77% -116%. Benzophenone-3, butylmethoxydibenzoylmethane, ethylhexylsalicylatec and homosalate were found in the detected cosmetic samples, and the concentration of homosalate was the highest. The results indicated that this method had potential for applications due to its convenience, accuracy and sensitivity. Oxybenzone, butylmethoxydibenzoylmethane, 2-ethylhexyl salicylatec and homosalate were found in the detected cosmetic samples, and the concentration of homosalate was the highest.%建立了高效液相色谱法准确、快速、灵敏测定化妆品中11种紫外吸收剂的方法。采用C18色谱柱,以乙腈和0.1%甲酸作为流动相,311 nm作为检测波长,在11.5 min内完成11种紫外吸收剂的基线分离。在优化的实验条件下,目标化合物的保留时间和峰面积的相对标准偏差分别小于0.05%和1.20%;另外,所有目标化合物的检出限均低于2.24 mg/L,并在5~500 mg/L 内均具有良好的线性关系(R2>0.9990),样品加标回收率为77%~116%。上述结果表明,本方法具有简便、准确、灵敏的特点。对两种不同化妆品中2-羟基-4甲氧基二苯甲酮-5-磺酸、对-氨基苯甲酸等11种紫外吸收剂的测定结果表明,2-

  19. 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

  20. 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

  1. Development of new and improved labelling procedures for introducing isotopic hydrogen and carbon-11 into organic compounds

    International Nuclear Information System (INIS)

    been done in two ways, namely by investigating, (i) the direct insertion of the carbonyl group into amines and (ii) by the palladium(II)-mediated cross coupling carbonylations of organostannanes with either aryl iodides or diaryliodonium salts. [11C]Carbon monoxide insertion into lithiated amines was found to be impractical. Palladium(II)-mediated cross coupling 11C-carbonylation was found to provide an efficient means to label substituted benzophenones. High radiochemical yields were achieved under very mild reaction conditions and in short reaction times (1 min). When various substituted diaryliodonium salts were used to partner phenyltributylstannane, the expected [11C]ketones were produced in moderate radiochemical yields (30 - 43%). By the use of variously substituted arylstannanes with diphenyliodonium bromide, several [11C]ketones were rapidly synthesised in exceptionally high radiochemical yields (typically 98%). (author)

  2. 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

  3. Ionic liquids: radiation chemistry, solvation dynamics and reactivity patterns

    International Nuclear Information System (INIS)

    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 (MeBu3N+)(NTf2-). Rate constants for solvated electron capture by benzophenone, pyrene and phenanthrene were on the order of 1.6x108 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 109 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 that the diffusion rate for the

  4. Determination of the migration of seven photoinitiators in food packaging materials into aqueous solvent%食品包装材料中7种光引发剂向水性模拟液中的迁移测定

    Institute of Scientific and Technical Information of China (English)

    刘芃岩; 黄恩洁; 陈艳杰

    2012-01-01

    为了考察食品包装材料中光引发剂向食品中迁移的情况,以水性模拟液作为迁移溶剂,用65 μm聚二甲基硅氧烷/二乙烯基苯(PDMS-DVB)纤维头进行固相微萃取结合气相色谱-质谱(SPME/GC-MS)分析方法同时测定食品包装材料中7种光引发剂(PIs)的迁移量.方法的检出限为0.001 2 ~0.006 9 μg/L,线性范围为0.03 ~ 1.0μg/L(r2>0.990 9),在3种浓度的添加水平下,加标回收率为70.8%~ 112.0%,相对标准偏差不大于14.0%.利用建立的方法对20个实际样品进行测定,发现所有样品中均检出二苯甲酮,其中10个样品中检出4-甲基二苯甲酮,3个样品中检出1-羟基环己基苯基甲酮,1个样品中检出安息香双甲醚.该方法的灵敏度高,样品前处理过程简单,无需使用有机溶剂,为食品接触材料表面印刷油墨中PIs向水性样品中的迁移测定提供了参考.%The quantity of photoinitiators ( PIs) migrated into hydrosoluble foods from packaging materials is usually very small. It is hardly detectable by using the current methods. For this reason, the article describes a new effective method for detecting the migration of PIs. In this method, the migration experiment was done in aqueous food simulation. After the PIs in printing inks used in food contact materials were extracted from the solution via solid-phase microextraction (SPME) using 65 μm polydimethylsiloxane/divinylbenzene ( PDMS-DVB)-coated fiber, their migration amounts were determined by gas chromatography-mass spectrometry (GC-MS) in the selected ion monitoring mode (SIM). The PIs determined by SPME/GC-MS were benzophenone (BP) , 1-hydroxycyclohexyl-phenylketone (CPK), ethyl-4-dimethyl-amino-benzoate (EDMAB), 4-methylbenzophenone (4-MBP), 2,2-dimethoxy-2-phenylacetophenone (2,2-DMPA) , methyl 2-benzoylbenzoate (OMBB) and 2-ethylhexyl-4-dimethyl-aminobenzoate ( EHDAB). The limits of detection (S/N = 3) were between 0. 001 2 and 0. 006 9 |xg/L. The linearity

  5. A Development of Rapid, Practical and Selective Process for Preparation of Z-Oximes

    International Nuclear Information System (INIS)

    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 at room or reflux temperature