Sample records for benzophenone

  1. Photopolymerization induced by a benzophenone derivative photoinitiator

    Institute of Scientific and Technical Information of China (English)


    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. Two new benzophenone glucosides from Cratoxylon Cochinchinensis

    Institute of Scientific and Technical Information of China (English)

    Hai Yang Yu; San Lin Jin; Xue Zhang; Yuan Liu; Yang Fu Ou; Nai Li Wang; Xin heng Yao


    Two new benzophenone glucosides were isolated from the 60%ethanol extract of the dried stems of Cratoxylum cochinchinense.The structures were elucidated as 3-O-/3-O-β-D-glucopyranosyl-2',4,6'-trihydroxy-benzophenone and 3-O-β-D-glucopyranosyl-2',5.6'-trihydroxybenzophenone on the basis of spectral and chemical methods.

  3. Polyimides Derived from Novel Asymmetric Benzophenone Dianhydrides (United States)

    Chuang, Chun-Hua (Inventor)


    This invention relates to the composition and processes for preparing thermoset polyimides derived from an asymmetric dianhydride, namely 2,3,3',4'-benzophenone dianhydride (a-BTDA) with at least one diamine, and a monofunctional terminal endcaps. The monofunctional terminating groups include 4-phenylethynylphthalic anhydride ester-acid derivatives, phenylethyl trimellitic anhydride (PETA) and its ester derivatives as well as 3-phenylethynylaniline. The process of polyimide composite comprises impregnating monomer reactants of dianhydride or its ester-acid derivatives, diamine and with monofunctional reactive endcaps into glass, carbon, quartz or synthetic fibers and fabrics, and then stack up into laminates and subsequently heated to between C. either at atmosphere or under pressure to promote the curing and crosslinking of the reactive endcaps to form a network of thermoset polyimides.

  4. Lycopene control of benzophenone-sensitized lipid peroxidation (United States)

    Cvetković, Dragan; Marković, Dejan


    Lycopene antioxidant activity in the presence of two different mixtures of phospholipids in hexane solution, under continuous regime of UV-irradiation from three different ranges (UV-A, UV-B, and UV-C) has been evaluated in this work. Lycopene expected role was to control lipid peroxidation, by scavenging free radicals generated by UV-irradiation, in the presence and in the absence of selected photosensitizer, benzophenone. This work shows that lycopene undergoes to UV-induced destruction (bleaching), highly dependent on the incident photons energy input, more expressed in the presence than in the absence of benzophenone. The further increase ("excess") of its bleaching is undoubtedly related to the further increase of its antioxidant activity in the presence of benzophenone, having the same cause: increase of (phospholipids peroxidation) chain-breaking activities.

  5. Polarization and spectral shift of benzophenone in supercritical water. (United States)

    Fonseca, T L; Georg, H C; Coutinho, K; Canuto, S


    Monte Carlo simulation and quantum mechanics calculations based on the INDO/CIS and TD-DFT methods were utilized to study the solvatochromic shift of benzophenone when changing the environment from normal water to supercritical (P = 340.2 atm and T = 673 K) condition. Solute polarization increases the dipole moment of benzophenone, compared to gas phase, by 88 and 35% in normal and supercritical conditions, giving the in-solvent dipole value of 5.8 and 4.2 D, respectively. The average number of solute-solvent hydrogen bonds was analyzed, and a large decrease of 2.3 in normal water to only 0.8 in the supercritical environment was found. By using these polarized models of benzophenone in the two different conditions of water, we performed MC simulations to generate statistically uncorrelated configurations of the solute surrounded by the solvent molecules and subsequent quantum mechanics calculations on these configurations. When changing from normal to supercritical water environment, INDO/CIS calculations explicitly considering all valence electrons of the 235 solvent water molecules resulted in a solvatochromic shift of 1425 cm(-1) for the most intense pi-pi* transition of benzophenone, that is, slightly underestimated in comparison with the experimentally inferred result of 1700 cm(-1). TD-B3LYP/6-311+G(2d,p) calculations on the same configurations but with benzophenone electrostatically embedded in the 320 water molecules resulted in a solvatochromic shift of 1715 cm(-1) for this transition, in very good agreement with the experimental result. When using the unpolarized model of the benzophenone, this calculated solvatochromic shift was only 640 cm(-1). Additional calculations were also made by using BHandHLYP/6-311+G(2d,p) to analyze the effect of the asymptotic decay of the exchange functional. This study indicates that, contrary to the general expectation, there is a sizable solute polarization even in the low-density regime of supercritical condition and

  6. A Single Amino Acid Substitution Converts Benzophenone Synthase into Phenylpyrone Synthase*


    Klundt, Tim; Bocola, Marco; Lütge, Maren; Beuerle, Till; Liu, Benye; Beerhues, Ludger


    Benzophenone metabolism provides a number of plant natural products with fascinating chemical structures and intriguing pharmacological activities. Formation of the carbon skeleton of benzophenone derivatives from benzoyl-CoA and three molecules of malonyl-CoA is catalyzed by benzophenone synthase (BPS), a member of the superfamily of type III polyketide synthases. A point mutation in the active site cavity (T135L) transformed BPS into a functional phenylpyrone synthase (PPS). The dramatic ch...

  7. Conformational control of benzophenone-sensitized charge transfer in dinucleotides


    Merz, Thomas; Wenninger, Matthias; Weinberger, Michael; Riedle, Eberhard; Wagenknecht, Hans-Achim; Schuetz, Martin


    Charge transfer in DNA cannot be understood without addressing the complex conformational flexibility, which occurs on a wide range of timescales. In order to reduce this complexity four dinucleotide models 1X consisting of benzophenone linked by a phosphodiester to one of the natural nucleosides X = A, G, T, C were studied in water and methanol. The theoretical work focuses on the dynamics and electronic structure of 1G. Predominant conformations in the two solvents were obtained by molecula...

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

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    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:; 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


    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)


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    Georges C. Accrombessi


    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.

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

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    L. F. Vieira Ferreira


    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.

  11. Growth, crystalline perfection and characterization of benzophenone oxime crystal (United States)

    Rajasekar, M.; Muthu, K.; Meenatchi, V.; Bhagavannarayana, G.; Mahadevan, C. K.; Meenakshisundaram, SP.

    Single crystals of benzophenone oxime (BPO) have been grown by slow evaporation solution growth technique from ethanol at room temperature. The single crystal X-ray diffraction study reveals that the crystal belongs to monoclinic system and cell parameters are, a = 9.459 Å, b = 8.383 Å, c = 26.690 Å, v = 2115 Å3 and β = 92.807°. The structure and the crystallinity of the materials were further confirmed by powder X-ray diffraction analysis. The various functional groups present in the molecule are confirmed by FT-IR analysis. The TG/DSC studies reveal the purity of the material and the crystals are transparent in the entire visible region having a lower optical cut-off at ˜300 nm. The crystalline perfection was evaluated by high-resolution X-ray diffraction (HRXRD). The crystal is further characterized by Kurtz powder technique, dielectric studies and microhardness analysis.

  12. Inhibitory activity of benzophenones from Anemarrhena asphodeloides on pancreatic lipase. (United States)

    Jo, Yang Hee; Kim, Seon Beom; Ahn, Jong Hoon; Liu, Qing; Hwang, Bang Yeon; Lee, Mi Kyeong


    Pancreatic lipase is a key enzyme for lipid absorption by hydrolysis of total dietary fats. Therefore, inhibition of pancreatic lipase is suggested to be an effective therapy in the regulation of obesity. The EtOAc-soluble fraction of Anemarrhena asphodeloides rhizomes significantly inhibited pancreatic lipase activity as assessed using porcine pancreatic lipase as an in vitro assay system. Further fractionation of the EtOAc-soluble fraction of A. asphodeloides led to the isolation of a new benzophenone glycoside, zimoside A (1), together with the eleven known compounds iriflophenone (2), 2,4',6-trihydroxy-4-methoxybenzophenone (3), foliamangiferoside A (4), (2,3-dihydroxy-4-methoxyphenyl)(4-hydroxyphenyl)-methanone (5), 1,4,5,6,-tetrahydroxyxanthone (6), isosakuranetin (7), 4-hydroxybenzoic acid (8), 4-hydroxyacetophenone (9), vanillic acid (10), tyrosol (11) and 5-hydroxymethyl-2-furaldehyde (12). Among the isolated compounds, 3, 5 and 10 showed significant inhibition of pancreatic lipase activity.

  13. Formation pathways of brominated products from benzophenone-4 chlorination in the presence of bromide ions

    Institute of Scientific and Technical Information of China (English)

    Ming Xiao; Dongbin Wei; Liping Li; Qi Liu; Huimin Zhao; Yuguo Du


    The brominated products,formed in chlorination treatment of benzophenone-4 in the presence of bromide ions,were identified,and the formation pathways were proposed.Under disinfection conditions,benzophenone-4 would undertake electrophilic substitution generating mono-or di-halogenated products,which would be oxidized to esters and further hydrolyzed to phenol derivatives.The generated catechol intermediate would be transformed into furan-like heterocyclic product.The product species were pH-dependent,while benzophenone-4 ehmination was chlorine dose-dependent.When the chlorination treatment was performed on ambient water spiked with benzophenone-4 and bromide ions,most of brominated byproducts could be detected,and the acute toxicity significantly increased as well.

  14. Photolysis of incorporated benzophenone derivatives inside compressed lipid monolayers

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    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.


    Institute of Scientific and Technical Information of China (English)

    Bao-jun Qu


    The radical intermediates, the crosslink microstructures, and the reaction mechanism of benzophenone (BP)-photoinitiated crosslinking of low-density polyethylene (LDPE) and model compounds (MD) have been reviewed in detail.The spin-trapping electron spin resonance (ESR) spectra obtained from the LDPE/BP systems with spin-trap agents showthat two kinds of polymer radical intermediates are mainly formed: tertiary carbon and secondary carbon radicals. The spin-trapping ESR studies of MD/BP systems give further evidence that photocrosslinking reactions of PE predominantly takeplace at sites of tertiary carbon, secondary carbon, and especially allylic carbon when available. The high resolution 13C-NMR spectra obtained from LDPE and MD systems show that the crosslink microstructures have H- and Y-type links andthat their concentrations are of the same order. The fluorescence, ESR, 13C and 1H-NMR spectra from the PE and MDsystems demonstrate that the main photoreduction product of BP (PPB) is benzpinacol formed by the recombination of twodiphenylhydroxymethyl (K*) radical intermediates. Two new PPB products: an isomer of benzpinacol with quinoid structure,1-phenylhydroxymethylene-4-diphenylhydroxymethyl-2,5-cyclohexadiene and three kinds of a-alkyl-benzhydrols have beendetected and identified. These results provide new experimental evidence for elucidating the reaction mechanism in the BP-photoinitiated crosslinking of polyethylene.

  16. Determination of personal care products -benzophenones and parabens- in human menstrual blood. (United States)

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


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

  17. Conformational control of benzophenone-sensitized charge transfer in dinucleotides. (United States)

    Merz, Thomas; Wenninger, Matthias; Weinberger, Michael; Riedle, Eberhard; Wagenknecht, Hans-Achim; Schütz, Martin


    Charge transfer in DNA cannot be understood without addressing the complex conformational flexibility, which occurs on a wide range of timescales. In order to reduce this complexity four dinucleotide models 1X consisting of benzophenone linked by a phosphodiester to one of the natural nucleosides X = A, G, T, C were studied in water and methanol. The theoretical work focuses on the dynamics and electronic structure of 1G. Predominant conformations in the two solvents were obtained by molecular dynamics simulations. 1G in MeOH adopts mainly an open geometry with a distance of 12–16 Å between the two aromatic parts. In H2O the two parts of 1G form primarily a stacked conformation yielding a distance of 5–6 Å. The low-lying excited states were investigated by electronic structure theory in a QM/MM environment for representative snapshots of the trajectories. Photo-induced intramolecular charge transfer in the S1 state occurs exclusively in the stacked conformation. Ultrafast transient absorption spectroscopy with 1X reveals fast charge transfer from S1 in both solvents with varying yields. Significant charge transfer from the T1 state is only found for the nucleobases with the lowest oxidation potential: in H2O, charge transfer occurs with 3.2 × 10(9) s(-1) for 1A and 6.0 × 10(9) s(-1) for 1G. The reorganization energy remains nearly unchanged going from MeOH to the more polar H2O. The electronic coupling is rather low even for the stacked conformation with H(AB) = 3 meV and explains the moderate charge transfer rates. The solvent controls the conformational distribution and therefore gates the charge transfer due to differences in distance and stacking.

  18. Multifunctional finishing of cotton with 3,3',4,4'-benzophenone tetracarboxylic acid: functional performance. (United States)

    Hou, Aiqin; Sun, Gang


    3,3',4,4'-Benzophenone tetracarboxylic acid (BPTCA) can directly react with hydroxyl groups on cotton cellulose to form ester bonds, which could crosslink cellulose and provide wrinkle-free functions to the cotton fabrics. BPTCA, as a derivative of photo-active benzophenone, can absorb ultraviolet lights and offer ultraviolet (UV) protective and photo-sensitive functions on the treated materials. Finishing conditions such as agent concentration, curing temperature and time, could affect ester bond formation and crosslinking of cellulose. Wrinkle-free and UV protective functions in relationship to the functional agent, as well as surface morphology of BPTCA treated cotton were investigated as well.

  19. Photolysis of benzophenone with two-step two-laser excitation

    Institute of Scientific and Technical Information of China (English)


    The first laser excites a molecule to a lower triplet state and another sequential laser excites it resonantly to higher triplet states or makes it ionization. This two-step two-laser method provides a novel way to study the electron transfer or charge transfer of excited molecules. The higher excited benzophenone and its radical cation can be observed under the time-resolved ab sorption method when it was excited to lower triplet state by one laser and another one exciting it to higher triplet states resonantly. The higher excited benzophenone molecules undergoing inter molecular hydrogen abstraction with iso-propylalcohol molecules are faster than the lower ones.

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

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    Kei Shimoda


    Full Text Available 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 diphenylmethyl β-D-glucopyranoside were 85 and 15%, respectively.

  1. Benzophenones as Generic Host Materials for Phosphorescent Organic Light-Emitting Diodes. (United States)

    Jhulki, Samik; Seth, Saona; Ghosh, Avijit; Chow, Tahsin J; Moorthy, Jarugu Narasimha


    Despite the fact that benzophenone has traditionally served as a prototype molecular system for establishing triplet state chemistry, materials based on molecular systems containing the benzophenone moiety as an integral part have not been exploited as generic host materials in phosphorescent organic light-emitting diodes (PhOLEDs). We have designed and synthesized three novel host materials, i.e., BP2-BP4, which contain benzophenone as the active triplet sensitizing molecular component. It is shown that their high band gap (3.91-3.93 eV) as well as triplet energies (2.95-2.97 eV) permit their applicability as universal host materials for blue, green, yellow, and red phosphors. While they serve reasonably well for all types of dopants, excellent performance characteristics observed for yellow and green devices are indeed the hallmark of benzophenone-based host materials. For example, maximum external quantum efficiencies of the order of 19.2% and 17.0% were obtained from the devices fabricated with yellow and green phosphors using BP2 as the host material. White light emission, albeit with rather poor efficiencies, has been demonstrated as a proof-of-concept by fabrication of co-doped and stacked devices with blue and yellow phosphors using BP2 as the host material.

  2. Self-assembled benzophenone bis-urea macrocycles facilitate selective oxidations by singlet oxygen. (United States)

    Geer, Michael F; Walla, Michael D; Solntsev, Kyril M; Strassert, Cristian A; Shimizu, Linda S


    This manuscript investigates how incorporation of benzophenone, a well-known triplet sensitizer, within a bis-urea macrocycle, which self-assembles into a columnar host, influences its photophysical properties and affects the reactivity of bound guest molecules. We further report the generation of a remarkably stable organic radical. As expected, UV irradiation of the host suspended in oxygenated solvents efficiently generates singlet oxygen similar to the parent benzophenone. In addition, this host can bind guests such as 2-methyl-2-butene and cumene to form stable solid host-guest complexes. Subsequent UV irradiation of these complexes facilitated the selective oxidation of 2-methyl-2-butene into the allylic alcohol, 3-methyl-2-buten-1-ol, at 90% selectivity as well as the selective reaction of cumene to the tertiary alcohol, α,α'-dimethyl benzyl alcohol, at 63% selectivity. However, these products usually arise through radical pathways and are not observed in the presence of benzophenone in solution. In contrast, typical reactions with benzophenone result in the formation of the reactive singlet oxygen that reacts with alkenes to form endoperoxides, diooxetanes, or hydroperoxides, which are not observed in our system. Our results suggest that the confinement, the formation of a stable radical species, and the singlet oxygen photoproduction are responsible for the selective oxidation processes. A greater understanding of the mechanism of this selective oxidation could lead to development of greener oxidants.

  3. A new benzophenone glycoside from the leaves of Psidium guajava L.

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    Hui Zheng Fu; Jing Zhi Yang; Chuang Jun Li; Dong Ming Zhang


    A new benzophenone glycoside, 2,6-dihydroxy-4-O-β-D-glucopyranosylbenzophenone (1), was isolated from the leaves of guajava L. Its structure was elucidated by spectral and chemical methods. 1 showed significant activities to secretion of NO in mouse peritoneal macrophages in 10 μmol/L.

  4. A novel alkenoic acid ester and a new benzophenone from Ranunculus ternatus

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    A novel alkenoic acid ester, (E)-4-hydroxy-dodec-2-enedioic acid-12-O-methyl ester and a new benzophenone, ethyl (S)-3-[2-(3,4-dihydroxybenzoyl)-4,5-dihydroxyphenyl]-2-hydroxypropanoate, together with a known compound, (E)-4-hydroxy-dodec-2-enedioic acids were isolated from the roots of Ranunculus ternatus. Their structures were elucidated by spectroscopic methods.

  5. Computational determination of the dominant triplet population mechanism in photoexcited benzophenone

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    Sergentu, Dumitru-Claudiu; Maurice, Remi; Havenith, Remco W. A.; Broer, Ria; Roca-Sanjuan, Daniel


    In benzophenone, intersystem crossing occurs efficiently between the S-1(n pi(star)) state and the T-1 state of dominant n pi(star) character, leading to excited triplet states after photoexcitation. The transition mechanism between S-1(n pi(star)) and T-1 is still a matter of debate, despite severa

  6. [Measurement of 11 benzophenone ultraviolet-filters in cosmetics by high performance liquid chromatography]. (United States)

    Qu, Baocheng; Bian, Haitao; Mao, Xiqin; Li, Jin


    A sample preparation and analytical method with liquid-liquid extraction (LLE) and high performance liquid chromatography (HPLC) was developed to detect 11 benzophenone ultraviolet-filters in cosmetics. The target compounds were extracted by the mixed solutions of tetrahydrofuran (TH)/methanol/water or dichloromethane/water at proper ratios. The extracts were centrifuged and filtered to remove matrix compounds, and then analyzed by HPLC. The separation of analytes was carried out on a Diamonsil-C18 column (150 mm x 4.6 mm, 5 μm) with 0.1% (v/v) formic acid aqueous solution (containing 10 mmol/L ammonium acetate) as mobile phase A and methanol containing 0.1% (v/v) formic acid as mobile phase B. The spiked recoveries of the method (n = 7) were 93.4%-103.8% with the relative standard deviations of 0.1%-4.2%. The limits of detection (LODs) were in the range of 4.0-30 μg/g and the limits of quantitation (LOQs) ranged from 15 to 100 μg/g. The method was applied to the determination of 42 cosmetic samples randomly purchased from the supermarket in Dalian. Five benzophenone series were always detected, in which the content of benzophenone-3 in sunscreen cream and the content of benzophenone-2 in perfume were very high and reached 2 785 μg/g and 2 106 μg/g, respectively. The results showed that the developed method is efficient, reliable and sensitive, which can be applied to the determination of benzophenones in cosmetics.

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


    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.

  8. Stability and toxicity of selected chlorinated benzophenone-type UV filters in waters. (United States)

    Zhuang, Rensheng; Žabar, Romina; Grbović, Gorica; Dolenc, Darko; Yao, Jun; Tišler, Tatjana; Trebše, Polonca


    In our study, the transformation of two most widely used UV filters, benzophenone-3 (BP3) and benzophenone-4 (BP4), in chlorinated water with disinfection reagents sodium hypochlorite (NaClO) and trichloroisocyanuric acid (TCCA) was studied. Based on the HPLC/MS and UV-Vis analysis the formation of two different chlorinated products (5-chloro-2-hydroxy-4-methoxybenzophenone and 3,5-dichloro-2-hydroxy-4-methoxybenzophenone) was established. Identity of chlorinated products was confirmed by means of comparison of retention times with independently synthesized standards. Photostability study showed that dichloro-derivative in water is less stable then parent compounds, which is not the case for monochloro-derivatives. Toxicity of chlorinated compounds tested by Vibrio fischeri was found to be in the same range as that of the starting compounds. Preliminary testing of real water samples from swimming pools and sea swimming areas confirmed the presence of BP3 and its 3,5-dichloro derivative.

  9. Evaluation of Benzophenone-N-ethyl Morpholine Ethers as Antibacterial and Antifungal Activities

    Directory of Open Access Journals (Sweden)

    A. Bushra Begum


    Full Text Available Microorganisms are closely associated with the health and welfare of human beings. Whereas some microorganisms are beneficial, others are detrimental. Bacterial infections often produce inflammation and pains and in some instances, infections result in high mortality. Any subtle change in the drug molecule, which may not be detected by chemical methods, can be revealed by a change in the antimicrobial activity and hence microbiological assays are very useful. A series of substituted hydroxy benzophenones and benzophenone-N-ethyl morpholine ethers were screened for their antibacterial and antifungal activities. Antibacterial activity against S. aureus, E. aerogenes, M. luteus, K. pneumonia, and S. typhimurium, S. paratyphi-B and P. vulgaris bacterial strains and antifungal activity against C. albicans, B. cinerea, M. pachydermatis, C. krusei fungal strains were carried out. The bioassays indicated that most of the synthesized compounds showed potential antibacterial and antifungal agents.

  10. Ten-year trends in urinary concentrations of triclosan and benzophenone-3 in the general U.S. population from 2003 to 2012. (United States)

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


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

  11. UHPLC-MS/MS method for the determination of bisphenol A and its chlorinated derivatives, bisphenol S, parabens, and benzophenones in human urine samples. (United States)

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


    In the present work, a new method based on a sample treatment by dispersive liquid-liquid microextraction (DLLME) for the extraction of six bisphenols (bisphenol A, bisphenol S, and monochloro-, dichloro-, trichloro-, and tetrachlorobisphenol A), four parabens (methyl-, ethyl-, propyl-, and butylparaben), and six benzophenones (benzophenone-1, benzophenone-2, benzophenone-3, benzophenone-6, benzophenone-8, and 4-hydroxybenzophenone) in human urine samples, followed by ultrahigh-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) analysis, is validated. An enzymatic treatment allows determining the total content of the target EDCs. The extraction parameters were accurately optimized using multivariate optimization strategies. Ethylparaben ring-(13)C6, benzophenone-d10, and bisphenol A-d16 were used as surrogates. Limits of quantification ranging from 0.1 to 0.6 ng mL(-1) and interday variabilities (evaluated as relative standard deviations) from 2.0 to 13.8% were obtained. The method was validated using matrix-matched standard calibration followed by a recovery assay with spiked samples. Recovery rates ranged from 94 to 106%. A good linearity, for concentrations up to 300 ng mL(-1) for parabens and 40 ng mL(-1) for benzophenones and bisphenols, was also obtained. The method was satisfactorily applied for the determination of target compounds in human urine samples from 20 randomly selected individuals.

  12. A Single Amino Acid Substitution Converts Benzophenone Synthase into Phenylpyrone Synthase* (United States)

    Klundt, Tim; Bocola, Marco; Lütge, Maren; Beuerle, Till; Liu, Benye; Beerhues, Ludger


    Benzophenone metabolism provides a number of plant natural products with fascinating chemical structures and intriguing pharmacological activities. Formation of the carbon skeleton of benzophenone derivatives from benzoyl-CoA and three molecules of malonyl-CoA is catalyzed by benzophenone synthase (BPS), a member of the superfamily of type III polyketide synthases. A point mutation in the active site cavity (T135L) transformed BPS into a functional phenylpyrone synthase (PPS). The dramatic change in both substrate and product specificities of BPS was rationalized by homology modeling. The mutation may open a new pocket that accommodates the phenyl moiety of the triketide intermediate but limits polyketide elongation to two reactions, resulting in phenylpyrone formation. 3-Hydroxybenzoyl-CoA is the second best starter molecule for BPS but a poor substrate for PPS. The aryl moiety of the triketide intermediate may be trapped in the new pocket by hydrogen bond formation with the backbone, thereby acting as an inhibitor. PPS is a promising biotechnological tool for manipulating benzoate-primed biosynthetic pathways to produce novel compounds. PMID:19710020

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

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


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

  14. 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: [Faculty of Technology, 16000 Leskovac (Serbia)


    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.

  15. Substantivity of sunscreens -in vitro evaluation of the transdermal permeation characteristics of some benzophenone derivatives. (United States)

    Monti, D; Saettone, M F; Centini, M; Anselmi, C


    Synopsis The in vitro permeation through excised hairless mouse skin of a series of 4-O-(N, N-dimethylaminoalkyl)-benzophenones, non-quaternarized and quaternarized, and of two commercial benzophenone sunscreens, taken as reference compounds, was investigated. The aim of the study was to verify the skin penetration of the highly skin-substantive quaternary ammonium derivatives, in comparison with their parent, non-quaternarized compounds. While the quaternary derivatives proved unable to permeate the skin during the period of observation (45 h), their parent amine hydrochlorides and the reference sunscreens (2-hydroxy-4-methoxy-benzophenone-5-sulphonic acid and 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone 5,5'-sodium disulphonate), showed appreciable transdermal fluxes. These data indicate that the presence of a quaternary ammonium group in a molecule, besides inducing a high affinity for cutaneous keratin, may result in hindered or reduced transdermal (and possibly systemic) absorption. Both features may contribute in improving the safety of a cosmetic sunscreen. Résumé On a analysé la pénétration in vitro au travers de peau excisée de souris sans poils d'une gamme de 4-O-(N, N-dimethylaminoalkyl)benzophenones quaternisés et non quaternisés ainsi que de 2 écrans solaires au benzophénone commercialisés utilisés comme témoins. Cette étude avait pour but de vérifier la pénétration dermique de dérivés d'ammonium quaternaire hautement substantifs sur la peau, par rapport à des composés non quatenaires de la même famille. Tandis que les dérivés quaternaires se sont avérés incapables de pénétrer la peau durant la période d'observation (45 heures), les hydrochlorures d'amine et les écrans solaires témoins (2-hydroxy-4-methoxybenzophenone-5-acide sulfonique et 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone 5,5'-disulphonate de sodium), ont montré des flux transdermiques appréciales. Ces données indiquent que la présence d'un groupe d

  16. 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: [Department of Physics, University of Pune, Pune 411007 (India)


    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.

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

    Directory of Open Access Journals (Sweden)

    Kei Shimoda


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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  19. 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


    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.

  20. 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


    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.

  1. New Metabolites and Bioactive Chlorinated Benzophenone Derivatives Produced by a Marine-Derived Fungus Pestalotiopsis heterocornis (United States)

    Lei, Hui; Lin, Xiuping; Han, Li; Ma, Jian; Ma, Qingjuan; Zhong, Jialiang; Liu, Yonghong; Sun, Tiemin; Wang, Jinhui; Huang, Xueshi


    Four new compounds, including two isocoumarins, pestaloisocoumarins A and B (1, 2), one sesquiterpenoid degradation, isopolisin B (4), and one furan derivative, pestalotiol A (5), together with one known isocoumarin, gamahorin (3), and three chlorinated benzophenone derivatives, pestalachloride B (6), pestalachloride E (7) and a mixture of pestalalactone atropisomers (8a/8b), were isolated from a culture of the fungus Pestalotiopsis heterocornis associated with sponge Phakellia fusca. These new chemical structures were established using NMR and MS spectroscopic data, as well as single-crystal X-ray crystallographic analysis and CD Cotton effects. All of the isolated compounds were evaluated for their antimicrobial and cytotoxic activities. Isocoumarins 1–3, showed antibacterial activities against Gram-positive bacteria Staphylococcus aureus and Bacillus subtilis with MIC values ranging from 25 to 100 μg/mL and weak antifungal activities. Chlorinated benzophenone derivatives 6–8 exhibited antibacterial activities against S. aureus and B. subtilis with MIC values ranging from 3.0 to 50 μg/mL and cytotoxicities against four human cancer cell lines with IC50 values of 6.8–87.8 μM. PMID:28335391

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

    Directory of Open Access Journals (Sweden)

    Hui Lei


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

  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. Simplified matrix solid phase dispersion procedure for the determination of parabens and benzophenone-ultraviolet filters in human placental tissue samples. (United States)

    Vela-Soria, F; Rodríguez, I; Ballesteros, O; Zafra-Gómez, A; Ballesteros, L; Cela, R; Navalón, A


    In recent decades, the industrial development has resulted in the appearance of a large amount of new chemicals that are able to produce disorders in the human endocrine system. These substances, so-called endocrine disrupting chemicals (EDCs), include many families of compounds, such as parabens and benzophenone-UV filters. Taking into account the demonstrated biological activity of these compounds, it is necessary to develop new analytical procedures to assess the exposure in order to establish, in an accurate way, relationships between EDCs and harmful health effects in population. In the present work, a new method based on a simplified sample treatment by matrix solid phase dispersion (MSPD) followed by ultrahigh performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) analysis, is validated for the determination of four parabens (methyl-, ethyl-, propyl- and butylparaben) and six benzophenone-UV filters (benzophenone-1, benzophenone-2, benzophenone-3, benzophenone-6, benzophenone-8 and 4-hydroxybenzophenone) in human placental tissue samples. The extraction parameters were accurately optimized using multivariate optimization strategies. Ethylparaben ring-13C6 and benzophenone-d10 were used as surrogates. The found limits of quantification ranged from 0.2 to 0.4 ng g(-1) and inter-day variability (evaluated as relative standard deviation) ranged from 5.4% to 12.8%. The method was validated using matrix-matched standard calibration followed by a recovery assay with spiked samples. Recovery rates ranged from 96% to 104%. The method was satisfactorily applied for the determination of compounds in human placental tissue samples collected at the moment of delivery from 10 randomly selected women.

  5. Garcinia benzophenones inhibit the growth of human colon cancer cells and synergize with sulindac sulfide and turmeric. (United States)

    Einbond, Linda Saxe; Mighty, Jason; Kashiwazaki, Ryota; Figueroa, Mario; Jalees, Filza; Acuna, Ulyana Munoz; Le Gendre, Onica; Foster, David A; Kennelly, Edward J


    Previous studies indicate that extracts and purified components from Garcinia species inhibit the growth of human colon cancer cells. Garcinia benzophenones activate the expression of genes in the endoplasmic reticulum and cellular energy stress (mTOR) pathways. This study examines the growth inhibitory and synergistic effects of Garcinia benzophenones, alone or combined with chemopreventive agents, on human colon cancer cells. To find optimal combination treatments, HT29 colon cancer cells were treated with benzophenones alone, or combined with chemopreventive agents, and cell growth measured using the MTT assay. To reveal effects on signaling pathways, we assessed effects of the MEK inhibitor U0126 and the ER IP3 receptor antagonist heparin, as well as effects on the phosphorylation of 4E-BP-1 (mTOR pathway), using Western blot analysis. New and known benzophenones from Garcinia intermedia inhibited the growth of human colon cancer cells; an alcohol extract of Garcinia xanthochymus, as well as purified guttiferones (guttiferone E and xanthochymol), preferentially inhibited the growth of colon cancer versus nonmalignant intestinal epithelial cells. Guttiferone E exhibited synergy with the NSAID sulindac sulfide and xanthochymol, with the spice turmeric. Guttiferone A did not alter phosphorylation of 4E-BP-1, indicating that the mTORC1 pathway is not involved in its action. The effects of xanthochymol were enhanced by U0126, at low doses, and were blocked by heparin, indicating that the MEK pathway is involved, while the ER IP3 receptor is critical for its action. These studies indicate the potential of benzophenones, alone or combined with sulindac sulfide or turmeric, to prevent and treat colon cancer.

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

    Directory of Open Access Journals (Sweden)

    Hung-Chun Tong


    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.

  7. Benzophenone-based photochemical micropatterning of biomolecules to create model substrates and instructive biomaterials. (United States)

    Turgeon, Aurora J; Harley, Brendan A; Bailey, Ryan C


    The extracellular matrix (ECM) is a dynamic and heterogeneous environment that controls many aspects of cell behavior. Not surprisingly, many different approaches have focused on creating model substrates that recapitulate the biomolecular, topographical, and mechanical properties of the ECM for in vitro studies of cell behavior. This chapter details a general, versatile method for the spatially controlled deposition of multiple biomolecules onto both planar and topographically complex support structures with micrometer resolution. This approach is based upon the well-understood photochemical UV crosslinking of benzophenone (BP) to solution-phase biomolecules. This is a molecularly general strategy that can be utilized to immobilize biomolecules onto any surface prefunctionalized with BP. Examples described herein include modification of planar and corrugated glass substrates as well as collagen-glycosaminoglycan biomaterials configured either as highly porous scaffolds or nonporous membranes with a variety of biomolecular targets, including proteins, glycoproteins, and carbohydrates.

  8. New Benzophenones and Xanthones from Cratoxylum sumatranum ssp. neriifolium and Their Antibacterial and Antioxidant Activities. (United States)

    Tantapakul, Cholpisut; Maneerat, Wisanu; Sripisut, Tawanun; Ritthiwigrom, Thunwadee; Andersen, Raymond J; Cheng, Ping; Cheenpracha, Sarot; Raksat, Achara; Laphookhieo, Surat


    Two new benzophenones (1 and 2) and four new xanthones (4-6 and 17) together with 24 known compounds (3, 7-16, and 18-30) were isolated from the roots and twigs of Cratoxylum sumatranum ssp. neriifolium. Their structures were elucidated by spectroscopic methods. Compounds 5 and 26 showed antibacterial activity against Micrococcus luteus, Bacillus cereus, and Staphylococcus epidermis with minimum inhibitory concentrations ranging from 4 to 8 μg/mL, whereas compounds 7, 20, and 26 displayed selective antibacterial activities against Staphylococcus aureus (8 μg/mL), Salmonella typhimurium (4 μg/mL), and Pseudomonas aeruginosa (4 μg/mL), respectively. The radical scavenging effects of some isolated compounds were investigated. Compounds 11 and 21 exhibited potent activity against 2,2-diphenyl-1-picrylhydrazyl (DPPH) with IC50 values of 7.0 ± 1.0 and 6.0 ± 0.2 μM, respectively.

  9. 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


    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...... not affect the vitellogenin concentration in TG 234. After 12 d exposure of adult male zebrafish, a slight but yet significant increase in the vitellogenin concentration was observed at 268 µg/L but not at 63 µg/L and 437 µg/l BP-3. Skewing of the sex ratio is a marker of an endocrine mediated 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....

  10. Benzophenone based fluorophore for selective detection of Sn2 + ion: Experimental and theoretical study (United States)

    Jadhav, Amol G.; Shinde, Suvidha S.; Lanke, Sandip K.; Sekar, Nagaiyan


    Synthesis of novel benzophenone-based chemosensor is presented for the selective sensing of Sn2 + ion. Screening of competitive metal ions was performed by competitive experiments. The specific cation recognition ability of chemosensor towards Sn2 + was investigated by experimental (UV-visible, fluorescence spectroscopy, 1H NMR, 13C NMR, FTIR and HRMS) methods and further supported by Density Functional Theory study. The stoichiometric binding ratio and binding constant (Ka) for complex is found to be 1:1 and 1.50 × 104, respectively. The detection limit of Sn2 + towards chemosensor was found to be 0.3898 ppb. Specific selectivity and superiority of chemosensor over another recently reported chemosensor is presented.

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

    Institute of Scientific and Technical Information of China (English)


    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. Polyisoprenylated benzophenones and an unusual polyisoprenylated tetracyclic xanthone from the fruits of Garcinia cambogia. (United States)

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


    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.

  13. New Ent-Kaurane-Type Diterpene Glycosides and Benzophenone from Ranunculus muricatus Linn. (United States)

    Wu, Bi-Ling; Zou, Hui-Liang; Qin, Fang-Min; Li, Hong-Yu; Zhou, Guang-Xiong


    Two new ent-kaurane diterpene glycosides, ranunculosides A (1) and B (2), and a new benzophenone, ranunculone C (3), were isolated from the aerial part of Ranunculus muricatus Linn. The chemical structures of compounds 1-3 were established to be (2S)-ent-kauran-2β-ol-15-en-14-O-β-d-glucopyranoside, (2S,4S)-ent-kauran-2β,18-diol-15-en-14-O-β-d-glucopyranoside, and (R)-3-[2-(3,4-dihydroxybenzoyl)-4,5-dihydroxy-phenyl]-2-hydroxylpropanoic acid, respectively, by spectroscopic data and chemical methods. The absolute configuration of 1 was determined by the combinational application of RP-HPLC analysis and Mosher's method.

  14. New Ent-Kaurane-Type Diterpene Glycosides and Benzophenone from Ranunculus muricatus Linn.

    Directory of Open Access Journals (Sweden)

    Bi-Ling Wu


    Full Text Available Two new ent-kaurane diterpene glycosides, ranunculosides A (1 and B (2, and a new benzophenone, ranunculone C (3, were isolated from the aerial part of Ranunculus muricatus Linn. The chemical structures of compounds 1–3 were established to be (2S-ent-kauran-2β-ol-15-en-14-O-β-d-glucopyranoside, (2S,4S-ent-kauran-2β,18-diol-15-en-14-O-β-d-glucopyranoside, and (R-3-[2-(3,4-dihydroxybenzoyl-4,5-dihydroxy-phenyl]-2-hydroxylpropanoic acid, respectively, by spectroscopic data and chemical methods. The absolute configuration of 1 was determined by the combinational application of RP-HPLC analysis and Mosher’s method.

  15. Benzophenone-N-ethyl piperidine ether analogues--synthesis and efficacy as anti-inflammatory agent. (United States)

    Khanum, Shaukath A; Girish, V; Suparshwa, S S; Khanum, Noor Fatima


    A sequence of substituted benzophenone-N-ethyl piperidine ether analogues has been synthesized and evaluated as orally active anti-inflammatory agents with reduced side effects. The anti-inflammatory and ulcerogenic activities of the compounds were compared with naproxen, indomethacin, and phenylbutazone. These analogues showed an interesting anti-inflammatory activity in carrageenan-induced foot pad edema assay. In the air-pouch test, some of the analogues reduced the total number of leukocytes of the exudate, which indicates inhibition of prostaglandin production. Side effects of the compounds were examined on gastric mucosa, in the liver and stomach. None of the compounds illustrated significant side effects compared with standard drugs like indomethacin and naproxen.

  16. Benzophenone Synthase and Chalcone Synthase Accumulate in the Mesophyll of Hypericum perforatum Leaves at Different Developmental Stages


    Belkheir, Asma K.; Gaid, Mariam; Liu, Benye; Hänsch, Robert; Beerhues, Ludger


    The active medicinal constituents in Hypericum perforatum, used to treat depression and skin irritation, include flavonoids and xanthones. The carbon skeletons of these compounds are formed by chalcone synthase (CHS) and benzophenone synthase (BPS), respectively. Polyclonal antisera were raised against the polyketide synthases from Hypericum androsaemum and their IgG fractions were isolated. Immunoblotting and immunotitration were used to test the IgGs for crossreactivity and monospecificity ...

  17. Biosynthesis of biphenyls and benzophenones--evolution of benzoic acid-specific type III polyketide synthases in plants. (United States)

    Beerhues, Ludger; Liu, Benye


    Type III polyketide synthases (PKSs) generate a diverse array of secondary metabolites by varying the starter substrate, the number of condensation reactions, and the mechanism of ring closure. Among the starter substrates used, benzoyl-CoA is a rare starter molecule. Biphenyl synthase (BIS) and benzophenone synthase (BPS) catalyze the formation of identical linear tetraketide intermediates from benzoyl-CoA and three molecules of malonyl-CoA but use alternative intramolecular cyclization reactions to form 3,5-dihydroxybiphenyl and 2,4,6-trihydroxybenzophenone, respectively. In a phylogenetic tree, BIS and BPS group together closely, indicating that they arise from a relatively recent functional diversification of a common ancestral gene. The functionally diverse PKSs, which include BIS and BPS, and the ubiquitously distributed chalcone synthases (CHSs) form separate clusters, which originate from a gene duplication event prior to the speciation of the angiosperms. BIS is the key enzyme of biphenyl metabolism. Biphenyls and the related dibenzofurans are the phytoalexins of the Maloideae. This subfamily of the Rosaceae includes a number of economically important fruit trees, such as apple and pear. When incubated with ortho-hydroxybenzoyl (salicoyl)-CoA, BIS catalyzes a single decarboxylative condensation with malonyl-CoA to form 4-hydroxycoumarin. A well-known anticoagulant derivative of this enzymatic product is dicoumarol. Elicitor-treated cell cultures of Sorbus aucuparia also formed 4-hydroxycoumarin when fed with the N-acetylcysteamine thioester of salicylic acid (salicoyl-NAC). BPS is the key enzyme of benzophenone metabolism. Polyprenylated benzophenone derivatives with bridged polycyclic skeletons are widely distributed in the Clusiaceae (Guttiferae). Xanthones are regioselectively cyclized benzophenone derivatives. BPS was converted into a functional phenylpyrone synthase (PPS) by a single amino acid substitution in the initiation/elongation cavity. The

  18. 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


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  20. Use of pooled samples to assess human exposure to parabens, benzophenone-3 and triclosan in Queensland, Australia. (United States)

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


    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.

  1. Reactions of excited-state benzophenone ketyl radical in a room-temperature ionic liquid. (United States)

    Takahashi, Kenji; Tezuka, Hiroaki; Kitamura, Shingo; Satoh, Toshifumi; Katoh, Ryuzi


    The photochemistry of the benzophenone ketyl radical in D(1) excited state, BPH(D(1)), was studied by means of two-color dual-pulse laser flash photolysis (355 and 532 nm) in a room-temperature ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (Bmim-TFSA), and in methanol. Upon excitation with the 532 nm pulse, BPH(D(1)) emitted strong fluorescence. The transient absorption and fluorescence spectra of BPH(D(1)) were measured with nanosecond and sub-nanosecond time resolution, respectively. The observed Stokes shift was 1700 cm(-1) in Bmim-TFSA, and this shift was close to that in acetonitrile. The fluorescence lifetime of BPH(D(1)) was determined to be 5 ns in Bmim-TFSA, and again the value was close to that in acetonitrile. The rate constant of the reaction of BPH(D(1)) with CCl(4) in Bmim-TFSA was determined to be (2.1 +/- 0.4) x 10(9) M(-1) s(-1), which was 10 times the rate constant calculated on the basis of the bulk viscosity of Bmim-TFSA. The results are discussed in terms of the effective microscopic viscosity of the ionic liquid that was recently reported for the cage effect.

  2. Transformation of benzophenone-type UV filters by chlorine: Kinetics, products identification and toxicity assessments. (United States)

    Li, Jian; Ma, Li-yun; Xu, Li


    The present study focused on the kinetics, transformation pathways and toxicity of several benzophenone-type ultraviolet filters (BPs) during the water chlorination disinfection process. The transformation kinetics of the studied three BPs was found to be second-order reaction, which was dependent on the concentration of BPs and chlorine. The second-order rate constants increased from 86.7 to 975 M(-1) s(-1) for oxybenzone, 49.6-261.7 M(-1) s(-1) for 4-hydroxybenzophenone and 51.7-540 M(-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.

  3. Garcinia xanthochymus Benzophenones Promote Hyphal Apoptosis and Potentiate Activity of Fluconazole against Candida albicans Biofilms. (United States)

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


    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.

  4. Photolysis of benzophenone with two-step two-laser excitation

    Institute of Scientific and Technical Information of China (English)

    CAI; Xichen


    [1]Carmichael, I., Hug, G. L., Triplet-triplet absorption spectra of organic molecules in condensed phases, J. Phys. Chem. Ref. Data, 1986, 15(1): 1-20.[2]Nikogosyan, D. N., Two-quantum UV photochemistry of nucleic acids: comparison with conventional low-intensity UV photochemistry and radiation chemistry, Int. J. Radiat. Biol., 1990, 57(2): 233-299.[3]Yao, S. D., Sheng, S. G., Cai, J. H. et al., Nanosecond pulse radiolysis studies in China, Radiat. Phys. Chem., 1995, 46:105-109.[4]Baumann, H.. Merckel, C., Timpe, H. -J., The laser versus the lamp: reactivity of the diphenyl ketyl radical in the ground and excited states. Chem. Phys. Lett., 1984, 103(6): 497-502.[5]Barral-Tosh, S., Chattopadhyay, S. K., Das, P. K., A laser flash photolysis study of paraquat reduction by photogenerated aromatic ketyl radicals and carbonyl triplets, J. Phys. Chem., 1984, 88: 1404-1408.[6]Elisei. F., Favaro, G., Ion-forming processes on 248 nm laser excitation of benzophenone in aqueous solution: a time-resolved absorption and conductivity study, J. Photochem. Photobiol. A: Chem., 1991, 59:243-253.

  5. Friedolanostane, friedocycloartane and benzophenone constituents of the bark and leaves of Garcinia benthami. (United States)

    Nguyen, Hiep D; Trinh, Binh T D; Tran, Quyen N; Nguyen, Hoan D; Pham, Hung D; Hansen, Poul Erik; Duus, Fritz; Connolly, Joseph D; Nguyen, Lien-Hoa D


    Friedolanostanes, (22Z,24E)-3β-acetoxy-9α-hydroxy-17,14-friedolanosta-14,22,24-trien-26-oic acid, (22Z,24E)-3β,9α-dihydroxy-17,14-friedolanosta-14,22,24-trien-26-oic acid, (22Z,24E)-9α-hydroxy-3-oxo-17,14-friedolanosta-14,22,24-trien-26-oic acid, a friedocycloartane, (22Z,24E)-3α-hydroxy-17,13-friedocycloarta-12,22,24-trien-26-oic acid, and a benzophenone, benthaphenone, together with known compounds (22Z,24E)-3α,9α-dihydroxy-17,13-friedolanosta-12,22,24-trien-26-oic acid, methyl (24E)-3α,23-dihydroxy-17,14-friedolanosta-8,14,24-trien-26-oate, glutinol, lupeol, and stigmasterol, were isolated from leaves and bark of Garcinia benthami. Their structures were elucidated using spectroscopic techniques, mainly 1-D and 2-D NMR spectroscopy, and chemical correlations.

  6. 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


    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.

  7. Measurement of urinary biomarkers of parabens, benzophenone-3, and phthalates in a Belgian population. (United States)

    Dewalque, Lucas; Pirard, Catherine; Charlier, Corinne


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

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

    Directory of Open Access Journals (Sweden)

    Lucas Dewalque


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

  9. The Life of Pi Star: Exploring the Exciting and Forbidden Worlds of the Benzophenone Photophore. (United States)

    Dormán, György; Nakamura, Hiroyuki; Pulsipher, Abigail; Prestwich, Glenn D


    The widespread applications of benzophenone (BP) photochemistry in biological chemistry, bioorganic chemistry, and material science have been prominent in both academic and industrial research. BP photophores have unique photochemical properties: upon n-π* excitation at 365 nm, a biradicaloid triplet state is formed reversibly, which can abstract a hydrogen atom from accessible C-H bonds; the radicals subsequently recombine, creating a stable covalent C-C bond. This light-directed covalent attachment process is exploited in many different ways: (i) binding/contact site mapping of ligand (or protein)-protein interactions; (ii) identification of molecular targets and interactome mapping; (iii) proteome profiling; (iv) bioconjugation and site-directed modification of biopolymers; (v) surface grafting and immobilization. BP photochemistry also has many practical advantages, including low reactivity toward water, stability in ambient light, and the convenient excitation at 365 nm. In addition, several BP-containing building blocks and reagents are commercially available. In this review, we explore the "forbidden" (transitions) and excitation-activated world of photoinduced covalent attachment of BP photophores by touring a colorful palette of recent examples. In this exploration, we will see the pros and cons of using BP photophores, and we hope that both novice and expert photolabelers will enjoy and be inspired by the breadth and depth of possibilities.

  10. Analysis of benzophenone and 4-methylbenzophenone in breakfast cereals using ultrasonic extraction in combination with gas chromatography-tandem mass spectrometry (GC-MS(n)). (United States)

    Van Hoeck, E; De Schaetzen, T; Pacquet, C; Bolle, F; Boxus, L; Van Loco, J


    Benzophenone (BP) and 4-methylbenzophenone (4MBP) are photo-initiators that are generally used to cure ink on carton boards. In this contribution, a fast and reliable method for the determination of BP and 4MBP in breakfast cereals is described. The sample was extracted ultrasonically using a mixture of dichloromethane and acetonitrile (1:1), followed by a clean-up of the extract using solid phase extraction with a silica cartridge. Finally, the extract was analysed by GC-MS(n). Benzophenone-d(10) was used as internal standard. The presented method is validated in terms of linearity, recovery, repeatability and intra-laboratory reproducibility, specificity, limit of detection and limit of quantification. In conclusion, this method is able to detect both BP and 4MBP at very low concentrations (LOD=2microg kg(-1)) in breakfast cereals.

  11. Kinetics of Chlorination of Benzophenone-3 in the Presence of Bromide and Ammonia. (United States)

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


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

  12. Transformation pathways and acute toxicity variation of 4-hydroxyl benzophenone in chlorination disinfection process. (United States)

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


    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.

  13. Degradation of benzophenone-3 by the ozonation in aqueous solution: kinetics, intermediates and toxicity. (United States)

    Guo, Yang; Lin, Qiaoxin; Xu, Bingbing; Qi, Fei


    Benzophenone-3 (BP-3) is a popular ultraviolet absorbing chemical and has an adverse impact on aquatic ecosystems and human health. We determined the reaction kinetic constants of BP-3 and its de-proton pattern reacting with the molecular ozone or hydroxyl radical (·OH) for the first time. The obtained constant of the molecular ozone reacting with BP-3 or BP-3(-) was 1.03(±0.21) × 10(2) or 1.85(±0.098) × 10(5) M(-1) s(-1), respectively. And, the constant for BP-3 reacting with ·OH was 9.74(±0.21) × 10(9) or 10.13(±0.25) × 10(9) M(-1) s(-1) as using 4-chlorobenzoic acid and benzotriazole as reference compounds, respectively. The intermediates generated in the molecular ozone (12 kinds) or ·OH oxidation (18 kinds) were identified by LC-MS/MS. The removal efficiency of BP-3 in ozonation was dependent on the initial concentration of ozone, BP-3, and matrix water quality. The detoxification of BP-3 ozonation was depended on initial ozone dose using Chlorella vulgaris as the probe. Higher ozone dose increased the toxicity of the solution for more BP-3 being degraded and more intermediates formed, suggesting that the sole ozonation is not an effect approach for the degradation of BP-3 and some other energy should be combined.

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

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


    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.

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

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


    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.

  16. Novel organosoluble polyimide based on an asymmetric bis(ether amine): 3, 4'-Bis(4-aminophenoxy)-benzophenone

    Institute of Scientific and Technical Information of China (English)

    Qian Qian Bu; Shu Jiang Zhang; Hui Li; Yan Feng Li


    A new kind of asymmetrical ether diamine,3,4'-bis(4-aminophenoxy)benzophenone (BABP),was synthesized from the nucleophilic substitution reaction of 4-chloronitrobenzene and 3,4'-dihydroxybenzophenone in the presence of potassium carbonate,followed by catalytic reduction with SnCl2-6H2O and concentrated hydrochloric acid.The prepared diamine was employed in the preparation of a novel polyimide containing asymmetrical diaryl ether segments via the polycondensation of it with BTDA by a two-step method.The resulting polyimide exhibits excellent solubility,film-forming capability and high thermal resistance.

  17. 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


    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...... carried out at a constant temperature of 34°C. It was found that the migration of benzophenone after more than 30 days was 4.8 times higher at a relative humidity of 64%-71%, and 7.3 times higher at a relative humidity of >73%, compared with that at a relative humidity of 39%-49%. Diffusion and partition...

  18. Synthesis and antiproliferative activity of benzophenone tagged pyridine analogues towards activation of caspase activated DNase mediated nuclear fragmentation in Dalton's lymphoma. (United States)

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


    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.

  19. Reaction of benzophenone triplet with aliphatic amines. What a potent neurotoxin can tell us about the reaction mechanism. (United States)

    Grimm, Michelle L; Allen, William J; Finn, Meghan; Castagnoli, Neal; Tanko, James M


    A photochemical model study of benzophenone triplet ((3)BP) with the MAO-B substrate 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine [MPTP (1)] and two of it's derivatives, 1-cyclopropyl-4-phenyl-1,2,3,6-tetrahydropyridine (2) and (±)-[trans-2-phenylcyclopropyl-4-phenyl-1,2,3,6-tetrahydropyridine (3) were performed. Literature precedent and calculations reported herein suggest that the barrier to ring opening for aminyl radical cations derived from N-cyclopropyl derivatives of tertiary amines (such as MPTP) will be low. The LFP results reported herein demonstrate that pathways for the reaction of (3)BP with 1, 2, and 3 are very similar. In each instance, disappearance of (3)BP is accompanied solely by appearance of bands corresponding to the diphenylhydroxylmethyl radical and neutral radical derived from MPTP and it's two derivatives 2 and 3. These results suggest that the reaction between benzophenone triplet and tertiary aliphatic amines proceed via a simple hydrogen atom transfer reaction. Additionally these model examinations provide evidence that oxidations of N-cyclopropyl derivatives of MPTP catalyzed by MAO-B may not be consistent with a pure SET pathway.

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

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


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

  1. Photoaffinity labeling of Ras converting enzyme 1 (Rce1p) using a benzophenone-containing peptide substrate. (United States)

    Kyro, Kelly; Manandhar, Surya P; Mullen, Daniel; Schmidt, Walter K; Distefano, Mark D


    Isoprenylation is a post-translational modification that increases protein hydrophobicity and helps target certain proteins to membranes. Ras converting enzyme 1 (Rce1p) is an endoprotease that catalyzes the removal of a three residue fragment from the C-terminus of isoprenylated proteins. To obtain structural information about this membrane protein, photoaffinity labeling agents are being prepared and employed. Here, we describe the synthesis of a benzophenone-containing peptide substrate analogue for Rce1p. Using a continuous spectrofluorometric assay, this peptide was shown to be a substrate for Rce1p. Mass spectrometry was performed to confirm the site of cleavage and structure of the processed probe. Photolysis of the biotinylated compound in the presence of membranes containing Rce1p followed by streptavidin pull-down and Western blot analysis indicated that Rce1p had been labeled by the probe. Photolysis in the presence of both the biotinylated, benzophenone-containing probe and a farnesylated peptide competitor reduced the extent of labeling, suggesting that labeling is occurring in the active site.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  3. 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:, E-mail: [Inorganic and Physical Chemistry Department, Indian Institute of Science, Bangalore 560012 (India); Verma, Chandra, E-mail:, E-mail: [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)


    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

  4. Reactivity of Benzophenone Ketyl Free Radicals in an Elongated Elastomer Film. (United States)

    Levin, Peter P; Efremkin, Alexei F; Kasparov, Valery V; Khudyakov, Igor V


    The effect of polymer film elongation leading to the thinning of the film up to three times on the decay of transients was studied. Kinetics of benzophenone (B) triplet state (3)B* and ketyl free radical BH• in soft rubber poly(ethylene-co-butylene) (abbreviated as E) was investigated by nanosecond laser flash photolysis. We monitored decay kinetics of the triplet state of (3)B* and of BH• decay in the polymer cage and decay of BH• in the polymer bulk. The fast exponential decay of (3)B*(lifetime τT ≈ 200 ns) is accompanied by hydrogen atom abstraction from E with the formation of BH• and a polymer free radical R•. The decay of BH• in the polymer cage occurs during τc ≈ 1 μs. Cage recombination, in turn, was followed by a cross-termination of BH• in the polymer bulk (τb ≈ 100 μs under our conditions) and is characterized by a rate constant kb ≈ 10(8) M(-1) s(-1). We studied changes of rates of transients decay upon elongation (thinning) of E. Decay of (3)B* is practically independent of elongation of the film. Recombination of BH• in the solvent bulk occurs with a two times lower kb than in a nonelongated E. The decrease in kb is ascribed mainly to a lower fractional polymer free volume Vf in elongated E compared with that in nonelongated E. Dependencies of log10 kb versus [Formula: see text], where [Formula: see text] is the thickness of the film, turned out to be linear with a negative slope. At the same [Formula: see text] recombination proceeds slower in the elongated elastomer compared with the nonelongated elastomer. Cage effect increases twice as well due to a lower rate of radicals escape from the polymer cage in the elongated film. We observed relatively large effects of external magnetic field (B = 0.2T) on the kinetics of cage recombination and recombination in the polymer bulk. Magnetic field effect on recombination rates in the cage and in the solvent bulk does not depend on elongation.

  5. Benzophenone Synthase and Chalcone Synthase Accumulate in the Mesophyll of Hypericum perforatum Leaves at Different Developmental Stages (United States)

    Belkheir, Asma K.; Gaid, Mariam; Liu, Benye; Hänsch, Robert; Beerhues, Ludger


    The active medicinal constituents in Hypericum perforatum, used to treat depression and skin irritation, include flavonoids and xanthones. The carbon skeletons of these compounds are formed by chalcone synthase (CHS) and benzophenone synthase (BPS), respectively. Polyclonal antisera were raised against the polyketide synthases from Hypericum androsaemum and their IgG fractions were isolated. Immunoblotting and immunotitration were used to test the IgGs for crossreactivity and monospecificity in H. perforatum leaf protein extract. Immunofluorescence localization revealed that both CHS and BPS are located in the mesophyll. The maximum fluorescence levels were observed in approx. 0.5 and 1 cm long leaves, respectively. The fluorescence intensity observed for CHS significantly exceeded that for BPS. Using histochemical staining, flavonoids were detected in the mesophyll, indicating that the sites of biosynthesis and accumulation coincide. Our results help understand the biosynthesis and underlying regulation of active H. perforatum constituents. PMID:27446151

  6. Benzophenone Synthase and Chalcone Synthase Accumulate in the Mesophyll of Hypericum perforatum Leaves at Different Developmental Stages. (United States)

    Belkheir, Asma K; Gaid, Mariam; Liu, Benye; Hänsch, Robert; Beerhues, Ludger


    The active medicinal constituents in Hypericum perforatum, used to treat depression and skin irritation, include flavonoids and xanthones. The carbon skeletons of these compounds are formed by chalcone synthase (CHS) and benzophenone synthase (BPS), respectively. Polyclonal antisera were raised against the polyketide synthases from Hypericum androsaemum and their IgG fractions were isolated. Immunoblotting and immunotitration were used to test the IgGs for crossreactivity and monospecificity in H. perforatum leaf protein extract. Immunofluorescence localization revealed that both CHS and BPS are located in the mesophyll. The maximum fluorescence levels were observed in approx. 0.5 and 1 cm long leaves, respectively. The fluorescence intensity observed for CHS significantly exceeded that for BPS. Using histochemical staining, flavonoids were detected in the mesophyll, indicating that the sites of biosynthesis and accumulation coincide. Our results help understand the biosynthesis and underlying regulation of active H. perforatum constituents.

  7. Dielectric spectroscopy in benzophenone: the beta relaxation and its relation to the mode-coupling Cole-Cole peak. (United States)

    Pardo, L C; Lunkenheimer, P; Loidl, A


    We report a thorough characterization of the glassy dynamics of benzophenone by broadband dielectric spectroscopy. We detect a well-pronounced beta relaxation peak developing into an excess wing with increasing temperature. A previous analysis of results from Optical-Kerr-effect measurements of this material within the mode-coupling theory revealed a high-frequency Cole-Cole peak. We address the question if this phenomenon also may explain the Johari-Goldstein beta relaxation, a so-far unexplained spectral feature inherent to glass-forming matter, mainly observed in dielectric spectra. Our results demonstrate that according to the present status of theory, both spectral features seem not to be directly related.

  8. Isolation, structural elucidation, MS profiling, and evaluation of triglyceride accumulation inhibitory effects of benzophenone C-glucosides from leaves of Mangifera indica L. (United States)

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


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

  9. 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


    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.

  10. Type I photosensitized reactions of oxopurines. Kinetics and thermodynamics of the reaction with triplet benzophenone by time-resolved photoacoustic spectroscopy (United States)

    Murgida, Daniel H.; Erra Balsells, Rosa; Crippa, Pier Raimondo; Viappiani, Cristiano


    Benzophenone photosensitized reactions of caffeine, theophylline and theobromine were investigated in acetonitrile by time-resolved laser-induced photoacoustics. In the three cases global quenching rate constants of triplet benzophenone were measured as a function of temperature and it was observed that this is a non-activated process. Besides, for theobromine and theophylline heats for NH hydrogen abstraction reactions were determined. In agreement with semiempirical calculation predictions, hydrogen abstraction is thermodynamically more favorable and faster for theophylline (Δ H=-265 kJ mol -1, kr=9.6×10 8 M -1 s -1) than for theobromine (Δ H=-168 kJ mol -1, kr=3.7×10 8 M -1 s -1).

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

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


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

  12. Phototransformation of the sunlight filter benzophenone-3 (2-hydroxy-4-methoxybenzophenone) under conditions relevant to surface waters

    Energy Technology Data Exchange (ETDEWEB)

    Vione, Davide, E-mail: [Università degli Studi di Torino, Dipartimento di Chimica, Via P. Giuria 5, 10125 Torino (Italy); Università degli Studi di Torino, Centro Interdipartimentale NatRisk, Via L. Da Vinci 44, 10095 Grugliasco (Italy); Caringella, Rosalinda; De Laurentiis, Elisa; Pazzi, Marco; Minero, Claudio [Università degli Studi di Torino, Dipartimento di Chimica, Via P. Giuria 5, 10125 Torino (Italy)


    The UV filter benzophenone-3 (BP3) has UV photolysis quantum yield Φ{sub BP3} = (3.1 ± 0.3) · 10{sup −5} and the following second-order reaction rate constants: with {sup •} OH, k{sub BP3,{sup •}} {sub OH} = (2.0 ± 0.4) · 10{sup 10} M{sup −1} s{sup −1}; with the triplet states of chromophoric dissolved organic matter ({sup 3}CDOM*), k{sub BP3,{sup 3}CDOM*} = (1.1 ± 0.1) · 10{sup 9} M{sup −1} s{sup −1}; with {sup 1}O{sub 2}, k{sub BP3,{sup 1}O{sub 2}} = (2.0 ± 0.1) · 10{sup 5} M{sup −1} s{sup −1}, and with CO{sub 3}{sup −•} , k{sub BP3,CO{sub 3{sup −}{sup •}}} < 5 · 10{sup 7} M{sup −1} s{sup −1}. These data allow the modelling of BP3 photochemical transformation, which helps filling the knowledge gap about the environmental persistence of this compound. Under typical surface-water conditions, direct photolysis and reactions with {sup •} OH and {sup 3}CDOM* would be the main processes of BP3 phototransformation. Reaction with {sup •} OH would prevail at low DOC, direct photolysis at intermediate DOC (around 5 mg C L{sup −1}), and reaction with {sup 3}CDOM* at high DOC. If the reaction rate constant with CO{sub 3}{sup −•} is near the upper limit of experimental measures (5 · 10{sup 7} M{sup −1} s{sup −1}), the CO{sub 3}{sup −•} degradation process could be somewhat important for DOC < 1 mg C L{sup −1}. The predicted half-life time of BP3 in surface waters under summertime conditions would be of some weeks, and it would increase with increasing depth and DOC. BP3 transformation intermediates were detected upon reaction with {sup •} OH. Two methylated derivatives were tentatively identified, and they were probably produced by reaction between BP3 and fragments arising from photodegradation. The other intermediates were benzoic acid (maximum concentration ∼ 10% of initial BP3) and benzaldehyde (1%). Highlights: • Benzophenone-3 is mainly photodegraded by direct photolysis, {sup •} OH and {sup 3}CDOM*.

  13. Acute Toxicity and Ecological Risk Assessment of Benzophenone and N,N-Diethyl-3 Methylbenzamide in Personal Care Products

    Directory of Open Access Journals (Sweden)

    Hong-Qin Sun


    Full Text Available Benzophenone (BP and N,N-diethyl-3-methylbenzamide (DEET are two chemicals often used in personal care products (PCPs. There is a lack of systematic ecotoxicological evaluations about the two chemicals to aquatic organisms. In the present study, the acute toxic effects on Chlorella vulgaris, Daphnia Magana, and Brachydanio rerio were tested and the ecotoxicological risks were evaluated. For BP, the 96-h half-maximal effective concentration (EC50 on C. vulgaris was 6.86 mg/L; the 24-h median lethal concentration (LC50 on D. magana was 7.63 mg/L; the 96-h LC50 on B. rerio was 14.73 mg/L. For DEET, those were 270.72 mg/L, 40.74 mg/L, and 109.67 mg/L, respectively. The mixture toxicity of BP and DEET, on C. vulgaris, D. magana, and B. rerio all showed an additive effect. The induced predicted no-effect concentrations (PNECs for BP and DEET by assessment factor (AF method are 0.003 mg/L and 0.407 mg/L, respectively. Both are lower than the concentrations detected from environment at present, verifying that BP and DEET are low-risk chemicals to the environment.

  14. Synthesis of Lanthanide Coordination Polymers with Benzophenone-4,4'-dicarboxylate:Effect of Lanthanide Contraction on Structures

    Institute of Scientific and Technical Information of China (English)

    WANG, Yi-Bo(王轶博); JIN, Lin-Pei(金林培)


    Four lanthanide coordination polymers with benzophenone-4,4'-dicarboxylic acid (H2bpndc) and 1,10-phenanthroline(phen),[Ln2(bpndc)3(phen)](Ln=La(1),Pr(2) and Tb(3)),[Yb(bpndc)1.5(phen)]·0.5H2O(4) were obtained through solvothermal synthesis. The crystallographic data show that 1, 2, and 3 are isostructural, the Ln(Ⅲ)ions in 1, 2 and 3 are all eight- and ten-coordinated, respectively, and thus the Ln(Ⅲ) ions are connected by bpndc ligands, resulting in an interpenetrating 3D structure. While in 4, the Yb(Ⅲ) ions are eight-coordinated and connected by bpndc ligands into a 3D structure with 1D rhombic channels, which result from the effect of lanthanide contraction from La(Ⅲ) to Yb(Ⅲ) ions, and the bpndc ligands in 1, 2, 3, and 4 display three types of coordination modes.

  15. Competition between "Meta Effect" Photochemical Reactions of Selected Benzophenone Compounds Having Two Different Substituents at Meta Positions. (United States)

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


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

  16. Ecological risk assessment associated to the removal of endocrine-disrupting parabens and benzophenone-4 in wastewater treatment. (United States)

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


    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.

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

    Directory of Open Access Journals (Sweden)

    Cristina Félez


    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.

  18. Decay kinetics of benzophenone triplets and corresponding free radicals in soft and rigid polymers studied by laser flash photolysis. (United States)

    Levin, Peter P; Efremkin, Alexei F; Sultimova, Natalie B; Kasparov, Valery V; Khudyakov, Igor V


    The kinetics of transients formed under photoexcitation of benzophenone (B) dissolved in three different polymers was studied by ns laser flash photolysis. These polymers were the soft rubbers poly (ethylene-co-butylene) (EB), polystyrene block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS) and hard polystyrene (PS). We monitored the decay kinetics of triplet state (3)B(*) and of ketyl radicals BH(●). We observed exponential decay of (3)B(*) and two-stage decay kinetics of BH(●) in EB. The first stage is a fast cage recombination of a radical pair (BH(●), radical of polymer R(●)). The second slow stage of BH(●) decay follows the second-order law with a relatively high rate constant, which corresponds to recombination of BH(●) in a homogeneous liquid with a viscosity of only ~0.1 P (about five times of 2-propanol viscosity). Application of a magnetic field (MF) of 0.2 T leads to deceleration of both stages of BH(●) decay in EB by approximately 20%. Decay kinetics of both transients were observed in SEBS. There was no MF effect on BH(●) decay in SEBS. We only observed (3)B(*) in PS. Decay kinetics of (3)B(*) in this case were described as polychromatic dispersive first-order kinetics. We discuss the effects of polymer structure on transient kinetics and the MF effect.

  19. Serum Testosterone Concentrations and Urinary Bisphenol A, Benzophenone-3, Triclosan, and Paraben Levels in Male and Female Children and Adolescents: NHANES 2011–2012 (United States)

    Scinicariello, Franco; Buser, Melanie C.


    Background: Exposure to environmental phenols (e.g., bisphenol A, benzophenone-3, and triclosan) and parabens is widespread in the population. Many of these chemicals have been shown to have anti-androgenic effects both in vitro and in vivo. Objective: We examined the association of bisphenol A (BPA), benzophenone-3 (BP-3), triclosan (TCS), and parabens with serum total testosterone (TT) levels in child and adolescent participants (ages 6–19 years) in the National Health and Nutrition Examination Survey (NHANES) 2011–2012. Methods: We performed multivariable linear regression to estimate associations between natural log–transformed serum TT and quartiles of urinary BPA, BP-3, TCS, and parabens in male and female children (ages 6–11 years) and adolescents (ages 12–19 years). Results: BP-3 and BPA were associated with significantly lower TT in male adolescents, and BPA was associated with significantly higher TT in female adolescents. TT was not consistently associated with TCS or total parabens in children or adolescents of either sex. Conclusions: To our knowledge, this is the first study to report an association of both BP-3 and BPA with serum TT in adolescents. Associations between BPA and TT differed according to sex in adolescents, with inverse associations in boys and positive associations in girls. BP-3 was associated with significantly lower TT in adolescent boys only. However, because of the limitations inherent to the cross-sectional study design, further studies are needed to confirm and elucidate on our findings. Citation: Scinicariello F, Buser MC. 2016. Serum testosterone concentrations and urinary bisphenol A, benzophenone-3, triclosan, and paraben levels in male and female children and adolescents: NHANES 2011–2012. Environ Health Perspect 124:1898–1904; PMID:27383665

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

    Directory of Open Access Journals (Sweden)

    Gwenneg Kerdivel

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

  1. Heterogeneous photocatalytic degradation of the endocrine-disrupting chemical Benzophenone-3: Parameters optimization and by-products identification. (United States)

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


    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 (photocatalytic degradation followed a pseudo-first order kinetics. After 300 min of treatment, ∼67% of the dissolved organic carbon was removed, which together with a reduction in toxicity and an increase in biodegradability confirmed that 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.

  2. 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:; 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)


    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.

  3. Comparative study on the photostability of arbutin and deoxy arbutin: sensitivity to ultraviolet radiation and enhanced photostability by the water-soluble sunscreen, benzophenone-4. (United States)

    Yang, Chao-Hsun; Chang, Nai-Fang; Chen, Yi-Shyan; Lee, Shu-Mei; Lin, Pei-Jin; Lin, Chih-Chien


    Arbutin and deoxy arbutin may release hydroquinone under some conditions. We therefore investigated the photostability of arbutin and deoxy arbutin in an aqueous solution. The results revealed arbutin and deoxy arbutin to be photolabile in an aqueous solution. Deoxy arbutin was less stable than arbutin when exposed to UV radiation. The hydroquinone concentration was also increased during the radiation period in both solutions. Benzophenone-4 could clearly improve the photostability of arbutin during the period of UV radiation, but only slightly enhance the photostability of deoxy arbutin.

  4. 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


    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.

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

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


    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.

  6. 7-Epiclusianona, a nova benzofenona tetraprenilada e outros constituintes químicos dos frutos de Rheedia gardneriana 7-Epiclusianone, the new tetraprenylated benzophenone and others chemical constituents from the fruits of Rheedia gardneriana

    Directory of Open Access Journals (Sweden)

    Marcelo Henrique dos Santos


    Full Text Available Phytochemical investigation of the fruits of Rheedia gardneriana led to the isolation of sesquiterpenes mixture, methyl esters of fatty acids (palmitate, estearate, oleate, linoleate, linolenate, sugars (galactose, glucose, fructose, triterpene (oleanolic acid, steroids mixture (stigmasterol and sitosterol and the new tetraprenylated benzophenone 7-epiclusianone.

  7. 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


    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.


    Institute of Scientific and Technical Information of China (English)

    HUANG Junlian; WU Qingfong


    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.

  9. 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.

    was performed for benzanthrone, 2,4,6-tribromophenol and benzophenone-2, which differ in the amount of available data. Main focus was on effects on the estrogen/androgen axis. Potential endocrine activity was evaluated based on literature data and additional in vitro and in vivo testing. In the following......, the main findings and the conclusions with regard to Appendix 7.8-5 are highlighted. (1) For benzanthrone, no binding to the estrogen receptor (ER) is predicted using QSAR methods, but potential metabolites with strong affinity to the ER were identified. At present, the endocrine activity...... of such metabolites is not considered in Appendix 7.8-5. Since many in vitro assays have limited metabolic capacity, this is a shortcoming for substances, for which no in vivo data are available. (2) Reporter gene assays indicate weak ER agonism of benzanthrone; in vitro results on androgen receptor mediated effects...

  10. Characterization of gallotannins and benzophenone derivatives from mango (Mangifera indica L. cv. 'Tommy Atkins') peels, pulp and kernels by high-performance liquid chromatography/electrospray ionization mass spectrometry. (United States)

    Berardini, Nicolai; Carle, Reinhold; Schieber, Andreas


    Polyphenolics were extracted from peels, pulp and kernels of mango fruits (Mangifera indica L. cv. 'Tommy Atkins') and characterized by high-performance liquid chromatography/electrospray ionization mass spectrometry. In the peel 18 gallotannins and five benzophenone derivatives were detected which were tentatively identified as galloylated maclurin and iriflophenone glucosides. Twenty-one and eight gallotannins were found in the kernels and pulp, respectively, whereas no evidence for the presence of benzophenone derivatives was obtained. Gallotannins quantified by the rhodanine assay amounted to 1.4 mg/g dm in the peels (expressed as gallic acid), while only small amounts (0.2 mg/g dm) were found in the pulp. In contrast, mango kernels contained 15.5 mg/g dm and thus proved to be a rich source of gallotannins.

  11. 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. (United States)

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


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

    Directory of Open Access Journals (Sweden)

    Chao Peng


    Full Text Available 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 Zn/Al-LDH containing HNOB anions (Zn/Al-HNOB−-LDH. X-ray diffraction results of Zn/Al-LDH containing CO32− anions (Zn/Al-CO32--LDH and Zn/Al-CO32--LDH/styrene-butadiene-styrene (SBS modified asphalt disclosed that asphalt molecules entered into LDH interlayer galleries to form an expanded phase structure. UV-Vis absorbance patterns showed that Zn/Al-HNOB−-LDH has a better capacity of blocking UV light due to the synergetic effect of HNOB and Zn/Al-LDH. The chemical fractions analysis, conventional physical tests, and rheological tests of SBS modified asphalt, Zn/Al-CO32--LDH/SBS modified asphalt, and Zn/Al-HNOB−-LDH/SBS modified asphalt before and after UV aging testified that Zn/Al-HNOB−-LDH can improve the UV aging resistance of SBS modified asphalt more significantly.

  14. Determination of four paraben-type preservatives and three benzophenone-type ultraviolet light filters in seafoods by LC-QqLIT-MS/MS. (United States)

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


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

  15. Improvement in UV protection retention capability and reduction in skin penetration of benzophenone-3 with mesoporous silica as drug carrier by encapsulation. (United States)

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


    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.

  16. Prediction of the metabolic clearance of benzophenone-2, and its interaction with isoeugenol and coumarin using cryopreserved human hepatocytes in primary culture. (United States)

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


    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.

  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. (United States)

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


    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), 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.

  18. Simultaneous determination of multiclass preservatives including isothiazolinones and benzophenone-type UV filters in household and personal care products by micellar electrokinetic chromatography. (United States)

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


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

  19. The effect of 4,4'-bis(N,N-diethylamino) benzophenone on the degree of conversion in liquid photopolymer for dental 3D printing (United States)

    Lee, Du-Hyeong; Mai, Hang Nga; Yang, Jin-Chul


    PURPOSE The purpose of this preliminary study was to investigate the effects of adding 4,4'-bis(N,N-diethylamino) benzophenone (DEABP) as a co-initiator to a binary photoinitiating system (camphorquinone-amine) to analyze on the degree of conversion (DC) of a light-cured resin for dental 3D printing. MATERIALS AND METHODS Cylindrical specimens (N=60, n=30 per group, ø5 mm × 1 mm) were fabricated using bisphenol A glycerolate dimethacrylate (BisGMA) both with and without DEABP. The freshly mixed resins were exposed to light in a custom-made closed chamber with nine light-emitting diode lamps (wavelength: 405 nm; power: 840 mW/cm2) for polymerization at each incidence of light-irradiation at 10, 30, 60, 180, and 300 seconds, while five specimens at a time were evaluated at each given irradiation point. Fourier-transform infrared (FTIR) spectroscopy was used to measure the DC values of the resins. Two-way analysis of variance and the Duncan post hoc test were used to analyze statistically significant differences between the groups and given times (α=.05). RESULTS In the DEABP-containing resin, the DC values were significantly higher at all points in time (P3D printing. PMID:26576255

  20. Liquid chromatography-tandem mass spectrometry method for identification and quantification of two biologically active polyisoprenylated benzophenones, isoxanthochymol and camboginol, in Garcinia species. (United States)

    Chattopadhyay, Sunil K; Kumar, Satyanshu


    A sensitive liquid chromatography/electrospray ionization tandem mass spectrometrical (LC/ESI-MS/MS) method was developed for simultaneous identification and quantification of two polyisoprenylated benzophenones, isoxanthochymol and camboginol, in the extracts of the fruit rinds, stem bark, seed and leaves of Garcinia indica and in the fruit rinds of Garcinia cambogia. The separation of isoxanthochymol and camboginol was achieved on an RP-8 column using the solvent system consisting of a mixture of acetonitrile-water (80:20) and methanol-acetic acid (99.0:1.0) as a mobile phase in a gradient elution mode. A multiple reaction monitoring (MRM) method was developed for quantification of isoxanthochymol and camboginol in the above extracts of Garcinia species. Based on a signal-to-noise ratio of 3, the limits of detection in MRM mode for isoxanthochymol and camboginol were 2.0 and 5.0 ng/mL respectively. The method was validated in terms of linearity, accuracy and precision for 6 days. The method developed was found to be useful for identification and quantification of isoxanthochymol and camboginol in the extracts of the fruit rinds, stem bark, seed and leaves of Garcinia indica and in the fruit rinds of Garcinia cambogia.

  1. Evaluation of substrate and inhibitor binding to yeast and human isoprenylcysteine carboxyl methyltransferases (Icmts) using biotinylated benzophenone-containing photoaffinity probes. (United States)

    Hahne, Kalub; Vervacke, Jeffrey S; Shrestha, Liza; Donelson, James L; Gibbs, Richard A; Distefano, Mark D; Hrycyna, Christine A


    Isoprenylcysteine carboxyl methyltransferases (Icmts) are a class of integral membrane protein methyltransferases localized to the endoplasmic reticulum (ER) membrane in eukaryotes. The Icmts from human (hIcmt) and Saccharomyces cerevisiae (Ste14p) catalyze the α-carboxyl methyl esterification step in the post-translational processing of CaaX proteins, including the yeast a-factor mating pheromones and both human and yeast Ras proteins. Herein, we evaluated synthetic analogs of two well-characterized Icmt substrates, N-acetyl-S-farnesyl-L-cysteine (AFC) and the yeast a-factor peptide mating pheromone, that contain photoactive benzophenone moieties in either the lipid or peptide portion of the molecule. The AFC based-compounds were substrates for both hIcmt and Ste14p, whereas the a-factor analogs were only substrates for Ste14p. However, the a-factor analogs were found to be micromolar inhibitors of hIcmt. Together, these data suggest that the Icmt substrate binding site is dependent upon features in both the isoprenyl moiety and upstream amino acid composition. Furthermore, these data suggest that hIcmt and Ste14p have overlapping, yet distinct, substrate specificities. Photocrosslinking and neutravidin-agarose capture experiments with these analogs revealed that both hIcmt and Ste14p were specifically photolabeled to varying degrees with all of the compounds tested. Our data suggest that these analogs will be useful for the future identification of the Icmt substrate binding sites.

  2. 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


    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.

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

    Watanabe, Yoko; Kojima, Hiroyuki; Takeuchi, Shinji; Uramaru, Naoto; Sanoh, Seigo; Sugihara, Kazumi; Kitamura, Shigeyuki; Ohta, Shigeru


    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.

  4. 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. (United States)

    Esmaili-Hafshejani, Javad; Nezamzadeh-Ejhieh, Alireza


    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.

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

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


    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.

  6. Solid-phase extraction and field-amplified sample injection-capillary zone electrophoresis for the analysis of benzophenone UV filters in environmental water samples. (United States)

    Purrà, Miquel; Cinca, Roser; Legaz, Jessica; Núñez, Oscar


    A field-amplified sample injection-capillary zone electrophoresis (FASI-CZE) method for the analysis of benzophenone (BP) UV filters in environmental water samples was developed, allowing the separation of all compounds in less than 8 min. A 9- to 25-fold sensitivity enhancement was obtained with FASI-CZE, achieving limits of detection down to 21-59 μg/L for most of the analyzed BPs, with acceptable run-to-run and day-to-day precisions (relative standard deviations lower than 17%). In order to remove water sample salinity and to enhance FASI sensitivity, an off-line solid-phase extraction (SPE) procedure using a Strata X polymeric reversed-phase sorbent was used and afforded recoveries up to 72-90% for most BPs. With the combination of off-line SPE and FASI-CZE, limits of detection in the range 0.06-0.6 μg/L in a river water matrix, representing a 2,400- to 6,500-fold enhancement, were obtained. Method performance was evaluated by quantifying a blank river water sample spiked at 1 μg/L. For a 95% confidence level, no statistical differences were observed between found concentrations and spiked concentrations (probability at the confidence level, p value, of 0.60), showing that the proposed off-line SPE-FASI-CZE method is suitable for the analysis of BP UV filters in environmental water samples at low microgram per liter levels. The method was successfully applied to the analysis of BPs in river water samples collected up- and downstream of industrialized and urban areas, and in some drinking water samples.

  7. 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: [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)


    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

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

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


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

  9. An easy stereoselective access to beta,gamma-aziridino alpha-amino ester derivatives via mannich reaction of benzophenone imines of glycine esters with N-sulfonyl alpha-chloroaldimines. (United States)

    Kiss, Loránd; Mangelinckx, Sven; Sillanpää, Reijo; Fülöp, Ferenc; De Kimpe, Norbert


    Mannich-type addition of benzophenone imine glycinates across newly synthesized N-(p-toluenesulfonyl) alpha-chloroaldimines afforded gamma-chloro-alpha,beta-diamino ester derivatives with moderate diastereoselectivity as separable mixtures of anti and syn diastereomers. The gamma-chloro-alpha,beta-diamino esters were efficiently cyclized under basic conditions to the corresponding beta,gamma-aziridino alpha-amino ester derivatives, representing a new class of conformationally constrained heterocyclic alpha,beta-diamino acid derivatives. The relative configuration of the aziridines was determined via X-ray diffraction analysis. Mechanisms and intermediate transition states to explain the stereochemical outcome of the Mannich reaction with different substrates or under different conditions are proposed. The synthetic importance of the beta,gamma-aziridino alpha-amino ester derivatives is demonstrated by their conversion into the corresponding Boc-protected derivatives and ring opening reactions to alpha,beta-diamino esters and a gamma-amino alpha,beta-unsaturated amino ester.

  10. 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;


    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...... sunscreens at 10% (wt/wt) of each. Maximum plasma concentrations were 200 ng per mL BP-3, 20 ng per mL 4-MBC, and 10 ng per mL OMC for females and 300 ng per mL BP-3, 20 ng per mL 4-MBC, and 20 ng per mL OMC for men. All three sunscreens were detectable in urine. The reproductive hormones FSH, LH were...

  11. 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.


    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

  12. 4-乙烯基-4'-甲氧基二苯甲酮的光聚合性能研究%Study on photopolymerization properties of 4-vinyl-4'-methoxy benzophenone

    Institute of Scientific and Technical Information of China (English)

    邱德梅; 季永新


    By extraction, the residues of 4-vinyl-4' -methoxy benzophenone (4-VMBP) and benzophenone (BP) in the cured film were analyzed.By real-time infrared spectrum,the photopolymerization kinetics of 4-VMBP were studied, and the effects of amine concentration, initiator concentration, light distance, oxygen resistance and curing methods on the curing time of amino acid ester 6116 were researched.The results showed that the residues of 4-VCBP were an order of magnitude smaller than that of BP,4-VMBP and TEOA matched well, the favorable concentration of 4-VMBP and TEOA were both 4% , the curing time of ester was shortened without air and was double longer when light distance changed from 10 cm to 20 cm.The intermittent curing time was twice more than the continuous curing time.%用萃取法研究了4-乙烯基4'-甲氧基二苯甲酮(4-VMBP)和二苯甲酮(BP)在同化膜中的残留量;用实时红外法研究了 4-VMBP的光聚合动力学,考察了胺浓度、引发剂浓度、灯距、氧阻、固化方式对氨基丙烯酸酯6116同化时间的影响.结果表明,4-VCBP固化残留量比BP小一个数量级;4-VMBP和三乙醇胺(TEOA)匹配性最好;固化体系中4-VMBP和TEOA质量分数均为4%时较为合适;隔绝空气条件下,固化时间缩短;灯距从10cm调到20 cm,同化时间延长2倍多;间歇固化时间足连续同化的2倍多.

  13. 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: [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)


    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

  14. High-performance liquid chromatography and LC-ESI-MS method for identification and quantification of two isomeric polyisoprenylated benzophenones isoxanthochymol and camboginol in different extracts of Garcinia species. (United States)

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


    A rapid, sensitive and simple reverse-phase high-performance liquid chromatography-electrospray ionization mass spectrometric method has been developed for the identification and quantification of two isomeric polyisoprenylated benzophenones, isoxanthochymol and camboginol, in the extracts of the stem bark, seeds and seed pericarps of Garcinia indica and in the fruit rinds of Garcinia cambogia. The separation of isoxanthochymol and camboginol was achieved on a Perkin Elmer RP(8) column (10 x 2.1 mm with 5.0 microm particle size) using a solvent system consisting of a mixture of acetonitrile-water (80:20, v/v) and methanol-acetic acid (99.0:1.0, v/v) as a mobile phase in a gradient elution mode. The limits of detection and quantification were 5 and 10 microg/mL for isoxanthochymol and 50 and 100 microg/mL for camboginol, respectively. The intra- and inter-day precisions were 2.34 and 3.41% for isoxanthochymol and 3.35 and 3.66% for camboginol. The identity of the two isomeric compounds in the samples was determined on a triple quadrupole mass spectrometer with ESI interface operating in the negative ion mode. The method was used to identify and quantify isoxanthochymol and camboginol in the different extracts of two Garcinia species, Garcinia indica and Garcinia cambogia.

  15. Molecular structure, vibrational spectroscopic (FT-IR, FT-Raman), UV-vis spectra, first order hyperpolarizability, NBO analysis, HOMO and LUMO analysis, thermodynamic properties of benzophenone 2,4-dicarboxylic acid by ab initio HF and density functional method. (United States)

    Chaitanya, K


    The FT-IR (4000-450 cm(-1)) and FT-Raman spectra (3500-100 cm(-1)) of benzophenone 2,4-dicarboxylic acid (2,4-BDA) have been recorded in the condensed state. Density functional theory calculation with B3LYP/6-31G(d,p) basis set have been used to determine ground state molecular geometries (bond lengths and bond angles), harmonic vibrational frequencies, infrared intensities, Raman activities and bonding features of the title compounds. The assignments of the vibrational spectra have been carried out with the help of normal co-ordinate analysis (NCA) following the scaled quantum mechanical force field (SQMFF) methodology. The first order hyperpolarizability (β0) and related properties (β, α0 and Δα) of 2,4-BDA is calculated using HF/6-31G(d,p) method on the finite-field approach. The stability of molecule has been analyzed by using NBO analysis. The calculated first hyperpolarizability shows that the molecule is an attractive molecule for future applications in non-linear optics. The calculated HOMO and LUMO energies show that charge transfer occurs within these molecules. Mulliken population analysis on atomic charges is also calculated. Because of vibrational analyses, the thermodynamic properties of the title compound at different temperatures have been calculated. Finally, the UV-vis spectra and electronic absorption properties were explained and illustrated from the frontier molecular orbitals.

  16. 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


    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.

  17. Fast transient absorption spectroscopy of the early events in photoexcited chiral benzophenone-naphthalene dyads

    NARCIS (Netherlands)

    Perez-Ruiz, R.; Groeneveld, M.M.; van Stokkum, I.H.M.; Tormos, R.; Williams, R.M.; Miranda, M.A.


    Photoinduced intra-molecular energy transfer in two ketoprofen(KP)-naproxol(NPX) diastereomers proceeds via two pathways. Very fast singlet-triplet energy transfer (k = 1.2 x 10(11) s(-1)) from KP to NPX occurs for a small percentage (6%) and the major pathway is triplet-triplet energy transfer (k s

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

    DEFF Research Database (Denmark)

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


    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...

  19. Uterotrophic effects of benzophenone derivatives and a p-hydroxybenzoate used in ultraviolet screens. (United States)

    Koda, Tomoko; Umezu, Toyoshi; Kamata, Ryo; Morohoshi, Kaori; Ohta, Toshiko; Morita, Masatoshi


    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.

  20. The effect of glycerol, propylene glycol and polyethylene glycol 400 on the partition coefficient of benzophenone-3 (oxybenzone). (United States)

    Mbah, C J


    Sunscreen products are widely used to protect the skin from sun-related deleterious effects. The objective of the study was to investigate the potential effect of glycerol, propylene glycol and polyethylene glycol 400 on dermal absorption of oxybenzone by studying their effects on its partition coefficient. The partition coefficient was evaluated in a chloroform-water system at room temperature. It was found that glycerol and propylene glycol decreased the partition coefficient of oxybenzone, while an increase in partition coefficient was observed with polyethylene glycol 400. The findings suggest that polyethylene glycol 400 in contrast to glycerol and propylene glycol has the potential of increasing the vehicle-skin partition coefficient of oxybenzone when cosmetic products containing such an UV absorber are topically applied to the skin.

  1. Synthesis, characterization, DNA interaction and pharmacological studies of substituted benzophenone derived Schiff base metal(II complexes

    Directory of Open Access Journals (Sweden)

    P. Subbaraj


    Full Text Available A new bidentate NO type Schiff base ligand (HL, derived from 2-hydroxy-4-methoxyphenylphenylmethanone with aniline and its metal(II [M = Mn, Co, Ni, Cu and Zn] complexes has been synthesized. The synthesized ligand and the metal(II complexes were structurally characterized by analytical, spectral (FT-IR, UV–vis., 1H NMR, FAB-Mass, TGA/DTA and EPR as well as molar conductance and magnetic studies. All the complexes are non-electrolytes having 1:2 stoichiometry. They adopt tetrahedral and octahedral geometry. Thermal behavior of metal(II complexes (1a–1c shows loss of coordinated water molecules in the first step followed by the decomposition of ligand moieties in a respective manner and leads to form an air stable metal oxide as the final residue. Micro crystalline nature and the presence of coordinated water molecules have been confirmed by powder XRD, SEM and thermal analyses. The ligand and its complexes have efficient bio-efficacy, DNA binding and cleavage ability.

  2. 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


    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.

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

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

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

    Directory of Open Access Journals (Sweden)

    Theresa Beelders


    Full Text Available 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 spectrometry (ESI-MS and tandem MS detection. Three iriflophenone-di-O,C-hexoside isomers, three xanthone-dihydrochalcone derivatives and one dihydrochalcone are herein tentatively identified for the first time in C. genistoides. Of special interest is one iriflophenone-di-O,C-hexoside present in large amounts. New compounds (tentatively identified for the first time in this species, and also in the genus Cyclopia, include two aromatic amino acids, one flavone, an iriflophenone-di-C-hexoside, a maclurin-di-O,C-hexoside, two tetrahydroxyxanthone-C-hexoside isomers, a tetrahydroxyxanthone-di-O,C-hexoside, two symmetric tetrahydroxyxanthone-C-hexoside dimers, nine glycosylated flavanone derivatives and five glycosylated phenolic acid derivatives. The presence of new compound subclasses in Cyclopia, namely aromatic amino acids and glycosylated phenolic acids, was demonstrated. The HPLC-DAD method was successfully validated and applied to the quantitative analysis of the paired sample extracts. In-depth analysis of the chemical composition of C. genistoides hot water extracts gave a better understanding of the chemistry of this species that will guide further research into its medicinal properties and potential uses.

  5. Characterization of thin poly(pyrrole-benzophenone) film morphologies electropolymerized on indium tin oxide coated optic fibers for electrochemical and optical biosensing

    Energy Technology Data Exchange (ETDEWEB)

    Konry, T.; Heyman, Y. [Department of Biotechnology Engineering, Faculty of Engineering Science, Ben Gurion University of the Negev, P.O. Box 653, Beer Sheva 84105 (Israel); Cosnier, S.; Gorgy, K. [Departement de Chimie Moleculaire, UMR-5250, ICMG FR-2607, CNRS, Universite Joseph Fourier BP 53, 38041 Grenoble Cedex 9 (France); Marks, R.S. [Department of Biotechnology Engineering, Faculty of Engineering Science, Ben Gurion University of the Negev, P.O. Box 653, Beer Sheva 84105 (Israel); National Institute for Biotechnology in the Negev, Ben Gurion University of the Negev, P.O. Box 653, Beer Sheva 84105 (Israel)


    We report that electropolymerization parameters (duration and voltage) modulate the properties and morphological structures of photoactive polymers which influence both the efficiency of bioreceptor attachment to the polymer surface, and the resulting biosensor assay performance. We have compared two biosensor technologies, optical and electrochemical, for the detection of anti-cholera toxin antibodies using our singular conductive optic fibers, albeit at this stage in separate experiments. Both biosensor systems were more sensitive than conventional detection and pave the way for the possibility to one day make simultaneous optical and electrochemical sensing using the same biosensor. (author)

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

    DEFF Research Database (Denmark)

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


    in 2013. A total of 266 urine samples were collected from 55 children and were analysed for content of benzophenone (BP), benzophenone-1 (BP-1), benzophenone-2 (BP-2), benzophenone-3 (BP-3), 5-chloro-2-hydroxybenzophenone (BP-7), 4-methyl-benzophenone (4-MBP), 4-hydroxybenzophenone (4-HBP), 3......-(4-methylbenzylidene)-camphor (4-MBC), and 3-benzylidene camphor (3-BC) by LC-MS/MS. RESULTS: Of the analysed UV filters, the children excreted predominantly BP-1, BP-3 and 4-HBP. The urine levels were significantly higher in summer samples compared to winter samples, however exposure during winter was still evident...

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

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


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

  8. KPU-300, a Novel Benzophenone-Diketopiperazine-Type Anti-Microtubule Agent with a 2-Pyridyl Structure, Is a Potent Radiosensitizer That Synchronizes the Cell Cycle in Early M Phase.

    Directory of Open Access Journals (Sweden)

    Kohei Okuyama

    Full Text Available KPU-300 is a novel colchicine-type anti-microtubule agent derived from plinabulin (NPI-2358. We characterized the effects of KPU-300 on cell cycle kinetics and radiosensitization using HeLa cells expressing the fluorescent ubiquitination-based cell cycle indicator (Fucci. Cells treated with 30 nM KPU-300 for 24 h were efficiently synchronized in M phase and contained clearly detectable abnormal Fucci fluorescence. Two-dimensional flow-cytometric analysis revealed a fraction of cells distinct from the normal Fucci fluorescence pattern. Most of these cells were positive for an M phase marker, the phosphorylated form of histone H3. Cells growing in spheroids responded similarly to the drug, and the inner quiescent fraction also responded after recruitment to the growth fraction. When such drug-treated cells were irradiated in monolayer, a remarkable radiosensitization was observed. To determine whether this radiosensitization was truly due to the synchronization in M phase, we compared the radiosensitivity of cells synchronized by KPU-300 treatment and cells in early M phase isolated by a combined method that took advantage of shake-off and the properties of the Fucci system. Following normalization against the surviving fraction of cells treated with KPU-300 alone, the surviving fractions of cells irradiated in early M phase coincided. Taken together with potential vascular disrupting function in vivo, we propose a novel radiosensitizing strategy using KPU-300.

  9. Deoxygenation of benzoic acid on metal oxides. 2. Formation of byproducts.

    NARCIS (Netherlands)

    Lange, de M.W.; Ommen, van J.G.; Lefferts, L.


    Benzene, benzophenone, toluene and benzylalcohol are byproducts in the selective deoxygenation of benzoic acid to benzaldehyde on ZnO and ZrO2. In this paper, the pathways to the byproducts are discussed and a complete overview of the reaction network is presented. Benzene and benzophenone are produ

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

    DEFF Research Database (Denmark)

    Frederiksen, Hanne; Aksglaede, Lise; Sorensen, Kaspar;


    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...

  11. General, Unified, Multiscale Modeling to Predict the Sensitivity of Energetic Materials (United States)


    selected organic crystals: acenaphthene, trans-azobenzene, benzophenone, tolane, trans-stilbene, dibenzyl, diphenyl sulfone , 2,20-biphenol, urea, melamine crys- tals: acenaphthene, trans-azobenzene, benzophenone, tolane, trans-stilbene, diben- zyl, diphenyl sulfone , 2,2 ’-biphenol, urea, melamine ...scaling DFT energies to values calculated at the MP2/cc-pVQZ level, for dimmers like ethane, formaldehyde , benzene, water, etc. For PETN, in which 2 type

  12. Influence of anatomical site and topical formulation on skin penetration of sunscreens. (United States)

    Benson, Heather Ae; Sarveiya, Vikram; Risk, Stacey; Roberts, Michael S


    Sunscreen products are widely used to protect the skin from sun-related damage. Previous studies have shown that some sunscreen chemicals are absorbed across the skin to the systemic circulation. The current study shows that absorption into the skin of sunscreen chemicals applied to the face is up to four times greater than that of the same product applied to the back. This has implications for the way sunscreen products are formulated and may allow the use of less potent products on the face compared with the rest of the body. The effect of formulation vehicles on the release and skin penetration of the common sunscreen agent benzophenone-3 (common name oxybenzone) was also assessed. Penetration of benzophenone-3 across excised human epidermis and high-density polyethylene (HDPE) membrane was measured using in vitro Franz-type diffusion cells. Penetration and epidermal retention was measured following application of infinite and finite (epidermis only) doses of benzophenone-3 in five vehicles: liquid paraffin, coconut oil, 50:50 ethanol:coconut oil, aqueous cream BP, and oily cream BP. Highest benzophenone-3 skin retention was observed for the ethanol:coconut oil combination. Maximal and minimal benzophenone-3 fluxes were observed from liquid paraffin and coconut oil, respectively. The alcohol-based vehicle exhibited low benzophenone-3 release from the vehicle but high skin penetration and retention.

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

    Energy Technology Data Exchange (ETDEWEB)

    Natarajan, V. [Department of Physics, Aditanar College of Arts and Science, Tiruchendur, Tamil Nadu (India); Arivanandhan, M., E-mail: [Research Institute of Electronics, Shizuoka University, 3-5-1 Johoku, Naka-ku, Hamamatsu 432-8011 (Japan); Sankaranarayanan, K. [Department of Physics, Alagappa University, Karaikudi 630 003, Tamil Nadu (India); Hayakawa, Y. [Research Institute of Electronics, Shizuoka University, 3-5-1 Johoku, Naka-ku, Hamamatsu 432-8011 (Japan)


    Highlights: {center_dot} Growth rate of the unidirectional organic crystals were measured and the variation in the growth rate was explained based on the attachment energy model. {center_dot} Anisotropic behaviors of hardness and laser damage threshold of the unidirectional materials were analyzed. {center_dot} The obtained results were explained based on the crystal structure of the material. - Abstract: Unidirectional benzophenone crystals were grown along <1 1 0>, <0 1 0> and <0 0 1> directions by uniaxially solution crystallization method at ambient temperature. The growth rate of the grown crystals was varied with orientation. The optical absorption coefficients of benzophenone were measured as a function of wavelength. The optical absorption study reveals that the benzophenone crystal has very low absorption in the wavelength range of interest. Moreover, the laser damage threshold and micro hardness for <1 1 0>, <0 1 0> and <0 0 1> oriented unidirectional benzophenone crystals were measured using a Q-switched Nd:YAG laser operating at 1064 nm radiation and Vicker's micro hardness tester, respectively. The laser damage threshold is larger for the <1 1 0> and <0 1 0> oriented crystals compared to <0 0 1> oriented crystal at 1064 nm wavelength. The result is consistent with the hardness variation observed for the three different crystallographic directions of benzophenone crystal. The relation between the laser damage profile and mechanical hardness anisotropy is discussed based on the crystal structure of benzophenone.

  14. A multiclass method for the analysis of endocrine disrupting chemicals in human urine samples. Sample treatment by dispersive liquid-liquid microextraction. (United States)

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


    The population is continuously exposed to endocrine disrupting chemicals (EDCs). This has influenced an increase in diseases and syndromes that are more frequent nowadays. Therefore, it is necessary to develop new analytical procedures to evaluate the exposure with the ultimate objective of establishing, in an accurate way, relationships between EDCs and harmful health effects. In the present work, a new method based on a sample treatment by dispersive liquid-liquid microextraction (DLLME) for the extraction of six parabens (methyl-, ethyl-, isopropyl-, propyl-, isobutyl and butylparaben), six benzophenones (benzophenone-1, benzophenone-2, benzophenone-3, benzophenone-6, benzophenone-8 and 4-hydroxybenzophenone) and two bisphenols (bisphenol A and bisphenol S) in human urine samples, followed by gas chromatography-tandem mass spectrometry (GC-MS/MS) analysis is proposed. An enzymatic treatment allows determining the total content of the target EDCs. The extraction parameters were accurately optimized using multivariate optimization strategies. Ethylparaben ring-(13)C6 and bisphenol A-d16 were used as surrogates. Found limits of quantification ranging from 0.2 to 0.5 ng mL(-1) and inter-day variability (evaluated as relative standard deviation) ranging from 2.0% to 14.9%. The method was validated using matrix-matched standard calibration followed by a recovery assay with spiked samples. Recovery rates ranged from 94% to 105%. A good linearity, for concentrations up to 300 ng mL(-1) for parabens and 40 ng mL(-1) for benzophenones and bisphenols, respectively, was obtained. The method was satisfactorily applied for the determination of target compounds in human urine samples from 20 randomly selected individuals.

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

    CERN Document Server

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


    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.

  16. Synthetic ultraviolet light filtering chemical contamination of coastal waters of Virgin Islands national park, St. John, U.S. Virgin Islands. (United States)

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


    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.

  17. 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


    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.

  18. Use of [superscript 1]H, [superscript 13]C, and [superscript 19]F-NMR Spectroscopy and Computational Modeling to Explore Chemoselectivity in the Formation of a Grignard Reagent (United States)

    Hein, Sara M.; Kopitzke, Robert W.; Nalli, Thomas W.; Esselman, Brian J.; Hill, Nicholas J.


    A discovery-based Grignard experiment for a second-year undergraduate organic chemistry course is described. The exclusive Grignard reagent formed by the reaction of 1-bromo-4-fluorobenzene (1) with Mg is 4-fluorophenylmagnesium bromide (2), which is treated with either benzophenone or CO[subscript 2] to produce the corresponding fluorinated…

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

    DEFF Research Database (Denmark)

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


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

  20. Synthesis and complexation characteristics of phenanthroline and bipyridine diols

    NARCIS (Netherlands)

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


    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

  1. Total Synthesis of balanol, Part 2

    DEFF Research Database (Denmark)

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


    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-o...

  2. MIS-based sensors with hydrogen selectivity (United States)

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


    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.

  3. Sunscreens

    DEFF Research Database (Denmark)

    Krause, Marianna; Klit, A; Jensen, Martin Blomberg


    of the malignant disorder for which sunscreens should protect, malignant melanoma, is rapidly increasing and (3) an increasing number of experimental studies indicating that several UV-filters might have endocrine disruptive effects. The selected UV-filters we review in this article are benzophenone-3 (BP-3), 3...

  4. Photoorganocatalysed and visible light photoredox catalysed trifluoromethylation of olefins and (hetero)aromatics in batch and continuous flow. (United States)

    Lefebvre, Quentin; Hoffmann, Norbert; Rueping, Magnus


    Trifluoromethylation of olefins and (hetero)aromatics with sodium triflinate as CF3 source and readily accessible benzophenone derivatives as photosensitisers has been developed in batch and flow. The use of an iridium-based photocatalyst enables the trifluoromethylation to proceed under visible light irradiation.


    NARCIS (Netherlands)



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

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

    DEFF Research Database (Denmark)

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


    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...

  7. Magnetic isotope effect on kinetic parameters and quantum beats of radical pairs in micellar solution studied by optically detected esr using pulsed microwave. (United States)

    Kitahama, Yasutaka; Sakaguchi, Yoshio


    We investigated the quantum beats, the oscillation between singlet and triplet states of radical pairs induced by the microwave field resonant to one of the component radicals. They were observed as the alternation of the yields of the component radicals by a nanosecond time-resolved optical absorption with the X-band (9.15 GHz) resonant microwave pulse. This technique was applied to the photochemical reaction of benzophenone, benzophenone-d(10), and benzophenone-carbonyl-(13)C in a sodium dodecylsulfate micellar solution with a step-by-step increase of the resonant microwave pulse width. The yields of the component radicals showed alternation with an increase of the microwave pulse width. This indicates that the radical pair retains spin coherence in the micellar solution. The magnetic isotope effect on the amplitude of the quantum beat was observed. The MW effect on the quantum beat of BP-(13)C decreases from 80% to 60% of that of BP by irradiation of the pi-pulse MW due to spin-locking. The kinetic parameters were also determined using the X- or Ku-band (17.44 GHz) region. They are almost similar to each other except for the intersystem recombination rate in the system of BP-(13)C, which may be slightly higher than those in other systems.


    Institute of Scientific and Technical Information of China (English)

    WU Shikang; FOUASSIER ,J. P.


    Time resolved laser spectroscopy and GC/MS were used to investigate the primary processes and the side reactions occurring in benzophenone and chlorothioxanthone/amine systems used as photoinitiators of radical polymerization. The discrepancy observed between the experimental data and the expected behaviour is accounted for by detrimental chemicalreaction involving the ketone triplet state, the ketyl radical and the amine - derived radical.

  9. A Guided-Inquiry Approach to the Sodium Borohydride Reduction and Grignard Reaction of Carbonyl Compounds (United States)

    Rosenberg, Robert E.


    The guided-inquiry approach is applied to the reactions of sodium borohydride and phenyl magnesium bromide with benzaldehyde, benzophenone, benzoic anhydride, and ethyl benzoate. Each team of four students receives four unknowns. Students identify the unknowns and their reaction products by using the physical state of the unknown, an…

  10. Comparison of in vitro and in vivo estrogenic activity of UV filters in fish. (United States)

    Kunz, Petra Y; Galicia, Hector F; Fent, Karl


    In this work, we evaluate whether in vitro systems are good predictors for in vivo estrogenic activity in fish. We focus on UV filters being used in sunscreens and in UV stabilization of materials. First, we determined the estrogenic activity of 23 UV filters and one UV filter metabolite employing a recombinant yeast carrying the estrogen receptor of rainbow trout (rtERalpha) and made comparisons with yeast carrying the human hERalpha for receptor specificity. Benzophenone-1 (BP1), benzophenone-2 (BP2), 4,4-dihydroxybenzophenone, 4-hydroxybenzophenone, 2,4,4-trihydroxy-benzophenone, and phenylsalicylate showed full dose-response curves with maximal responses of 81-115%, whereas 3-benzylidene camphor (3BC), octylsalicylate, benzylsalicylate, benzophenone-3, and benzophenone-4 displayed lower maximal responses of 15-74%. Whereas the activity of 17beta-estradiol was lower in the rtERalpha than the hERalpha assay, the activities of UV filters were similar or relatively higher in rtERalpha, indicating different relative binding activities of both ER. Subsequently, we analyzed whether the in vitro estrogenicity of eight UV filters is also displayed in vivo in fathead minnows by the induction potential of vitellogenin after 14 days of aqueous exposure. Of the three active compounds in vivo, 3BC induced vitellogenin at lower concentrations (435 microg/l) than BP1 (4919 microg/l) and BP2 (8783 microg/l). The study shows, for the first time, estrogenic activities of UV filters in fish both in vitro and in vivo. Thus we propose that receptor-based assays should be used for in vitro screening prior to in vivo testing, leading to environmental risk assessments based on combined, complementary, and appropriate species-related assays for hormonal activity.

  11. UV-crosslinkable photoreactive self-adhesive hydrogels based on acrylics

    Directory of Open Access Journals (Sweden)

    Czech Zbigniew


    Full Text Available Hydrogels are a unique class of macromolecular networks that can hold a large fraction of an aqueous solvent within their structure. They are suitable for biomedical area including controlled drug delivery and for technical applications as self-adhesive materials for bonding of wet surfaces. This paper describes photoreactive self-adhesive hydrogels based on acrylics crosslinked using UV radiation. They are prepared in ethyl acetate through radical polymerization of monomers mixture containing 2-ethylhexyl acrylate (2-EHA, butyl acrylate (BA, acrylic acid (AA and copolymerizable photoinitiator 4-acryloyloxy benzophenone (ABP at presence of radical starter 2.2’-azobis-diisobutyronitrile AIBN. The synthesized acrylic copolymers were determined by viscosity and GPC analysis and later modified using ethoxylated amines. 4-acryloyloxy benzophenone (ABP was used as crosslinking monomer. After UV crosslinking the properties of these novel synthesized hydrogels, such as tack, peel adhesion, shears strength, elongation and water adsorption were also studied.

  12. Concentrations of environmental phenols and parabens in milk, urine and serum of lactating North Carolina women. (United States)

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


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

  13. 4- {sup 18}F]fluoroarylalkylethers via an improved synthesis of n.c.a. 4- {sup 18}F]fluorophenol

    Energy Technology Data Exchange (ETDEWEB)

    Ludwig, Thomas; Ermert, Johannes E-mail:; Coenen, Heinz H


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

  14. One-step photochemical synthesis of permanent, nonleaching, ultrathin antimicrobial coatings for textiles and plastics. (United States)

    Dhende, Vikram P; Samanta, Satyabrata; Jones, David M; Hardin, Ian R; Locklin, Jason


    Antimicrobial copolymers of hydrophobic N-alkyl and benzophenone containing polyethylenimines were synthesized from commercially available linear poly(2-ethyl-2-oxazoline), and covalently attached to surfaces of synthetic polymers, cotton, and modified silicon oxide using mild photo-cross-linking. Specifically, these polymers were applied to polypropylene, poly(vinyl chloride), polyethylene, cotton, and alkyl-coated oxide surfaces using solution casting or spray coating and then covalently cross-linked rendering permanent, nonleaching antimicrobial surfaces. The photochemical grafting of pendant benzophenones allows immobilization to any surface that contains a C-H bond. Incubating the modified materials with either Staphylococcus aureus or Escherichia coli demonstrated that the modified surfaces had substantial antimicrobial capacity against both Gram-positive and Gram-negative bacteria (>98% microbial death).

  15. Recent Advance in Light Stabilization

    Institute of Scientific and Technical Information of China (English)

    CHIU Chris


    @@ 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.

  16. Recent Advance in Light Stabilization

    Institute of Scientific and Technical Information of China (English)

    CHIU; Chris


    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.  ……

  17. A gas chromatograph/mass spectrometry method for determining isotopic distributions in organic compounds used in the chemical approach to stable isotope separation

    Energy Technology Data Exchange (ETDEWEB)

    Martinez, A.M.; Spall, W.D.; Smith, B.F.


    A variety of gas chromatograph/mass spectrometry (GC/MS) methods have been developed to resolve benzene, benzophenone, anthracene, fluorenone, and their respective stable isotope analogs from other components by gas chromatography. The ratio of stable isotope-labeled material to natural isotopic abundance compounds is determined from the mass spectra averaged across the chromatographic peak. Both total ion and selective ion chromatographic approaches were used for relative data and comparison. 9 refs., 11 tabs.

  18. 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


    ) 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...... 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....

  19. Anti-Inflammatory Effect of 1,3,5,7-Tetrahydroxy-8-isoprenylxanthone Isolated from Twigs of Garcinia esculenta on Stimulated Macrophage


    Dan-Dan Zhang; Hong Zhang; Yuan-zhi Lao; Rong Wu; Jin-wen Xu; Ferid Murad; Ka Bian; Hong-Xi Xu


    Garcinia Linn. plants having rich natural xanthones and benzophenones with anti-inflammatory activity attracted a great deal of attention to discover and develop them as potential drug candidates. Through screening targeting nitric oxide accumulation in stimulated macrophage, we found that 1,3,5,7-tetrahydroxy-8-isoprenylxanthone (TIE) had potential anti-inflammatory effect. To understand how TIE elicits its anti-inflammatory activity, we uncovered that it significantly inhibits the productio...

  20. Prenatal exposure to environmental phenols and childhood fat mass in the Mount Sinai Children's Environmental Health Study. (United States)

    Buckley, Jessie P; Herring, Amy H; Wolff, Mary S; Calafat, Antonia M; Engel, Stephanie M


    Early life exposure to endocrine disrupting chemicals may alter adipogenesis and energy balance leading to changes in obesity risk. Several studies have evaluated the association of prenatal bisphenol A exposure with childhood body size but only one study of male infants has examined other environmental phenols. Therefore, we assessed associations between prenatal exposure to environmental phenols and fat mass in a prospective birth cohort. We quantified four phenol biomarkers in third trimester maternal spot urine samples in a cohort of women enrolled in New York City between 1998 and 2002 and evaluated fat mass in their children using a Tanita scale between ages 4 and 9years (173 children with 351 total observations). We estimated associations of standard deviation differences in natural log creatinine-standardized phenol biomarker concentrations with percent fat mass using linear mixed effects regression models. We did not observe associations of bisphenol A or triclosan with childhood percent fat mass. In unadjusted models, maternal urinary concentrations of 2,5-dichlorophenol were associated with greater percent fat mass and benzophenone-3 was associated with lower percent fat mass among children. After adjustment, phenol biomarkers were not associated with percent fat mass. However, the association between benzophenone-3 and percent fat mass was modified by child's sex: benzophenone-3 concentrations were inversely associated with percent fat mass in girls (beta=-1.51, 95% CI=-3.06, 0.01) but not boys (beta=-0.20, 95% CI=-1.69, 1.26). Although we did not observe strong evidence that prenatal environmental phenols exposures influence the development of childhood adiposity, the potential antiadipogenic effect of benzophenone-3 in girls may warrant further investigation.

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

    Directory of Open Access Journals (Sweden)

    Tatyana V. Abramova


    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.

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



    Literature lacks publications about polar compounds content in infusion or guava leaves tea. Because of that, a comparison between different times of infusion and a conventional ultrasound aqueous extract was carried out. Several polar compounds have been identified by HPLC-ESI-MS and their antioxidant activity was evaluated by FRAP and ABTS assays. Four different classes of phenolic compounds (gallic and ellagic acid derivatives, flavonols, flavanones, and flavan-3-ols) and some benzophenone...

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

    Directory of Open Access Journals (Sweden)

    Irene See


    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.

  4. Removal and seasonal variability of selected analgesics/anti-inflammatory, anti-hypertensive/cardiovascular pharmaceuticals and UV filters in wastewater treatment plant. (United States)

    Golovko, Oksana; Kumar, Vimal; Fedorova, Ganna; Randak, Tomas; Grabic, Roman


    Seasonal removal efficiency of 16 pharmaceuticals and personal care products was monitored in a wastewater treatment plant in České Budějovice, Czech Republic, over a period of 1 year (total amount of samples, n = 272). The studied compounds included four UV filters, three analgesics/anti-inflammatory drugs and nine anti-hypertensive/cardiovascular drugs. In most cases, elimination of the substances was incomplete, and overall removal rates varied strongly from -38 to 100%. Therefore, it was difficult to establish a general trend for each therapeutic group. Based on the removal efficiencies (REs) over the year, three groups of target compounds were observed. A few compounds (benzophenon-1, valsartan, isradipine and furosemide) were not fully removed, but their REs were greater than 50%. The second group of analytes, consisting of 2-phenylbenzimidazole-5-sulfonic acid, tramadol, sotalol, metoprolol, atenolol and diclofenac, showed a very low RE (lower than 50%). The third group of compounds showed extremely variable RE (benzophenon-3 and benzophenon-4, codeine, verapamil, diltiazem and bisoprolol). There were significant seasonal trends in the observed REs, with reduced efficiencies in colder months.

  5. Heterogeneous and Photochemical Reactions Involving Surface Adsorbed Organics: Common Lignin Pyrolysis Products With Nitrogen Dioxide. (United States)

    Hinrichs, R. Z.; Nichols, B. R.; Rapa, C.; Costa, V.


    Solid-air interfaces, such as airborne particulate matter and ground level surfaces, provide unique supports for tropospheric heterogeneous chemistry. These interfaces commonly contain surface adsorbed organics, such as lignin pyrolysis products, that can significantly alter their physical and chemical properties. Attenuated total reflectance infrared spectroscopy (ATR-FTIR) provides an ideal tool for monitoring chemical changes in thin organic films during heterogeneous and photochemical reactions. Phenolic compounds, with and without co- adsorbed photosensitizers, were exposed to NO2 concentrations in the parts-per-billion range at 300 K and 20% relative humidity. Catechol, when mixed with benzophenone or dicyclohexylketone, formed 4- nitrocatechol as the dominant product under dark conditions. Deuterating the catechol alcohol groups caused the initial rate of reaction to decrease by a factor of 3.3±0.5, consistent with formation of the ortho- semiquinone radical as the rate determining step. The rate of 4-nitrocatechol formation did not increase under illuminated conditions, even with the presence of benzophenone a well known photosensitizer. UV-A/visible radiation did, however, initiate a photochemical reaction between benzophenone and 4-nitrocatechol, likely forming high molecular weight polymerization products. In contrast, 2-ethoxyphenol displayed no reactivity with NO2, even under illuminated conditions with a photosensitizer. Implications for the fate of lignin pyrolysis products, which are prevalent in biomass combustion smoke, will be discussed.

  6. Allergic and photoallergic contact dermatitis from ketoprofen: evaluation of cross-reactivities by a combination of photopatch testing and computerized conformational analysis. (United States)

    Foti, C; Bonamonte, D; Conserva, A; Stingeni, L; Lisi, P; Lionetti, N; Rigano, L; Angelini, G


    Allergic contact dermatitis (ACD) and photo-ACD are cell-mediated delayed hypersensitivity reactions of the skin caused by a wide range of substances. Topical ketoprofen (KP), a nonsteroidal anti-inflammatory drug (NSAID), can induce ACD and photo-ACD. Patients with ACD and/or photo-ACD to KP frequently show concomitant sensitization to other substances. The aim of this study was to identify the substances most frequently associated with sensitization to KP, and to evaluate, by means of computerized conformational analysis, whether this association could be due to cross-allergy. 15 subjects with ACD and photo-ACD to KP were tested with the SIDAPA (Società Italiana di Dermatologia Allergologica Professionale ed Ambientale) patch test standard series, including fragrance mix and its components (eugenol, isoeugenol, oak moss, geraniol, hydroxycitronellal, amylcinnamaldehyde, cinnamyl alcohol and cinnamaldehyde) and with the SIDAPA photopatch test series. Allergic reactions to cinnamyl alcohol were noted in all patients, whereas some patients also showed positive reactions to fenticlor, octocrylene and benzophenone-10. Computerized conformational analysis demonstrated that the structure of cinnamyl alcohol is similar to that of KP, whereas the structures of benzophenone-10, octocrylene and fenticlor are completely different. These results suggest that in patients with contact allergy to KP, concomitant positive reactions to cinnamyl alcohol are due to cross-sensitization, whereas simultaneous allergic reactions to fenticlor, octocrylene and benzophenone-10 should be regarded as co-sensitizations.

  7. Photo-cross-linkable thermoresponsive star polymers designed for control of cell-surface interactions. (United States)

    Park, Sangwoo; Cho, Hong Yul; Yoon, Jeong Ae; Kwak, Yungwan; Srinivasan, Abiraman; Hollinger, Jeffrey O; Paik, Hyun-jong; Matyjaszewski, Krzysztof


    Star polymers with thermoresponsive arms, consisting of 2-(2-methoxyethoxy)ethyl methacrylate (MEO₂MA) and oligo(ethylene glycol) methacrylate with ~4 ethylene oxide units (OEOMA₃₀₀, M(n) = 300), were synthesized via atom transfer radical polymerization (ATRP). 25% of the arms contained benzophenone chain-end functionality at the star periphery. A mixture of linear poly(MEO₂MA-co-OEOMA₃₀₀)-Br macroinitiators without and with benzophenone end-group macroinitiators were (MI and Bzp-MI, respectively) cross-linked with ethylene glycol dimethacrylate to form star polymers. Formation of star polymers was monitored by GPC, and the presence of benzophenone functionality in the stars was confirmed by ¹H NMR. The UV-vis spectroscopy revealed that the star polymers exhibit the low critical solution temperature (LCST) at 27 °C, slightly lower than LCST of either MI or Bzp-MI. Commercially available tissue culture grade polystyrene surface was modified by depositing a thin film of functionalized stars and UV cross-linking (λ = 365 nm). The star polymers covalently attached onto surfaces allowed a control of cell shrinkage and attachment in response to temperature changes.

  8. Migration of photoinitiators from cardboard into dry food: evaluation of Tenax® as a food simulant. (United States)

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


    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.

  9. Time weighted average concentration monitoring based on thin film solid phase microextraction. (United States)

    Ahmadi, Fardin; Sparham, Chris; Boyaci, Ezel; Pawliszyn, Janusz


    Time weighted average (TWA) passive sampling with thin film solid phase microextraction (TF-SPME) and liquid chromatography tandem mass spectrometry (LC-MS/MS) was used for collection, identification, and quantification of benzophenone-3, benzophenone-4, 2-phenylbenzimidazole-5-sulphonic acid, octocrylene, and triclosan in the aquatic environment. Two types of TF-SPME passive samplers, including a retracted thin film device using a hydrophilic lipophilic balance (HLB) coating, and an open bed configuration with an octadecyl silica-based (C18) coating, were evaluated in an aqueous standard generation (ASG) system. Laboratory calibration results indicated that the thin film retracted device using HLB coating is suitable to determine TWA concentrations of polar analytes in water, with an uptake that was linear up to 70 days. In open bed form, a one-calibrant kinetic calibration technique was accomplished by loading benzophenone3-d5 as calibrant on the C18 coating to quantify all non-polar compounds. The experimental results showed that the one-calibrant kinetic calibration technique can be used for determination of classes of compounds in cases where deuterated counterparts are either not available or expensive. The developed passive samplers were deployed in wastewater-dominated reaches of the Grand River (Kitchener, ON) to verify their feasibility for determination of TWA concentrations in on-site applications. Field trials results indicated that these devices are suitable for long-term and short-term monitoring of compounds varying in polarity, such as UV blockers and biocide compounds in water, and the data were in good agreement with literature data.

  10. Environmental Phenols And Pubertal Development In Girls (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.


    Environmental exposures to many phenols are documented worldwide and exposures can be quite high (>1 micromolar 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

  11. A Versatile Photoactivatable Probe Designed to Label the Diphosphate Binding Site of Farnesyl Diphosphate Utilizing Enzymes (United States)

    Henry, Olivier; Lopez-Gallego, Fernando; Agger, Sean A.; Schmidt-Dannert, Claudia; Sen, Stephanie; Shintani, David; Cornish, Katrina; Distefano, Mark D.


    Farnesyl diphosphate (FPP) is a substrate for a diverse number of enzymes found in nature. Photoactive analogues of isoprenoid diphosphates containing either benzophenone, diazotrifluropropionate or azide groups have been useful for studying both the enzymes that synthesize FPP as well as those that employ FPP as a substrate. Here we describe the synthesis and properties of a new class of FPP analogues that links an unmodified farnesyl group to a diphosphate mimic containing a photoactive benzophenone moiety; thus, importantly, these compounds are photoactive FPP analogues that contain no modifications of the isoprenoid portion of the molecule that may interfere with substrate binding in the active site of an FPP utilizing enzyme. Two isomeric compounds containing meta- and para-substituted benzophenones were prepared. These two analogues inhibit S. cerevisiae protein farnesyltransferase (ScPFTase) with IC50 values of 5.8 (meta isomer) and 3.0 µM (para isomer); the more potent analogue, the para isomer, was shown to be a competitive inhibitor of ScPFTase with respect to FPP with a KI of 0.46 µM. Radiolabeled forms of both analogues selectively labelled the β-subunit of ScPFTase. The para isomer was also shown to label E. coli farnesyl diphosphate synthase and Drosophila melanogaster farnesyl diphosphate synthase. Finally, the para isomer was shown to be an alternative substrate for a sesquiterpene synthase from Nostoc sp. strain PCC7120, a cyanobacterial source; the compound also labeled the purified enzyme upon photolysis. Taken together, these results using a number of enzymes demonstrate that this new class of probes should be useful for a plethora of studies of FPP-utilizing enzymes. PMID:19447628

  12. Synthesis of tin-containing polyimide films (United States)

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


    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.

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

    KAUST Repository

    Rajamanickam, V.P.


    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.

  14. Structure elucidation and antioxidant activity of the phenolic compounds from Rhynchosia suaveolens. (United States)

    Rammohan, Aluru; Gunasekar, Duvvuru; Reddy, Netala Vasudeva; Vijaya, Tartte; Devillee, Alexandre; Bodo, Bernard


    A new benzophenone, 2-hydroxy-3,4-dimethoxybenzophenone (1), together with a known C-glycosylxanthone, mangiferin (2) and two known C-glycosylflavones, isovitexin (3) and isoorientin (4), were isolated from the flowers of Rhynchosia suaveolens DC. (Fabaceae). The structure of the new compound (1) and the known compounds (2-4) were elucidated by extensive 1D and 2D NMR spectral studies. The plant extracts, as well as the isolated compounds, were evaluated for their total phenolic content (TPC), total flavonoid content (TFC) and DPPH radical scavenging activity. Among the isolated compounds, mangiferin (2) and isoorientin (4) showed significant radical scavenging activity comparable with that of ascorbic acid.


    Institute of Scientific and Technical Information of China (English)

    WU Shikang; DAI Guangsong; LIU Lusheng


    The absorption and fluorescence spectra of dibenzoyl methane have been studied. From the absorption spectra it was found that there are two peaks locating at 252 nm and 340 nm, respectively, similar to that of o-hydroxy benzophenone which can form intra-molecular hydrogen bond. Besides, an uncommonly large Stoke's shift of fluorescence can be observed in fluorescence spectra. The photostabilizing effects of dibenzoyl methane and UV-531 on the photodegradation of poly (cis-1, 4-butadiene) in solution have been investigated and compared. A possible mechanism was discussed.

  16. Synthesis of deuterium labelled lorazepam

    Energy Technology Data Exchange (ETDEWEB)

    Koeves, G.J. (Centre of Forensic Sciences, Toronto, ON (Canada))


    Synthesis of {sup 2}H{sub 3}-lorazepam was achieved by modification of literature procedures for the unlabelled drug. The key step in the seven step procedure was the initial one where upon selective exchange of 2-amino-5,2'-dichloro-benzophenone was obtained in deuterated acids. Purifications were carried out by preparative HPLC. The {sup 2}H{sub 3}-lorazepam is suitable for use as an internal standard in GC-MS-NICI-SIM quantitative analysis in forensic case work. (author).

  17. 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:; Alves, Arminda; Santos, Lúcia


    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

  18. Functional barrier in two-layer recycled PP films for food packaging applications (United States)

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


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


    Institute of Scientific and Technical Information of China (English)

    ZHAO Jingbo; ZHAO Tong; QIU Kunyuan


    The homopolymerization of 5-methyl-5-hexen-2,4-dione (methacryloylacetone, MAA),a vinyl monomer having β-diketone group, was carried out in the presence of benzophenone (BP)/N, N-dimenthyl-4-toluidine (DMT) system. Graft polymerization of acrylamide initiated by ceric ion onto the homopolymer film was investigated and the mechanism of the grafting reaction was proposed on the basis of ESR study. The grafted copolymer was characterized by means of grafting percentage, water absorption, XPS spectra and scanning electron photomicrographs.

  20. Characterizing a fast-response, low-afterglow liquid scintillator for neutron time-of-flight diagnostics in fast ignition experiments

    Energy Technology Data Exchange (ETDEWEB)

    Abe, Y., E-mail:; Hosoda, H.; Arikawa, Y.; Nagai, T.; Kojima, S.; Sakata, S.; Inoue, H.; Iwasa, Y.; Iwano, K.; Yamanoi, K.; Fujioka, S.; Nakai, M.; Sarukura, N.; Shiraga, H.; Norimatsu, T.; Azechi, H. [Institute of Laser Engineering, Osaka University, 2-6 Yamada-oka, Suita, Osaka 565-0871 (Japan)


    The characteristics of oxygen-enriched liquid scintillators with very low afterglow are investigated and optimized for application to a single-hit neutron spectrometer for fast ignition experiments. It is found that 1,2,4-trimethylbenzene has better characteristics as a liquid scintillator solvent than the conventional solvent, p-xylene. In addition, a benzophenon-doped BBQ liquid scintillator is shown to demonstrate very rapid time response, and therefore has potential for further use in neutron diagnostics with fast time resolution.

  1. Topical dexketoprofen as a cause of photocontact dermatitis. (United States)

    López-Abad, R; Paniagua, Ma J; Botey, E; Gaig, P; Rodriguez, P; Richart, C


    We reported on the case of a patient who developed a cutaneous eruption in a photoexposed area 1 week after a continous topical treatment with dexketoprofen (Enangel). Photopatch tests were positive for dexketoprofen, ketoprofen and piketoprofen and patch test was positive for piketoprofen. Control photopatch testing with dexketoprofen in 15 healthy volunteers was negative. Dexketoprofen, ketoprofen and piketoprofen are non-steroidal anti-inflamatory drugs (arylpropionic acid derivatives) often used as topical anti-inflammatory agents. It appears that the benzophenone moiety of their chemical structure is the cause of their photosensitivity and cross-photoreaction.

  2. Hyperbranched Polymers by Type II Photoinitiated Self-Condensing Vinyl Polymerization. (United States)

    Aydogan, Cansu; Ciftci, Mustafa; Yagci, Yusuf


    Type II photoinitiated self-condensing vinyl polymerization for the preparation of hyperbranched polymers is explored using 2-hydroxyethyl methacrylate (HEMA) or 2-(dimethylamino)ethyl methacrylate (DMAEMA), and methyl methacrylate as hydrogen donating inimers and comonomer, respectively, in the presence of benzophenone and camphorquinone under UV and visible light. Upon irradiation at the corresponding wavelength, the excited photoinitiator abstracts hydrogen from HEMA or DMAEMA leading to the formation of initiating radicals. Depending on the concentration of inimers, type of the photoinitiator, and irradiation time, hyperbranched polymers with different branching densities and cross-linked polymers are formed.

  3. (2-Hydroxy-4-methoxyphenyl(2-hydroxyphenylmethanone

    Directory of Open Access Journals (Sweden)

    Richard Betz


    Full Text Available The title compound, C14H12O4, is an asymmetric substitution product of benzophenone. Both hydroxy groups are orientated towards the O atom of the keto group. Intramolecular as well as intermolecular O—H...O hydrogen bonds can be observed in the crystal structure, with the latter connecting the molecules into chains along the crystallographic b axis. C—H...O contacts [C...O = 3.3297 (18 Å] are also apparent. The closest centroid–centroid distance between two aromatic systems is 4.9186 (9 Å.

  4. 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


    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...

  5. The Al(I) molecule, Ph2COAl and its anion (United States)

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


    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+.

  6. 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: [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)


    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

  7. Spin-orbit coupling and paramagnetic relaxation in micellized triplet radical pairs. Determination of relaxation parameters from magnetic field dependences of the decay kinetics (United States)

    Levin, P. P.; Kuzmin, V. A.


    The geminate recombination kinetics of the radical pairs produced by quenching of triplet benzophenone or 4-bromobenzophenone by 4-phenylphenol and 4-phenylaniline in aqueous micellar solutions of sodium dodecyl sulfate has been examined using the laser flash technique. Application of an external magnetic field results in the retardation of geminate recombination up to 20 times. The magnetic field dependences are considered in terms of a simple kinetic scheme, which includes the singlet-triplet evolution in the separated states of a pair due to hyperfine coupling and relaxation mechanisms as well as intersystem recombination process due to the spin-orbit coupling in the contact states of a pair.

  8. Regioselective synthesis of 1-alkyl- or 1-aryl-1H-indazoles via copper-catalyzed cyclizations of 2-haloarylcarbonylic compounds. (United States)

    Viña, Dolores; del Olmo, Esther; López-Pérez, José L; San Feliciano, Arturo


    [reaction: see text] A general method for the one-step regioselective synthesis of 1-alkyl- or 1-aryl-1H-indazoles from ortho-halogenated alkanoylphenones, benzophenones, and arylcarboxylic acids, via copper-catalyzed amination, was developed by using 0.2% mol of CuO in the presence of K(2)CO(3). The reaction involves amination followed by intramolecular dehydration. Different functionalized alkyl aryl ketones, diaryl ketones, and benzoic acid derivatives were efficiently coupled with several hydrazines. Ligands commonly employed as catalysts for intermolecular amination were shown to be ineffective for this cyclization.

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

    Directory of Open Access Journals (Sweden)

    Heng Xue


    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.


    Institute of Scientific and Technical Information of China (English)

    张克立; 袁继兵; 袁良杰; 孙聚堂


    Barium benzoate was synthesized in semi-solid phase reaction. The complex was characterized by elemental analysis, IR, X-ray powder diffraction. It is layered structure, monoclinic system. The mechanism of thermal decomposition for barium benzoate was studied by using TG, DTA, IR and gas chromatography-mass spectrometer. The thermal decompositon of barium benzoate in nitrogen proceeded in one stage: it decomposed to form BaCO3 and organic compounds. The organic compounds obtained from decomposition reaction are mainly benzophenone, triphenylmethane and so on.

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

    KAUST Repository

    Ma, Ting


    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.

  12. A novel method to prepare SPR sensor chips based on photografting molecularly imprinted polymer

    Institute of Scientific and Technical Information of China (English)

    Qing Quan Wei; Tian Xin Wei


    A novel method to prepare surface plasmon resonance (SPR) sensor chips based on grafted imprinted polymer is explored. Benzophenone photografting system is used to grow molecularly imprinted polymer (MIP) films from the modified surface of gold substrate. The surface morphology and thickness of MIP films were investigated by scanning electronic microscope (SEM). The adsorption properties of sensor chip were studied by SPR spectroscopy. The results demonstrate that nano-MIP films can be constructed on the surface of gold substrate with the good adsorption of template molecules.

  13. 2-[(2-Hydroxy-2,2-diphenylethyl(methylamino]-N,N-dimethylethanaminium bromide

    Directory of Open Access Journals (Sweden)

    Carsten Strohmann


    Full Text Available The title compound, C19H27N2O+·Br−, is the hydrobromide of the trapping product of lithiated N,N,N′,N′-tetramethylethylenediamine (TMEDA with benzophenone. Thereby, the N atom of the NMe2 group is selectively protonated and the respective trapping product represents a potential tridentate ligand with one O and two N donor atoms. The H atoms at N (H2N and O (H1O are involved in hydrogen bonds with the Br−. The molecular structure shows all donor atoms to be arranged on one side of the molecule, thus indicating a potential threefold coordination of a Lewis acid.


    Institute of Scientific and Technical Information of China (English)

    LI Tong; LUO Bin; LI Shanjun; CHU Guobei


    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.

  15. Addition-type polyimides from solutions of monomeric reactants (United States)

    Delvigs, P.; Serafini, T. T.; Lightsey, G. R.


    The monomeric reactants approach was used to fabricate addition-type polyimide/graphite fiber composites with improved mechanical properties and thermal stability characteristics over those of composites derived from addition-type amide acid prepolymers. A screening study of 24 different monomer combinations was performed. The results of a more extensive investigation of a selected number of monomer combinations showed that the combination providing the best thermomechanical properties was 5-norbornene-2,3-dicarboxylic acid monomethyl ester/4,4'-methylenedianiline/3,3'4,4'-benzophenone tetracarboxylic acid dimethyl ester at a molar ratio of 2/3.09/2.09.

  16. Distribution and seasonal occurrence of UV filters in rivers and wastewater treatment plants in Korea. (United States)

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


    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.

  17. Ketoprofen removal by O₃ and O₃/UV processes: kinetics, transformation products and ecotoxicity. (United States)

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


    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.

  18. Photodegradation of malachite green under natural sunlight irradiation: kinetic and toxicity of the transformation products. (United States)

    Pérez-Estrada, L A; Agüera, A; Hernando, M D; Malato, S; Fernández-Alba, A R


    This article describes the photolytic degradation of malachite green (MG), a cationic triphenylmethane dye used worldwide as a fungicide and antiseptic in the aquaculture industry. Photolysis experiments were performed by direct exposure of a solution of MG in water to natural sunlight. The main transformation products (TPs) generated during the process were identified by liquid chromatography time-of-flight mass spectrometry (LC-TOF-MS) and gas chromatography mass spectrometry (GC-MS). The 28 TPs identified with this strategy indicate that MG undergoes three main reactions, N-demethylation, hydroxylation and cleavage of the conjugated structure forming benzophenone derivatives. These processes involve hydroxyl radical attack on the phenyl ring, the N,N-dimethylamine group and the central carbon atom. The Vibrio fischeri acute toxicity test showed that the solution remains toxic after MG has completely disappeared. This toxicity could be assigned, at least in part, to the formation of 4-(dimethylamine)benzophenone, which has an EC(50,30 min) of 0.061 mg l(-1), and is considered "very toxic to aquatic organisms" by current EU legislation.

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

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


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

  20. Construction of Nontoxic Polymeric UV-Absorber with Great Resistance to UV-Photoaging (United States)

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


    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. 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


    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.

  2. [Degradation of Organic Sunscreens 2-hydroxy-4-methoxybenzophenone by UV/ H2O2 Process: Kinetics and Factors]. (United States)

    Feng, Xin-xin; Du, Er-deng; Guo, Ying-qing; Li, Hua-jie; Liu, Xiang; Zhou, Fang


    Organic sunscreens continue to enter the environment through people's daily consumption, and become a kind of emerging contaminants. The photochemical degradation of benzophenone-3 (BP-3) in water by UV/H2O2 process was investigated. Several factors, including the initial BP-3 concentration, H2O2 concentration, UV light intensity, coexisting cations and anions, humic acid and tert-butyl alcohol, were also discussed. The results showed that BP-3 degradation rate constant decreased with increasing initial BP-3 concentration, while increased with increasing H2O2 dosage and UV intensity. Coexisting anions could reduce the degradation rate, while coexisting ferric ions could stimulate the production of OH through Fenton-like reaction, further significantly accelerated BP-3 degradation process. The BP-3 degradation would be inhibited by humic acid or tert-butyl alcohol. The electrical energy per order (E(Eo)) values were also calculated to evaluate the cost of BP-3 degradation by UV/H2O2 process. The addition of ferric ions significantly reduced the value of E(Eo). The investigation of processing parameter could provide a reference for the practical engineering applications of benzophenone compounds removal by UV/H2O2 process.

  3. 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)


    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.

  4. Synthesis and biological evaluation of indole-2-carboxamides bearing photoactivatable functionalities as novel allosteric modulators for the cannabinoid CB1 receptor. (United States)

    Qiao, Chang-Jiang; Ali, Hamed I; Ahn, Kwang H; Kolluru, Srikanth; Kendall, Debra A; Lu, Dai


    5-Chloro-3-ethyl-N-(4-(piperidin-1-yl)phenethyl)-1H-indole-2-carboxamide (ORG27569, 1) is a prototypical allosteric modulator for the cannabinoid CB1 receptor. Based on this indole-2-carboxamide scaffold, we designed and synthesized novel CB1 allosteric modulators that possess photoactivatable functionalities, which include benzophenone, phenyl azide, aliphatic azide and phenyltrifluoromethyldiazrine. To assess their allosteric effects, the dissociation constant (KB) and allosteric binding cooperativity factor (α) were determined and compared to their parent compounds. Within this series, benzophenone-containing compounds 26 and 27, phenylazide-containing compound 28, and the aliphatic azide containing compound 36b showed allosteric binding parameters (KB and α) comparable to their parent compound 1, 7, 8, and 9, respectively. We further assessed these modulators for their impact on G-protein coupling activity. Interestingly, these compounds exhibited negative allosteric modulator properties in a manner similar to their parent compounds, which antagonize agonist-induced G-protein coupling. These novel CB1 allosteric modulators, possessing photoactivatable functionalities, provide valuable tools for future photo-affinity labeling and mapping the CB1 allosteric binding site(s).

  5. Contact urticaria, allergic contact dermatitis, and photoallergic contact dermatitis from oxybenzone. (United States)

    Landers, Maeran; Law, Sandra; Storrs, Frances J


    There is little literature regarding conventional patch tests and photopatch tests to oxybenzone resulting in both immediate- and delayed-type hypersensitivity reactions. A patient was patch-tested and photopatch-tested to various sunscreen chemicals. Both immediate- and delayed-type hypersensitivity reactions were observed with oxybenzone. The positive patch tests were also photoaccentuated. Oxybenzone, a common sunscreen allergen, can result in both contact urticaria and delayed-type hypersensitivity on both conventional patch testing and photopatch testing. Allergic contact dermatitis to sunscreen chemicals has traditionally included contact urticaria, allergic contact dermatitis, and photoallergic contact dermatitis. Due to the recognition of p-aminobenzoic acid (PABA) and its esters as sensitizers, the presence of benzophenones in "PABA-free" sunscreens has become more prevalent, especially in sunscreens with a sun protection factor (SPF) greater than 8. In our patient, immediate- and delayed-type hypersensitivity reactions were seen to oxybenzone (2-hydroxy-4-methoxybenzophenone, 2-benzoyl-5-methoxyphenol, benzophenone-3, Eusolex 4360, Escalol 567, EUSORB 228, Spectra-Sorb UV-9, Uvinul M-40) upon conventional patch testing and photopatch testing.

  6. Cu(II), Co(II), Ni(II), Mn(II), and Fe(II) metal complexes containing N,N'-(3,4-diaminobenzophenon)-3,5-Bu(t)(2)-salicylaldimine ligand: Synthesis, structural characterization, thermal properties, electrochemistry, and spectroelectrochemistry. (United States)

    Tas, E; Kilic, A; Durgun, M; Küpecik, L; Yilmaz, I; Arslan, S


    The synthesis, structure, spectroscopic and electro-spectrochemical properties of steric hindered Schiff-base ligand [N,N'-(3,4-benzophenon)-3,5-Bu(t)(2)-salicylaldimine (LH(2))] and its mononuclear Cu(II), Co(II), Ni(II), Mn(II) and Fe(II) complexes are described in this work. The new dissymmetric steric hindered Schiff-base ligand containing a donor set of NONO was prepared through reaction of 3,4-diaminobenzophenon with 3,5-Bu(t)(2)-salicylaldehyde. Certain metal complexes of this ligand were synthesized by treating an ethanolic solution of the ligand with an equimolar amount of metal salts. The ligand and its complexes were characterized by FT-IR, UV-vis, (1)H NMR, elemental analysis, molar conductivity and thermal analysis methods in addition to magnetic susceptibility, electrochemistry and spectroelectrochemistry techniques. The tetradentate and mononuclear metal complexes were obtained by reacting N,N'-(3,4-benzophenon)-3,5-Bu(t)(2)-salicylaldimine (LH(2)) with some metal acetate in a 1:1 mole ratio. The molar conductance data suggest metal complexes to be non-electrolytes.

  7. Ring expansion reactions of pentaphenylborole with dipolar molecules as a route to seven-membered boron heterocycles. (United States)

    Huang, Kexuan; Martin, Caleb D


    Reactions of pentaphenylborole with isocyanates, benzophenone, and benzaldehyde produced new seven-membered heterocycles in high yields. For 1-adamantyl isocyanate, a BNC5 heterocycle was obtained from the insertion of the C-N moiety into the five-membered borole, whereas for 4-methoxyphenyl isocyanate, a BOC5 heterocycle was generated from the insertion of the C-O unit. These reactions are believed to occur via a mechanism wherein coordination of the nucleophile to the borole (1-adamantyl, N-coordination or O-coordination for 4-methoxyphenyl) is followed by ring expansion to afford the observed seven-membered heterocycles. The selectivity to form B-O- or B-N-containing heterocycles is based on the polarization of the isocyanate implying tunable reactivity for the system. Having observed that isocyanates react as 1,2-dipoles with pentaphenylborole, we examined benzophenone and benzaldehyde, which both reacted to insert C-O units into the ring. This represents a new efficient method for preparing rare seven-membered boracycles.

  8. Spontaneous association of hydrophobized dextran and poly-beta-cyclodextrin into nanoassemblies. Formation and interaction with a hydrophobic drug. (United States)

    Daoud-Mahammed, S; Ringard-Lefebvre, C; Razzouq, N; Rosilio, V; Gillet, B; Couvreur, P; Amiel, C; Gref, R


    New nanoassemblies were instantaneously prepared by mixing two aqueous solutions, one containing a beta-cyclodextrin polymer (pbetaCD), and the other a hydrophobically modified by alkyl chains dextran (MD). The formation mechanism and the inner structure of these nanoassemblies were analysed using surface tension measurements and (1)H NMR spectroscopy. The effect of a hydrophobic guest molecule, such as benzophenone (BZ), on the formation and stability of the nanoassemblies was also evaluated. MD exhibited the typical behaviour of a soluble amphiphilic molecule and adsorbed at the air/water interface. Whereas the injection of native beta-CDs in the solution beneath the adsorbed MD monolayer did not produce any change in the surface tension, that of the pbetaCD resulted in an increase in the surface tension, indicating the desorption of the polymer from the interface. This result accounts for a cooperative effect of beta-CDs linked together in the pbetaCD polymer on dextran desorption. The presence of benzophenone in the system hindered the sequestration of dextran alkyl moieties by beta-CD in the polymer without impeding the formation of associative nanoassemblies of 100-200 nm. (1)H NMR investigations demonstrated that, in the BZ-loaded nanoassemblies, the hydrophobic molecule was mainly located into the cyclodextrin cavities.

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

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


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

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

    Mohamed, Nasser H.; Bahners, Thomas; Wego, Andreas; Gutmann, Jochen S.; Ulbricht, Mathias


    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.

  11. Direct observation of slow intersystem crossing in an aromatic ketone, fluorenone. (United States)

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


    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.

  12. Effect of 2,4-dihydroxybenzophenone (BP1) on early life-stage development of the marine copepod Acartia tonsa at different temperatures and salinities

    DEFF Research Database (Denmark)

    Kusk, Kresten Ole; Avdolli, Manola; Wollenberger, Leah


    Benzophenone (BP)-type ultraviolet (UV) filters are widely used in cosmetic and sunscreen products and can enter the aquatic environment. Therefore, we investigated the subchronic toxicity of 2,4-dihydroxybenzophenone (BP1) on the marine calanoid copepod Acartia tonsa in an early life-stage devel......Benzophenone (BP)-type ultraviolet (UV) filters are widely used in cosmetic and sunscreen products and can enter the aquatic environment. Therefore, we investigated the subchronic toxicity of 2,4-dihydroxybenzophenone (BP1) on the marine calanoid copepod Acartia tonsa in an early life......-stage development study. Since developmental endpoints depend on environmental conditions, a preceding study of A. tonsa development was performed at three temperatures, four salinities, four light:dark regimes, six food densities, and four culture densities. Times elapsed until 50% of the population had reached...... a copepodite stage (DT(½) ) at the different conditions were calculated. The DT(½) values decreased from 296 h at 15°C to 89 h at 25°C and were also affected by salinity (126 h at 15‰ and 167 h at 30‰), whereas the light:dark regime and culture density influenced development only to a minor extent. BP1...

  13. Photo-Crosslinkable Shape-Memory Elastomers Containing Hydrogen-Bonding Side-Groups (United States)

    Li, Jiahui; Lewis, Christopher; Anthamatten, Mitchell


    Lightly crosslinked poly(butyl acrylate) networks containing self-complementary hydrogen bonding side-groups (e.g. ureidopyrimidinones) can exhibit unique shape-memory effects. Conventional free-radical solution polymerization of monomer mixtures offers a simple approach to achieving these networks, but presents the following limitations: (i) the H-bonding side- group content is limited by its solubility; (ii) prepared networks can only be studied in their crosslinked form; and (iii) upon solvent removal, intrinsic stress is generated making shape-memory responses difficult to interpret. Here, photo-polymerization of linear prepolymers is reported as an approach to overcome these limitations. A series of linear poly (butyl acrylate)s containing light-sensitive benzophenone side- groups and H-bonding side-groups were prepared using free radical polymerization. These pre-polymers can be fully characterized in solution (NMR, GPC). Moreover, following solvent removal, they can be molded into any desired shape and subsequently photo-crosslinked to form shape-memory elastomers. The impact of H-bonding side-group content and the benzophenone side-group content on the mechanical properties of the photo-crosslinked polymer will be discussed. A constitutive model is also developed to interpret the mechanical response of these shape-memory elastomers.

  14. Combination of retinyl palmitate and UV-filters: phototoxic risk assessment based on photostability and in vitro and in vivo phototoxicity assays. (United States)

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


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

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

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


    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.

  16. A photoactive isoprenoid diphosphate analogue containing a stable phosphonate linkage: synthesis and biochemical studies with prenyltransferases (United States)

    DeGraw, Amanda J.; Zhao, Zongbao; Strickland, Corey L.; Taban, A. Huma; Hsieh, John; Michael, Jefferies; Xie, Wenshuang; Shintani, David; McMahan, Colleen; Cornish, Katrina; Distefano, Mark D.


    A number of biochemical processes rely on isoprenoids, including the post-translational modification of signaling proteins and the biosynthesis of a wide array of compounds. Photoactivatable analogues have been developed to study isoprenoid utilizing enzymes such as the isoprenoid synthases and prenyltransferases. While these initial analogues proved to be excellent structural analogues with good cross linking capability, they lack the stability needed when the goals include isolation of cross-linked species, tryptic digestion, and subsequent peptide sequencing. Here, the synthesis of a benzophenone-based farnesyl diphosphate analogue containing a stable phosphonophosphate group is described. Inhibition kinetics, photolabeling experiments, as well as x-ray crystallographic analysis with a protein prenyltransferase are described, verifying this compound as a good isoprenoid mimetic. In addition, the utility of this new analogue was explored by using it to photoaffinity label crude protein extracts obtained from Hevea brasiliensis latex. Those experiments suggest that a small protein, Rubber Elongation Factor, interacts directly with farnesyl diphosphate during rubber biosynthesis. These results indicate that this benzophenone-based isoprenoid analogue will be useful for identifying enzymes that utilize farnesyl diphosphate as a substrate. PMID:17477573

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

    Directory of Open Access Journals (Sweden)

    Elixabet Díaz-de-Cerio


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

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

    DEFF Research Database (Denmark)

    Frederiksen, Hanne; Nielsen, Ole; Skakkebaek, Niels E;


    ), benzophenone-3 (BP-3), 5-chloro-2- hydroxybenzophenone (BP-7), 4-hydroxybenzophenone (4-HBP), 4-methyl-benzophenone (4-MBP), 3-(4- methylbenzylidene)-camphor (4-MBC) and 3-benzylidene camphor (3-BC) were monitored in 24h urine and two consecutive first morning samples from 129 healthy Danish children...... significantly correlated (R(2)=0.815). BP, 4-HBP and BP-2 were found in 43, 15 and 5% of the samples, respectively. The median (range) concentrations of the UV-filters in 24-h urine were as follows: BP-3, 0.92 (LOD-115); BP-1, 0.54 (LOD-44.6); BP,HBP,... between first morning and 24h urine levels of BP-3, BP-1 and 4-HBP from the same day was observed. CONCLUSION: Our project on UV filters analyzed by a new robust and sensitive LC-MS/MS method in Danish children and adolescents showed that almost all individuals were exposed to UV filters. Sun protection...

  19. Evaluation of fungal- and photo-degradation as potential treatments for the removal of sunscreens BP3 and BP1. (United States)

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


    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.

  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


    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. Microwave-Assisted Organocatalyzed Rearrangement of Propargyl Vinyl Ethers to Salicylaldehyde Derivatives: An Experimental and Theoretical Study. (United States)

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


    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.

  2. Probing the Catalytic Promiscuity of a Regio- and Stereospecific C-Glycosyltransferase from Mangifera indica. (United States)

    Chen, Dawei; Chen, Ridao; Wang, Ruishan; Li, Jianhua; Xie, Kebo; Bian, Chuancai; Sun, Lili; Zhang, Xiaolin; Liu, Jimei; Yang, Lin; Ye, Fei; Yu, Xiaoming; Dai, Jungui


    The catalytic promiscuity of the novel benzophenone C-glycosyltransferase, MiCGT, which is involved in the biosynthesis of mangiferin from Mangifera indica, was explored. MiCGT exhibited a robust capability to regio- and stereospecific C-glycosylation of 35 structurally diverse druglike scaffolds and simple phenolics with UDP-glucose, and also formed O- and N-glycosides. Moreover, MiCGT was able to generate C-xylosides with UDP-xylose. The OGT-reversibility of MiCGT was also exploited to generate C-glucosides with simple sugar donor. Three aryl-C-glycosides exhibited potent SGLT2 inhibitory activities with IC50  values of 2.6×, 7.6×, and 7.6×10(-7)  M, respectively. These findings demonstrate for the first time the significant potential of an enzymatic approach to diversification through C-glycosidation of bioactive natural and unnatural products in drug discovery.

  3. Correlation analysis of reactivity in the oxidation of some para- substituted benzhydrols by triethylammonium chlorochromate in non-aqueous media

    Directory of Open Access Journals (Sweden)

    S. Sheik Mansoor


    Full Text Available Triethylammonium chlorochromate (TriEACC oxidation of some para-substituted benzhydrols (BH in dimethylsulfoxide (DMSO leads to the formation of corresponding benzophenones. The reaction was run under pseudo-first-order conditions. The reaction is catalyzed by hydrogen ions. The hydrogen ion dependence has the form: kobs = a + b[H+]. Various thermodynamic parameters for the oxidation have been reported and discussed along with the validity of isokinetic relationship. Oxidation of benzhydrol was studied in 18 different organic solvents. The rate data showing satisfactory correlation with Kamlet–Taft solvatochromic parameters (α, β and π∗ suggests that the specific solute–solvent interactions play a major role in governing the reactivity, and the observed solvent effects have been explained on the basis of solute–solvent complexation. A suitable mechanism of oxidation has been proposed.

  4. Preparation and characterization of star ABC triblock copolymer of ethylene oxide,styrene and methyl methacrylate

    Institute of Scientific and Technical Information of China (English)

    黄骏廉; 黄晓宇; 胡文兵; 楼文奎


    A universally significant method,which combines the anionic polymerization with photoinduced charge transfer polymerization,for preparation of soluble star ABC triblock copolymer of ethylene oxide,styrene and methyl methacrylate,was described.The poly(ethylene oxide) (PEO) block was formed by initiation of phenoxy an-ions using p-aminophenol protected by Schiff’s base as the parent compound Then the charge transfer system composed of PEO chains with deprotected-amino end groups and benzophenone initiated the polymerization of styrene and methyl metnacrylate sequentially under UV irradiation.The formed star triblock copolymer of styrene,ethylene oxide and methyl methacrylate could be purified by thin-layer chromatography (TLC) and characterized by IR,1H NMR,GPC (gel permeation chromatogrphy) and PGC (pyrolysis gas chromatography).

  5. Addition Polyimides from Non-Mutagenic Diamines (United States)

    Delvigs, Peter; Klopotek, David L.; Hardy-Green, DeNise; Meador, Michael A. (Technical Monitor)


    Studies were conducted to find an acceptable non-mutagenic diamine to replace 4,4'-methylenedianiline (MDA), a suspect carcinogen, which is currently being used in PMR-15 polyimide applications. Several diamines containing fluorine and trifluoromethyl substituent groups were synthesized. The diamines were polymerized with the dimethyl ester of 3,3',4,4'-benzophenone tetracarboxylic acid (BTDE), using the monomethyl ester of nadic acid (NE) as an endcap. The effect of diamine structure on rheological properties, glass transition temperature, and thermo-oxidative stability was investigated. Unidirectional laminates were fabricated from selected resins, using carbon fiber as the reinforcement. The results indicate that some of the diamines containing trifluoromethyl groups are non-mutagenic, and have potential to replace MDA in PMR polyimides for long-term applications at temperatures up to 300 C.

  6. GLC determination of plasma drug levels after oral administration of clorazepate potassium salts. (United States)

    Hoffman, D J; Chun, A H


    Plasma nordiazepam levels resulting from the oral administration of clorazepate potassium salts were determined by a sensitive GLC assay. Nordiazepam and the internal standard (diazepam) were selectively extracted into ether at pH 9.2, hydrolyzed to their respective benzophenones, and quantified by electron-capture detection. The assay was used in a comparative bioavailability study of single equimolar oral doses of monopotassium and dipotassium salts of clorazepate in dogs. Both clorazepate salts were rapidly absorbed and exhibited mean peak total drug levels after 1 hr. Clorazepate levels accounted for about 50% of the total drug levels present. No statistical difference in the plasma drug levels of clorazepate mono- and dipotassium salts and the metabolite was found in dogs.


    Directory of Open Access Journals (Sweden)

    Jose Otavio Carrera Silva Junior et al.


    Full Text Available Studies have been demonstrating that Vismia guianensis (Aubl. Choisy, popularly known as seal, a species native to South America has high anticancer and antimicrobial potential. The objective of this study was to evaluate the antimicrobial activity of the ethanolic extract obtained from the leaves of V. guianensis, and trace its chemical profile. The phytochemical screening showed the presence of different phenolic compounds in the extract. The high performance liquid chromatography performed on the sub-fractions A and B from the ethyl acetate fraction traced the chemical composition profile of the ethanol extract, composed by benzophenone, xanthones and anthraquinones. The antimicrobial activity of the extract evaluated by agar diffusion method showed inhibition against Gram-positive bacteria: Streptococcus mitis (ATCC 903, Streptococcus sanguis (ATCC 10557 and Staphylococcus aureus (ATCC 6538 and the fungi: Candida albicans (ATCC 40175, Candida krusei (ATCC 40147 and Candida parapsilosis (ATCC 40038.

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

    DEFF Research Database (Denmark)

    Parker, Erica N; Song, Jiangli; Kishore Kumar, G D;


    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 9.9nM, 14.4nM, and 8.1nM, 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 10μM. Thiosemicarbazone analogue 8 significantly inhibited the invasive potential of PC-3ML prostate cancer cells by 92% at 5μ...

  9. Direct observation of f-pair magnetic field effects and time-dependence of radical pair composition using rapidly switched magnetic fields and time-resolved infrared methods. (United States)

    Woodward, Jonathan R; Foster, Timothy J; Salaoru, Adrian T; Vink, Claire B


    A rapidly switched (magnetic field was employed to directly observe magnetic fields from f-pair reactions of radical pairs in homogeneous solution. Geminate radical pairs from the photoabstraction reaction of benzophenone from cyclohexanol were observed directly using a pump-probe pulsed magnetic field method to determine their existence time. No magnetic field effects from geminate pairs were observed at times greater than 100 ns after initial photoexcitation. By measuring magnetic field effects for fields applied continuously only after this initial geminate period, f-pair effects could be directly observed. Measurement of the time-dependence of the field effect for the photolysis of 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone in cyclohexanol using time-resolved infrared spectroscopy revealed not only the presence of f-pair magnetic field effects but also the ability of the time dependence of the MARY spectra to observe the changing composition of the randomly encountering pairs throughout the second order reaction period.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  11. Spectroscopic (FT-IR, FT-Raman, UV-Visible) and quantum chemical studies of 4-Chloro-3-iodobenzophenone (United States)

    Venkata Prasad, K.; Muthu, S.; Santhamma, C.


    The vibrational analysis of the substituted Benzophenone molecule 4-Chloro-3-iodobenzophenone (4, 3-ClIBP) is carried out using both FT-IR and FT-Raman spectra and also quantum chemical calculations of the scaled frequencies using the DFT method B3LYP/LanL2DZ basis set. The natural bond orbital analysis of this molecule has been carried out to describe the various intramolecular interactions responsible for the stabilization of the molecule. The HOMO, LUMO energy gap have been computed with the TD-DFT theory and the differences are compared with UV-absorption spectra. The statistical thermodynamic functions are calculated for the range of 100-1000 k. The Fukui functions are evaluated to describe the activity of the sites.

  12. Size-controlled nanoassemblies based on cyclodextrin-modified dextrans. (United States)

    Wintgens, Véronique; Nielsen, Thorbjørn Terndrup; Larsen, Kim Lambertsen; Amiel, Catherine


    Nanoassemblies formed by host/guest interactions between two polymers in aqueous media are studied. Two types of polymers with the same dextran backbone are modified with adamantyl or βCD groups. The sizes of the spontaneously formed nanoassemblies depend on the βCD:Ada ratio and on the total concentration and composition of the mixtures. The results can be rationalized by assuming a core/shell structure of the nanoassemblies, the core resulting from associative phase separation of the two polymers and being stabilized by an external shell made of Ada-grafted dextran and containing ions adsorbed from the solution. Hydrophobic compounds such as benzophenone can be incorporated efficiently without inducing changes in properties of the nanoassemblies.

  13. Antiplasmodial Natural Products

    Directory of Open Access Journals (Sweden)

    Cláudio R. Nogueira


    Full Text Available Malaria is a human infectious disease that is caused by four species of Plasmodium. It is responsible for more than 1 million deaths per year. Natural products contain a great variety of chemical structures and have been screened for antiplasmodial activity as potential sources of new antimalarial drugs. This review highlights studies on natural products with antimalarial and antiplasmodial activity reported in the literature from January 2009 to November 2010. A total of 360 antiplasmodial natural products comprised of terpenes, including iridoids, sesquiterpenes, diterpenes, terpenoid benzoquinones, steroids, quassinoids, limonoids, curcubitacins, and lanostanes; flavonoids; alkaloids; peptides; phenylalkanoids; xanthones; naphthopyrones; polyketides, including halenaquinones, peroxides, polyacetylenes, and resorcylic acids; depsidones; benzophenones; macrolides; and miscellaneous compounds, including halogenated compounds and chromenes are listed in this review.

  14. Probing the interplay between factors determining reaction rates on silica gel using termolecular systems. (United States)

    Kirkpatrick, Iain; Worrall, David R; Williams, Siân L; Buck, Craig J T; Meseguer, Rafael G


    In this study we have compared energy and electron transfer reactions in termolecular systems using a nanosecond diffuse reflectance laser flash photolysis technique. We have previously investigated these processes on silica gel surfaces for bimolecular systems and electron transfer in termolecular systems. The latter systems involved electron transfer between three arene molecules with azulene acting as a molecular shuttle. In this study we present an alternative electron transfer system using trans β-carotene as an electron donor in order to effectively immobilise all species except the shuttle, providing the first unambiguous evidence for radical ion mobility. In the energy transfer system we use naphthalene, a structural isomer of azulene, as the shuttle, facilitating energy transfer from a selectively excited benzophenone sensitiser to 9-cyanoanthracene. Bimolecular rate constants for all of these processes have been measured and new insights into the factors determining the rates of these reactions on silica gel have been obtained.

  15. Recent Advances on Endocrine Disrupting Effects of UV Filters

    Directory of Open Access Journals (Sweden)

    Jiaying Wang


    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.

  16. 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)


    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.

  17. Synthesis of Some New Benzimidazole Derivatives of Pharmaceutical Interest

    Directory of Open Access Journals (Sweden)

    Fawzia Zakaria El-Ablack


    Full Text Available Reaction of 2-(aminomethylbenzimidazole dihydrochloride (1 with ethyl acetoacetate was studied to give diazepinone-benzimidazole derivative (2, while, treatment of 1 with phenylhydrazono ethylacetoacetate afforded phenylhydrazino diazepinone derivative (3. On the other hand, reaction of 1 with acetyl acetone resulted in the formation of diazepine derivative (4. The reaction of 1 with ethyl cyanoacetate was studied to give 3-aminodiazepinone derivative (5. Also the reaction of 1 with acetophenone and/or benzophenone has been investigated to give the fused imidazolines 6 and 7 respectively, while the reaction of 1 with cyclopentanone gave benzimidazolyl derivative (8. Treatment of 1 with chloroacetyl chloride gave the fused pyrazinone (9. The treatment of 1 with benzoin gave the derivative (10. The structures of the hitherto unknown compounds have been confirmed from analytical and spectral data. The newly synthesized compounds were screened for antibacterial and antifungal activity.

  18. Iron-Catalyzed Ortho C-H Methylation of Aromatics Bearing a Simple Carbonyl Group with Methylaluminum and Tridentate Phosphine Ligand. (United States)

    Shang, Rui; Ilies, Laurean; Nakamura, Eiichi


    Iron-catalyzed C-H functionalization of aromatics has attracted widespread attention from chemists in recent years, while the requirement of an elaborate directing group on the substrate has so far hampered the use of simple aromatic carbonyl compounds such as benzoic acid and ketones, much reducing its synthetic utility. We describe here a combination of a mildly reactive methylaluminum reagent and a new tridentate phosphine ligand for metal catalysis, 4-(bis(2-(diphenylphosphanyl)phenyl)phosphanyl)-N,N-dimethylaniline (Me2N-TP), that allows us to convert an ortho C-H bond to a C-CH3 bond in aromatics and heteroaromatics bearing simple carbonyl groups under mild oxidative conditions. The reaction is powerful enough to methylate all four ortho C-H bonds in benzophenone. The reaction tolerates a variety of functional groups, such as boronic ester, halide, sulfide, heterocycles, and enolizable ketones.

  19. Phototransformation of pesticides in prairie potholes: effect of dissolved organic matter in triplet-induced oxidation. (United States)

    Karpuzcu, M Ekrem; McCabe, Andrew J; Arnold, William A


    Photochemical reactions involving a variety of photosensitizers contribute to the abiotic transformation of pesticides in prairie pothole lakes (PPLs). Despite the fact that triplet excited state dissolved organic matter (DOM) enhances phototransformation of pesticides by acting as a photosensitizer, it may also decrease the overall phototransformation rate through various mechanisms. In this study, the effect of DOM on the phototransformation of four commonly applied pesticides in four different PPL waters was investigated under simulated sunlight using photoexcited benzophenone-4-carboxylate as the oxidant with DOM serving as an anti-oxidant. For atrazine and mesotrione, a decrease in phototransformation rates was observed, while phototransformations of metolachlor and isoproturon were not affected by DOM inhibition. Phototransformation rates and the extent of inhibition/enhancement by DOM varied spatially and temporally across the wetlands studied. Characterization of DOM from the sites and different seasons suggested that the DOM type and variations in the DOM structure are important factors controlling phototransformation rates of pesticides in PPLs.


    Institute of Scientific and Technical Information of China (English)

    WANG Erjian; FANG Peiji; FENG Xinde


    A kind of cationic compounds, having benzophenone end group and various length chain (PKT) (BP-CH2N + R2R'·X-, R&R' different chain length alkyl group)were used as photosensitizers. Various BP/TEA systems have been used for study, The efficiency of MMA photopolymerization initiated by them shows PKT > BP in homogeneous water solution and PKT> BP/CTAB in micellar water solution. The results obtained indicate that catalytic effects of PKT type functional micelles are far greater than that of common micelle with the enhancement of polymerization rate over 10 times compared with BP in water solution. The catalytic role,reaction character of PKT, effect of counter ions and retarding effect of oxygen have also been discussed.

  1. The examination of berberine excited state by laser flash photolysis (United States)

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


    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.

  2. Phenolics from Phaleria nisidai with Estrogenic Activity

    Directory of Open Access Journals (Sweden)

    Christopher Kitalong


    Full Text Available The methanol extract of P. nisidai leaves yielded a benzophenone rhamnoside , iriflophenone 2-O-α-L-rhamnopyranoside (1 in addition to g enkwanin 5-O-β-D-primeveroside (2 and mangiferin (3. The isolated compounds as well as the derived aglycones of 1 and 2 assigned as compounds 4 and 5, respectively, were tested for their estrogenic activity on ERα using an estrogen receptor competitive binding screen. Compounds 1 , 4 and 5 showed almost the same binding ability to ERα with IC 50 of 630 µM, 700 µM and 800 µM, respectively. Virtual docking with ERα revealed that compound 1, 4 and 5 strongly hydrogen bond with amino acids Glu353, Arg349, Gly521 and His524, in the estrogen receptor ligand binding domain, similar to that of mammalian estrogen 17β-estradiol.

  3. Theoretical study of tautomers and photoisomers of avobenzone by DFT methods. (United States)

    Trossini, Gustavo H G; Maltarollo, Vinicius G; Garcia, Ricardo D'A; Pinto, Claudinéia A S O; Velasco, Maria V R; Honorio, Kathia M; Baby, André R


    Organic ultraviolet (UV) filters such as cinnamates, benzophenones, p-aminobenzoic derivatives, and avobenzone (which have well-established and recognized UV-filtering efficacies) are employed in cosmetic/pharmaceutical products to minimize the harm caused by exposure of the skin to sunlight. In this study, a detailed investigation of the photostability and tautomerism mechanisms of avobenzone was performed utilizing DFT methods. The UV spectral profile of avobenzone was also simulated, and the results showed good agreement with experimental data. Furthermore, the calculations were able to distinguish tautomers and photoisomers of the studied organic filter based on their properties, thus showing the potential to develop new organic UV filters. Graphical Abstract Theoretical studies of avobenzone and its tautomers by TD-DFT.

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

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


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

  5. Synthesis and characterization of thermally stable second-order nonlinear optical side-chain polyimides containing thiazole and benzothiazole push-pull chromophores (United States)

    Tambe, S. M.; Kittur, A. A.; Inamdar, S. R.; Mitchell, G. R.; Kariduraganavar, M. Y.


    Push-pull nonlinear optical (NLO) chromophores containing thiazole and benzothiazole acceptors were synthesized and characterized. Using these chromophores a series of second-order NLO polyimides were successfully prepared from 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), pyromellitic dianhydride (PMDA) and 3,3'4,4'-benzophenone tetracarboxylic dianhydride (BTDA) by a standard condensation polymerization technique. These polyimides exhibit high glass transition temperatures ranging from 160 to 188 °C. UV-vis spectrum of polyimide exhibited a slight blue shift and decreases in absorption due to birefringence. From the order parameters, it was found that chromophores were aligned effectively. Using in situ poling and temperature ramping technique, the optical temperatures for corona poling were obtained. It was found that the optimal temperatures of polyimides approach their glass transition temperatures. These polyimides demonstrate relatively large d33 values range between 35.15 and 45.20 pm/V at 532 nm.

  6. Selective Patterning of Organic Light-Emitting Diodes by Physical Vapor Deposition of Photosensitive Materials (United States)

    Muroyama, Masakazu; Saito, Ichiro; Yokokura, Seiji; Tanaka, Kuniaki; Usui, Hiroaki


    A novel method of patterning polymeric thin films by the vapor deposition of a photosensitive layer followed by photopolymerization and development was proposed. This method was applied to the patterning of the emissive layer (EML) of an organic light-emitting diode (OLED). For the hole transport layer (HTL), N,N,N'-triphenyl-N'-(4-vinylphenyl)-biphenyl-4,4'-diamine (vTPD) and a zinc acrylate (ZnAc) crosslinker were coevaporated. The film was polymerized by postdeposition annealing to yield a polymeric HTL with a high resistance to organic solvents. On this HTL, the photosensitive EML was prepared by coevaporating a 9H-carbazole-9-ethylmethacrylate (CEMA) host material and 4-(dimethylamino)benzophenone (DABP) photoinitiator. UV irradiation on the EML through a photomask initiated radical polymerization, leaving a negative pattern of the irradiated region after immersion in tetrahydrofuran (THF). The photopatterning process was found to cause no damage to the film morphology or the device characteristics.

  7. Effects of acid diffusibility and affinity to cellulose on strength loss of polycarboxylic acid crosslinked fabrics. (United States)

    Ji, Bolin; Zhao, Cunyi; Yan, Kelu; Sun, Gang


    1,2,3,4-Butanetetracarboxylic acid (BTCA) imparts good anti-wrinkle property to cotton fabrics and results in significant strength loss due to cross-linking and acid degradation of cellulose simultaneously. However, benzophenone-3,3',4,4'- tetracarboxylic acid (BPTCA), an aromatic acid, crosslinks cellulose effectively but causes less strength loss to the products under similar conditions. The difference in damages to cellulose fibers was analyzed by using diffusibility and corresponding affinity of the acids to cellulose fibers, which were estimated by their molecular sizes and Hansen solubility parameters (HSP). Both experimental results and theoretical speculations revealed consistent agreement, indicating that smaller acid molecules could diffuse into cellulose fiber more rapidly and deeply, resulting in more acid degradation. Besides, the aliphatic acid such as BTCA has higher molecular affinity than BPTCA to cellulose, causing additional more degradation of cellulose. Both factors are potential reasons of the observed more severe tensile strength loss of the BTCA treated cotton fabrics.


    Institute of Scientific and Technical Information of China (English)

    ZHANG Zhenfeng; HU Xingzhou; YAN Qing


    Photoinduced grafting of acrylic and allyl monomers on polyethylene surface was generally studied by using benzophenone (BP) as a photoinitiator. The grafting process was carried out either in vapor-phase or in solution of the monomers. In the vapor-phase reaction with a filter used to cut off the short wavelength UV light, allyl amine is the most reactive of the four monomers used and acrylic amide is comparatively more reactive than acrylic acid and allyl alcohol. Acetone, as a solvent and carrier for initiator and monomers, however, shows its reactivity to participate the reaction. The solution grafting with a filter is much faster than the corresponding vapor-phase reaction, and a fully covered surface by the grafted polymer can be achieved in this way.

  9. A new screening method for flunitrazepam in vodka and tequila by fluorescence spectroscopy. (United States)

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


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

  10. Steric effects on intramolecular reactivity in cyclic dipeptides: Conformational analysis validated by a combined MD/DFT approach (United States)

    Lewandowska, A.; Carmichael, I.; Hörner, G.; Hug, G. L.; Marciniak, B.


    The present Molecular Dynamics (MD) simulation study addresses the geometric requirements of close-contact formation in short peptides. This process, that is probed herein by intramolecular H-atom transfer, initiated by triplet-excited ketones, demands close contact between the H-donating and H-accepting moieties. Thus, any deduction about the compound's reactivity based just on MD simulations, requires independent verification of the computed conformational preferences. In this study, a procedure was developed using diketopiperazine-linked benzophenone/tyrosine dyads. Specifically, it involves a comparison of the dyads' experimental 3J(H α-H β(a/b)) spin-spin coupling constants with the theoretical values obtained by weighting DFT-computed spin-spin coupling constants with the MD-computed probability distributions for the dyads' configurations.

  11. Novel Rhodafluors: Synthesis, Photophysical, pH and TD-DFT Studies. (United States)

    Patil, Supriya S; Thorat, Kishor G; Mallah, Ramnath; Sekar, Nagaiyan


    An efficient protocol for the synthesis of new rhodol derivatives has been developed. The synthesis involves condensation of 2-hydroxy benzophenone derivatives with 1, 3-dihydroxy benzene derivatives in solvents such as ionic liquid (N-methyl-2-pyrrolidonium hydrogen sulfate) and methane sulphonic acid. Both ionic liquid and methane sulphonic acid were found to be promising self-catalyzed solvents to bring out the conversion to form desired rhodols in excellent yields. In N-methyl-2-pyrrolidonium hydrogen sulfate reaction proceeds faster compared to methane sulphonic acid. The new fluorophores are investigated for their photophysical properties in various microenvironments and systematically characterized by means of density functional theory and time dependent density functional theory. Photophysical properties of the new rhodafluors found sensitive towards change in the pH of media and thus can be used as efficient pH sensors.

  12. Molecular design, synthesis and biological evaluation of BP-O-DAPY and O-DAPY derivatives as non-nucleoside HIV-1 reverse transcriptase inhibitors. (United States)

    Yang, Shiqiong; Pannecouque, Christophe; Daelemans, Dirk; Ma, Xiao-Dong; Liu, Yang; Chen, Fen-Er; De Clercq, Erik


    This paper reports the synthesis and antiviral evaluation of a series of non-nucleoside reverse transcriptase inhibitors (NNRTIs) that combine the peculiar structural features of diarylpyrimidine derivatives (DAPYs) and benzophenone derivatives (BPs). The DAPY derivatives bearing benzoyl or alkoxyl substitutes on the A-ring showed the inhibitory activity against wild-type HIV-1 at the cellular level within the range of EC50 values from micromolar to nanomolar. Among these compounds, 1u exhibited the most potent anti-HIV-1 activity (EC50 = 0.06 ± 0.01 μM, SI > 6260), which were about 1.8-fold more active than nevirapine (NVP) and delavirdine (DLV). In addition, the binding modes with HIV-1 RT and the preliminary SAR studies of these derivatives were also considered for further investigation.

  13. Determination of the Thermal Decomposition Products of Terephthalic Acid by Using Curie-Point Pyrolyzer (United States)

    Begüm Elmas Kimyonok, A.; Ulutürk, Mehmet


    The thermal decomposition behavior of terephthalic acid (TA) was investigated by thermogravimetry/differential thermal analysis (TG/DTA) and Curie-point pyrolysis. TG/DTA analysis showed that TA is sublimed at 276°C prior to decomposition. Pyrolysis studies were carried out at various temperatures ranging from 160 to 764°C. Decomposition products were analyzed and their structures were determined by gas chromatography-mass spectrometry (GC-MS). A total of 11 degradation products were identified at 764°C, whereas no peak was observed below 445°C. Benzene, benzoic acid, and 1,1‧-biphenyl were identified as the major decomposition products, and other degradation products such as toluene, benzophenone, diphenylmethane, styrene, benzaldehyde, phenol, 9H-fluorene, and 9-phenyl 9H-fluorene were also detected. A pyrolysis mechanism was proposed based on the findings.

  14. Migration study of optical brighteners from polymer packing materials to jam squeeze and fruit drink by spectrofluorimetry and RP-HPLC methods. (United States)

    Gandhimathi, M; Murugavel, K; Ravi, T K


    Optical brighteners are commonly used to modify the appearance and to improve polymer properties of packaging. They are not chemically bound to polymers and able to migrate from packaging into the foods. These migrants are potentially harmful to human health. In concern with human safety an approach was made to analyze three optical brighteners such as diphenylbutadiene, Uvitex-OB, benzophenone in commercial fruit juice and jam. The migration level of these optical brighteners from low density poly ethylene packaging into fruit juice and jam was studied. Two optimized and validated analytical techniques such as spectrofluorimetry and high performance liquid chromatography with photo diode array detector used for migration study. Both methods have shown high correlation coefficients (>0.999), over a concentration range of 0.1-3.2 μg/mL, 0.1-1 μg/mL, 0.05-3.2 μg/mL for diphenylbutadiene, Uvitex-OB and benzophenone respectively. The preliminary studies confirm that the low density poly ethylene layer taken for study contained of diphenylbutadiene and the other two were absent. The migration level of diphenylbutadiene was studied at room temperature and different elevated temperature from 30 °C to 60 °C for up to 3 weeks. At room temperature no migration of diphenylbutadiene was observed where as at higher temperature migration could be observed. The maximum quantity of diphenylbutadiene migrated was found to be 0.0462 mg/kg from tetrapak, and 0.0382 mg/kg from jam squeeze after 3 weeks treatment at 60 °C. The migration of diphenylbutadiene was found to be less than allowable concentration during the study period.

  15. Using oysters as anthropogenic indicators to evaluate the occurrence of the wastewater contamination of the estuaries (United States)

    Ding, Wang-Hsien


    The oyster (Crossostrea gigas) is an important aquacultural species in Taiwan. With an area of over 85% of the total inshore aquacultural field, its production, measured by quantity or economic value, ranks above all other aquacultural products in Taiwan. Since oyster's habitat is on shelves near the coast, the samples from a particular "oyster cultural site" can be applied to evaluate the pollution of a segment of the coastal water. Deficient wastewater treatment has caused untreated wastewaters to have flown in rivers into oyster cultural areas in estuaries as well as shallow coastal water. Therefore, the concentration of pollutants in the oysters can be used as anthropogenic indicators to evaluate the occurrence of the for wastewater contamination of the coastal water. In this study, two groups of anthropogenic organic compounds, chlorinated flame retardant (i.e., Dechlorane Plus) and benzophenone-type UV absorbing substances (i.e., 2-hydroxy-4-methoxybenzophenone), were determined in oyster samples as wastewater contamination pollutants. The method involves the use of matrix solid-phase dispersion prior to their determination by gas chromatography mass spectrometry. The results show that these two groups of compounds are ubiquitous in oysters with the concentrations of chlorinated flame retardant and benzophenone-type UV absorbing substances ranging from 0.3 to 3.6 ng/g and from 120 to 910 ng/g (lipid weight), respectively. Oysters are useful anthropogenic indicators of organic pollutants in Taiwan's marine environment. The ubiquity of these pollutants in Taiwan's coastal environment supports the need for greater awareness of bioaccumulation processes.

  16. Seasonal occurrence, removal efficiencies and preliminary risk assessment of multiple classes of organic UV filters in wastewater treatment plants. (United States)

    Tsui, Mirabelle M P; Leung, H W; Lam, Paul K S; Murphy, Margaret B


    Organic ultraviolet (UV) filters are applied widely in personal care products (PCPs), but the distribution and risks of these compounds in the marine environment are not well known. In this study, the occurrence and removal efficiencies of 12 organic UV filters in five wastewater treatment plants (WWTPs) equipped with different treatment levels in Hong Kong, South China, were investigated during one year and a preliminary environmental risk assessment was carried out. Using a newly developed simultaneous multiclass quantification liquid chromatography-tandem mass spectrometry (LC-MS/MS) method, butyl methoxydibenzoylmethane (BMDM), 2,4-dihydroxybenzophenone (BP-1), benzophenone-3 (BP-3), benzophenone-4 (BP-4) and 2-ethyl-hexyl-4-trimethoxycinnamate (EHMC) were frequently (≥80%) detected in both influent and effluent with mean concentrations ranging from 23 to 1290 ng/L and 18-1018 ng/L, respectively; less than 2% of samples contained levels greater than 1000 ng/L. Higher concentrations of these frequently detected compounds were found during the wet/summer season, except for BP-4, which was the most abundant compound detected in all samples in terms of total mass. The target compounds behaved differently depending on the treatment level in WWTPs; overall, removal efficiencies were greater after secondary treatment when compared to primary treatment with >55% and 70% removal), respectively. Reverse osmosis was found to effectively eliminate UV filters from effluent (>99% removal). A preliminary risk assessment indicated that BP-3 and EHMC discharged from WWTPs may pose high risk to fishes in the local environment.

  17. 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: [Departament de Quimica Ambiental, IDAEA-CSIC, C/ Jordi Girona 18-26, 08034 Barcelona (Spain); Badia-Fabregat, Marina, E-mail: [Departament d' Enginyeria Quimica, Escola d' Enginyeria, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Olivares, Alba, E-mail: [Departament de Quimica Ambiental, IDAEA-CSIC, C/ Jordi Girona 18-26, 08034 Barcelona (Spain); Pina, Benjamin, E-mail: [Departament de Quimica Ambiental, IDAEA-CSIC, C/ Jordi Girona 18-26, 08034 Barcelona (Spain); Blanquez, Paqui, E-mail: [Departament d' Enginyeria Quimica, Escola d' Enginyeria, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Vicent, Teresa, E-mail: [Departament d' Enginyeria Quimica, Escola d' Enginyeria, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Caminal, Gloria, E-mail: [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: [Departament de Quimica Ambiental, IDAEA-CSIC, C/ Jordi Girona 18-26, 08034 Barcelona (Spain); and others


    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

  18. 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: [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: [Environmental Chemistry Research Group Institute of Chemistry, University of Szeged, 6723 Szeged, Tisza Lajos krt. 103 (Hungary); Takács, Erzsébet, E-mail: [Radiation Chemistry Department, Centre for Energy Research, Hungarian Academy of Sciences, 1121 Budapest, Konkoly Thege M. út 29-33 (Hungary); Wojnárovits, László, E-mail: [Radiation Chemistry Department, Centre for Energy Research, Hungarian Academy of Sciences, 1121 Budapest, Konkoly Thege M. út 29-33 (Hungary); Dombi, András, E-mail: [Environmental Chemistry Research Group Institute of Chemistry, University of Szeged, 6723 Szeged, Tisza Lajos krt. 103 (Hungary); Gajda-Schrantz, Krisztina, E-mail: [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)


    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.

  19. Study on synthesis of a new UV-absorber%一种新型紫外线吸收剂的合成研究

    Institute of Scientific and Technical Information of China (English)

    宋欣荣; 丁莎; 马丹; 陈亚平


    A new water-soluble UV-absorber was synthesized through a series of reaction using toluene, benzoyl chloride and dimethyl allylamine as materials. The structure of dimethyl allyl p-benzoylbenzyl ammonium bromide was characterized with FT-IR, 1H NMR and UV spectroscopy. The effects of temperature, molar ratio of 4-bromomethyl benzophenone to dimethyl allylamine and reaction time on the yield of target product were investigated. The yield of the product reached 91.3% under the optimal reaction condition, molar ratio of 4-bromomethyl benzophenone to dimethyl allylamine, reaction temperature and time was 1:1.1, 60 ℃ and 3 h, respectively.%以甲苯、苯甲酰氯和二甲基烯丙基胺为原料,经过系列反应合成了新型的水溶性紫外线吸收剂,采用红外光谱、核磁共振光谱、紫外光谱等对其结构进行了表征.考察了温度、n(4-溴甲基二苯甲酮):n(二甲基烯丙基胺)和反应时间等因素对目标产物产率的影响.优化合成反应条件为:n(4-溴甲基二苯甲酮):n(二甲基烯丙基胺)=1∶1.1、60℃反应3h,产率达到91.3%.

  20. Syntheses, crystal structures and DNA-binding studies of Cu(II) and Zn(II) complexes bearing asymmetrical aroylhydrazone ligand (United States)

    Li, Yueqin; Yang, Zhiwei; Zhou, Minya; He, Jing; Wang, Xuehong; Wu, Yanlong; Wang, Zhuye


    Zn(II) and Cu(II) complexes with benzophenone benzoyl hydrazone (HBBH) and benzophenone salicylylhydrazone (HBSH) have been synthesized and characterized by different physico-chemical and spectroscopic techniques (UV-vis, IR and NMR). The molecular structures of these complexes [Zn(BBH)2, Cu(BBH)2 and Cu(BSH)2Cl2H2O] have also been determined by single X-ray diffraction technique. In Zn(BBH)2 and Cu(BBH)2 complexes, each ligand coordinates to metal through enol tautomeric form by azomethine-N and carbonylate-O resulting a 4-coordinate distorted tetrahedral geometry. While in Cu(BSH)2Cl2H2O, each ligand coordinates to metal through keto tautomeric form resulting distorted octahedral geometry in which two chlorine atoms occupy the axial positions. The DNA interaction propensity of the complexes with Herring sperm DNA, studied at physiological pH by spectrophotometric, spectrofluorometric, viscometric techniques and cyclic voltammetry, revealed intercalation as the possible binding mode. Fascinatingly, Cu(BSH)2Cl2H2O was found to exhibit greater binding strength than the others. A strong hyperchromism effect and a slight red shift were exhibited by all complexes. The intrinsic binding constants are of moderate values and are about 3.28 × 104 M-1, 4.73 × 104 M-1 and 5.80 × 104 M-1, respectively. Cyclic voltammetry studies of the complexes binding with DNA indicate quasireversible oxidation and reduction potentials. The results suggest that the binding affinity of complexes lies in the order Cu(BSH)2Cl2H2O > Cu(BBH)2 > Zn(BBH)2.

  1. Spectral properties and reactivity of diarylmethanol radical cations in aqueous solution. Evidence for intramolecular charge resonance. (United States)

    Bietti, Massimo; Lanzalunga, Osvaldo


    Spectral properties and reactivities of ring-methoxylated diarylmethane and diarylmethanol radical cations, generated in aqueous solution by pulse and gamma-radiolysis and by the one-electron chemical oxidant potassium 12-tungstocobalt(III)ate, have been studied. The radical cations display three bands in the UV, visible, and vis-NIR regions of the spectrum. The vis-NIR band is assigned to an intramolecular charge resonance interaction (CR) between the neutral donor and charged acceptor rings, as indicated by the observation that the relative intensity of the vis-NIR band compared to that of the UV and visible bands does not increase with increasing substrate concentration and that the position and intensity of this band is influenced by the ring-substitution pattern. In acidic solution (pH = 4), monomethoxylated diarylmethanol radical cations 1a.(+ -)1e.(+) decay by C(alpha)-H deprotonation [k = (1.7-1.9) x 10(4)s(-1)] through the intermediacy of a ketyl radical, which is further oxidized in the reaction medium to give the corresponding benzophenones, as evidenced by both time-resolved spectroscopic and product studies. With the dimethoxylated radical cation 2.(+), C(alpha)-H deprotonation is instead significantly slower (k = 6.7 x 10(2)s(-1)). In basic solution, 1a.(+)-1e.(+) undergo (-)OH-induced deprotonation from the alpha-OH group with k(OH.)approximately equal to 1.4 x 10(10)M(-1)s(-1), leading to a ketyl radical anion, which is oxidized in the reaction medium to the corresponding benzophenone.

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

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


    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.

  3. Multi-class determination of personal care products and pharmaceuticals in environmental and wastewater samples by ultra-high performance liquid-chromatography-tandem mass spectrometry. (United States)

    Gracia-Lor, Emma; Martínez, Marian; Sancho, Juan V; Peñuela, Gustavo; Hernández, Félix


    In this work, a multi-class method for the simultaneous determination of 17 emerging contaminants, including pharmaceuticals and personal care products, has been developed. Target analytes were two anti-inflammatories, a lipid regulator agent, two angiotensin II antagonists, two antiepileptic drugs and a diuretic. Among personal care products, four preservatives and five UV filters were included. The method is based on solid-phase extraction (SPE) using Oasis HLB cartridges followed by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). Up to three simultaneous transitions per compound were acquired to assure a reliable identification. A detailed study of the extraction process efficiency and matrix effects was carried out in surface water and effluent wastewater. The use of isotope-labeled internal standards (ILIS) was tested to compensate both potential SPE losses during sample extraction and signal suppression/enhancement observed, especially in EWW. Satisfactory correction in all water samples was only ensured when the own analyte ILIS was used. The use of analogues ILIS was a rather useful approach for correction in the majority of the samples tested when analyte ILIS was unavailable. The method was successfully validated in five different surface water (SW) samples and five effluent wastewater (EWW) samples spiked at two concentration levels (0.05 and 0.5 μg/L in SW; 0.1 and 0.5 μg/L in EWW). The developed method was applied to the analysis of 22 samples (SW and EWW) from the Spanish Mediterranean area and 51 reservoir water samples from Colombia. Personal care products were frequently detected, with the highest concentrations corresponding to benzophenone and benzophenone-4 (samples from Spain), and methylparaben (samples from Colombia). Several pharmaceuticals were detected in the Spanish samples, where irbesartan and valsartan - two Angiotensin II antagonists that are not commonly monitored in the aquatic environment

  4. Determination of low-level ink photoinitiator residues in packaged milk by solid-phase extraction and LC-ESI/MS/MS using triple-quadrupole mass analyzer. (United States)

    Shen, Dong-xu; Lian, Hong-zhen; Ding, Tao; Xu, Jin-zhong; Shen, Chong-yu


    A confirmatory and quantitative method based on liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI/MS/MS) has been developed for simultaneous determination of seven photoinitiator residues: benzophenone, (1-hydroxycyclohexyl)phenylketone (Irgacure 184), isopropylthioxanthone (ITX), 2-ethylhexyl-(4-dimethylamino)benzoate (EHA or EHDAB), 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone (Irgacure 907), (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (TPO) and 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone (Irgacure 369) in packaged milk and related packaging materials. Residues of photoinitiators were extracted from milk using acetonitrile, and further enriched and purified on HLB solid-phase extraction cartridges prior to being analyzed by LC-ESI/MS/MS with selected reaction monitoring mode, while photoinitiators in packaging materials were extracted using the same solvent. Satisfactory recovery (from 80 to 111%), intra- and inter-day precision (below 12%), and low limits of quantification (from 0.1 to 5.0 microg kg(-1)) were evaluated from spiked samples at three concentration levels (5.0, 10.0 and 25.0 microg kg(-1) for Irgacure 184 and 2.5, 5.0 and 25.0 microg kg(-1) for others). These excellent validation data suggested the possibility of using the LC-ESI/MS/MS method for simultaneous determination of low-level photoinitiator residues migrating from printed food-packaging materials into milk. The method has been successfully applied to the analysis of real samples of different fat contents ranging from 8 to 30 g L(-1). The photoinitiator residues were revealed to be higher in milk with higher fat content and the most important contaminations were benzophenone and ITX in concentration ranges of 2.84-18.35 and 0.83-8.87 microg kg(-1), respectively.

  5. Synthesis, characterization, thermal and DNA-binding properties of new zinc complexes with 2-hydroxyphenones. (United States)

    Mrkalić, Emina; Zianna, Ariadni; Psomas, George; Gdaniec, Maria; Czapik, Agnieszka; Coutouli-Argyropoulou, Evdoxia; Lalia-Kantouri, Maria


    The neutral mononuclear zinc complexes with 2-hydroxyphenones (ketoH) having the formula [Zn(keto)2(H2O)2] and [Zn(keto)2(enR)], where enR stands for a N,N'-donor heterocyclic ligand such as 2,2'-bipyridine (bipy), 1,10-phenanthroline (phen) or 2,2'-dipyridylamine (dpamH), have been synthesized and characterized by IR, UV and (1)H NMR spectroscopies. The 2-hydroxyphenones are chelated to the metal ion through the phenolate and carbonyl oxygen atoms. The crystal structures of [bis(2-hydroxy-4-methoxy-benzophenone)(2,2'-bipyridine)zinc(II)] dimethanol solvate and [bis(2-hydroxy-benzophenone)(2,2'-bipyridine)zinc(II)] dimethanol solvate have been determined by X-ray crystallography. The thermal stability of the zinc complexes has been investigated by simultaneous TG/DTG-DTA technique. The ability of the complexes to bind to calf-thymus DNA (CT DNA) has been studied by UV-absorption and fluorescence emission spectroscopy as well as viscosity measurements. UV studies of the interaction of the complexes with DNA have shown that they can bind to CT DNA and the corresponding binding constants to DNA have been calculated and evaluated. The complexes most probably bind to CT DNA via intercalation as concluded by studying the viscosity of a DNA solution in the presence of the complexes. Competitive studies with ethidium bromide (EB) have shown that the reported complexes can displace the DNA-bound EB, suggesting strong competition with EB for the intercalation site.

  6. 羧甲基壳聚糖基水溶性高分子紫外线吸收剂的合成与表征%Synthesis and characterization of carboxymethyl chitosan based water soluble ultraviolet absorbers

    Institute of Scientific and Technical Information of China (English)

    于淑娟; 杨芳; 梁春群; 莫羡忠


    以2,4-二羟基二苯甲酮(UV-O)与氯乙酰氯为原料合成了中间体2-羟基-4-氯乙酸酯基二苯甲酮,然后使其与羧甲基壳聚精反应,合成了一系列含有二苯甲酮结构的羧甲基壳聚糖基紫外线吸收剂(CMC-g-HCBP).采用IR,UV,XRD,1HNMR等对产物进行了结构表征.测定结果表明,接枝产物在240~400 nm内均有较强的紫外吸收,并在332 nm处有最大紫外吸收;产物有较好的光稳定性.%An intermediate, 2 - hydroxy - 4 - chloroacetate - benzophenone (HCBP) was synthesized by 2,4- dihydroxy- benzophenone (UV -O) and chloroacetyl chloride as starting materials. Then a series of carboxymethyl chitosan based water soluble ultraviolet absorbers (CMC - g - HCBP) were synthesized by grafting reaction of HCBP on carboxymethyl chitosan in isopropanol with the presence of sodium hydroxide. The structures of the intermediate (HCBP) and grafted products (CMC - g - HCBP) were characterized by IR,UV,XRD and 1HNMR. The results of ultraviolet absorption showed that anyone of the grafted products has a strong ultraviolet absorption capacity ranging from 240 ~400 nm,while the maximum absorption peak presents at 332 nm. The photostability test indicated that the grafted products have good stability.

  7. Strategies to balance covalent and non-covalent biomolecule attachment within collagen-GAG biomaterials. (United States)

    Pence, Jacquelyn C; Gonnerman, Emily A; Bailey, Ryan C; Harley, Brendan A C


    Strategies to integrate instructive biomolecular signals into a biomaterial are becoming increasingly complex and bioinspired. While a large majority of reports still use repeated treatments with soluble factors, this approach can be prohibitively costly and difficult to translate in vivo for applications where spatial control over signal presentation is necessary. Recent efforts have explored the use of covalent immobilization of biomolecules to the biomaterial, via both bulk (ubiquitous) as well as spatially-selective light-based crosslinking, as a means to both enhance stability and bioactivity. However, little is known about how processing conditions during immobilization impact the degree of unintended non-covalent interactions, or fouling, that takes place between the biomaterial and the biomolecule of interest. Here we demonstrate the impact of processing conditions for bulk carbodiimide (EDC) and photolithography-based benzophenone (BP) crosslinking on specific attachment vs. fouling of a model protein (Concanavalin A, ConA) within collagen-glycosaminoglycan (CG) scaffolds. Collagen source significantly impacts the selectivity of biomolecule immobilization. EDC crosslinking intensity and ligand concentration significantly impacted selective immobilization. For benzophenone photoimmobilization we observed that increased UV exposure time leads to increased ConA immobilization. Immobilization efficiency for both EDC and BP strategies was maximal at physiological pH. Increasing ligand concentration during immobilization process led to enhanced immobilization for EDC chemistry, no impact on BP immobilization, but significant increases in non-specific fouling. Given recent efforts to covalently immobilize biomolecules to a biomaterial surface to enhance bioactivity, improved understanding of the impact of crosslinking conditions on selective attachment versus non-specific fouling will inform the design of instructive biomaterials for applications across tissue

  8. Migration studies from paper and board food packaging materials. 1. Compositional analysis. (United States)

    Castle, L; Offen, C P; Baxter, M J; Gilbert, J


    A survey of 32 paper and board materials intended for food contact has been undertaken. Sample composition was analysed to identify chemicals with a potential to migrate to foods. Representative materials covering a range of uses such as aqueous and fatty foods, and use at ambient and elevated temperatures, were obtained from industry. The samples were examined in their unfinished state, even where the final form would have included lamination to plastics, printing, or other treatments. A comprehensive and systematic analytical approach was applied which included determination of volatiles by headspace GC-MS, extraction using water, ethanol and chloroform with subsequent analysis by GC-MS and HPLC, and multi-element screening by ICP-MS. The solvent extracts were also weighed to determine the total amount of material available for migration. A large number of volatile substances were identified with alkyl and aryl aldehydes predominating in the majority of samples. Substances identified in solvent extracts included 2,6-di-tert-butyl-4-hydroxytoluene (BHT), di-tert-butylphenol, benzophenone, 4,4'-bis(dimethyl amino) benzophenone (Michler's ketone), triphenyl methane, bicyclohexylphenylphenanthrene carboxylic acid (and its methyl ester) and abietic acid. Levels of these substances were however generally below 1 mg/kg paper. Of the inorganic elements, arsenic and mercury were not detected above the limits of determination of 1.8 and 0.4 mg/kg respectively in any of the 10 samples examined. Cadmium was detected in teabag tissue and in unbleached Kraft paper at 0.3 mg/kg. Chromium was present in seven samples at 1.1-7.8 mg/kg, whilst lead was present in nine of the 10 samples at levels ranging from 0.3 to 5.9 mg/kg.

  9. Rapid determination of nine parabens and seven other environmental phenols in urine samples of German children and adults. (United States)

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


    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.

  10. Occurrence, fate and ecotoxicological risk of personal care products in urban river-groundwater interface (United States)

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


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Sterna, L.L.


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

  12. A Multimedia Fate Model to Support Chemical Management in China: A Case Study for Selected Trace Organics. (United States)

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


    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.

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

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


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

  14. Determination of ultraviolet filters in water samples by vortex-assisted dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry. (United States)

    Zhang, Yufeng; Lee, Hian Kee


    For the first time, a simple solvent microextraction method termed vortex-assisted liquid-liquid microextraction (VADLLME) coupled with gas chromatography-mass spectrometry (GC-MS) has been developed and used for the analysis of six benzophenone ultraviolet (UV) filters (i.e. benzhydrol, 2,4-dihydroxybenzophenone, benzophenone, 2-hydroxy-4-methoxybenzophenone, ethylhexyl salicylate and homosalate) in water samples. The most favorable extraction variables in the VADLLME process were determined. In the extraction procedure, 40 μL of tetrachloroethene as extraction solvent were directly injected into a 15-mL centrifuge tube containing 10 mL of aqueous sample, adjusted to pH 4 for VADLLME. After VADLLME, the extract was evaporated under a gentle nitrogen gas stream and then reconstituted with N,O-bis-(trimethylsilyl)trifluoroacetamide (BSTFA), thus allowing the target analytes to be converted into their trimethylsilyl derivatives to optimize the GC-MS analysis. No centrifugation and disperser solvent were required in this microextraction procedure. Significantly, short extraction time and high extraction efficiency were achieved. This method opens up a potentially new horizon for on-site dispersive liquid-liquid microextraction. Under the optimum conditions, the proposed method provided good enrichment factors up to 310, with relative standard deviations ranging from 6.1 to 12.9%. The limits of quantification were in the range of 20-100 ng/L, depending on the analytes. The linearities were between 0.05 and 10 μg/L and 0.1 and 10 μg/L for different UV filters. Finally, the proposed method was successfully applied to the determination of UV filters from spiked genuine water samples and acceptable recoveries over the range of 71.0-120.0% were obtained.

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

    Energy Technology Data Exchange (ETDEWEB)

    Mohamed, Nasser H. [Deutsches Textilforschungszentrum Nord-West e.V., Adlerstr. 1, 47798 Krefeld (Germany); Bahners, Thomas, E-mail: [Deutsches Textilforschungszentrum Nord-West e.V., Adlerstr. 1, 47798 Krefeld (Germany); Wego, Andreas [Deutsches Textilforschungszentrum Nord-West e.V., Adlerstr. 1, 47798 Krefeld (Germany); Gutmann, Jochen S. [Deutsches Textilforschungszentrum Nord-West e.V., Adlerstr. 1, 47798 Krefeld (Germany); Universitaet Duisburg-Essen, Physikalische Chemie, Universitaetsstr. 2, 45141 Essen (Germany); Ulbricht, Mathias [Deutsches Textilforschungszentrum Nord-West e.V., Adlerstr. 1, 47798 Krefeld (Germany); Universitaet Duisburg-Essen Technische Chemie II, Essen (Germany)


    Highlights: Black-Right-Pointing-Pointer PET fibers were UV-grafted with dimethylaminopropyl methacrylamide (DMAPMA). Black-Right-Pointing-Pointer The graft yield could be controlled by irradiation time and monomer concentration. Black-Right-Pointing-Pointer The tertiary amino groups of the grafted PDMAPMA were quaternized with alkyl bromides. Black-Right-Pointing-Pointer The quaternization reaction had a high yield, when bromides with shorter alkyl chain were employed. Black-Right-Pointing-Pointer 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.

  16. The Extension of Colloid Chemistry from Aqueous to Non-Aqueous Media with Application to Nanofluid Research (United States)

    Clary, Dan

    containing benzophenone as a photosensitizer and oleoylsarcosine as a stabilizer resulted in metallic Cu particles with nanometer dimensions. Evidence is presented that implicates the hydrocarbon as the predominant H-atom donor in the generation of reductive benzophenone ketyl radicals and a kinetic model is constructed to rationalize the rate dependencies with respect to the Cu2+/Cu+ step. Rates of both Cu2+ consumption and Cu formation vary linearly with light intensity and exhibit a first-order dependence on benzophenone concentration but the latter step shows little dependence otherwise. The initial rate of reactant consumption decreases with increasing concentration of cupric ions or sarcosine. Quenching of the excited state of benzophenone by the stabilizer occurs with a rate constant of k4 = 1.6 x 105 M-1 s-1 and is explained by the formation of a contact ion pair between the reduced chromophore and oxidized sarcosine which ultimately decays by back electron transfer. UV irradiation of octane solutions containing Ag neodecanoate, Pd(acac) 2, or Pt(acac)2 in the presence of benzophenone and oleoyl sarcosine resulted in crystalline metal particles. Rates of metal formation in the absence of BP for Pd(acac)2 and Pt(acac)2 were ri = 3.4x10-8 M/s and ri = 4.7x10 -8 M/s, respectively, which are 2-4 times slower than the analgous reactions conducted in the presence of the chromophore. The direct irradiation of Ag(OOR), on the other hand, resulted in no reaction. In the presence of BP, silver atoms were formed with a rate constant of 4.2x10-7 M/s. The resulting octane colloids were evaluated for enhancements in thermal conductivity (TC) using the Thermal HotDisk method. Increases in krel of up to 10% were observed for the Ag and Pt systems at [M] = 5 mM which are far larger than what Maxwell's theory predicts for a colloid of such low volume fraction (˜5x10-5 vol%). (Abstract shortened by UMI.)

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  18. 光稳定剂对木粉/回收聚乙烯复合材料老化性能的影响%Effects of Photo Stabilizers on Aging Properties of WPC

    Institute of Scientific and Technical Information of China (English)

    邓云; 盛清泉


    The effect of commonly used photo stabilizers on ageing resistance of wood plastic composites were investigated by analyzing the properties of WPC before and after accelerated weathering with added 6 different photo stabilizers. The results showed that photo stabilizers could effectively increase the ageing resistance ability of WPC, and reduce the mechanical properties during the aging process. The effect of different photo stabilizers on the de-crease of WPC modulus of rupture have obvious difference during the aging process, hindered amine and benzophe-none have greater effect than azimino-benzene. The effect of different photo stabilizers on the increase of water ab-sorption rate of WPC also have significant difference during the aging process, the best was hindered amine, fol-lowed by benzophenon, and the worst was azimino-benzene. The effect of different photo stabilizers on the change of chromatic aberration showed no obvious differences.%选用了6种光稳定剂,通过分析老化前后添加不同光稳定剂的木塑复合材料性能变化,考察了常用光稳定剂品种对于木塑复合材料抗老化性能的影响.结果表明:光稳定剂能够有效增加WPC的抗老化能力,减少老化过程导致的力学性能下降;光稳定剂品种对于老化过程WPC静曲强度下降的影响有明显差异,位阻胺类与二苯甲酮类优于苯并三唑类;光稳定剂品种对于老化过程WPC吸水率的增加有明显差异,位阻胺类最优,二苯甲酮类次之,苯并三唑类最差;光稳定剂品种对于老化前后WPC色差的影响没有明显差别.

  19. Additive estrogenic effects of mixtures of frequently used UV filters on pS2-gene transcription in MCF-7 cells. (United States)

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


    In order to protect consumers from ultraviolet (UV) radiation and enhance light stability of the product, three to eight UV filters are usually added to consumer sunscreen products. High lipophilicity of the UV filters has been shown to cause bioaccumulation in fish and humans, leading to environmental levels of UV filters that are similar to those of PCBs and DDT. In this paper, estrogen-regulated pS2 gene transcription in the human mammary tumor cell line MCF-7 was used as a measure of estrogenicity of four individual UV filters. Since humans are exposed to more than one UV filter at a time, an equipotent binary mixture of 2-hydroxy-4-methoxy-benzophenone (BP-3) and its metabolite 2,4-dihydroxy benzophenone (BP-1), as well as an equipotent multi-component mixture of BP-1, BP-3, octyl methoxy cinnamate (OMC) and 3-(4-methylbenzylidene) camphor (4-MBC), were also evaluated for their ability to induce pS2 gene transcription in order to examine additivity. An estrogen receptor-mediated mechanism of action was expected for all UV filters. Therefore, our null-hypothesis was that combined estrogenic responses, measured as increased pS2 gene transcription in MCF-7 cells after exposure to mixtures of UV filters, are additive, according to a concentration-addition model. Not all UV filters produced a full concentration-response curve within the concentration range tested (100 nM-1 microM). Therefore, instead of using EC50 values for comparison, the concentration at which each compound caused a 50% increase of basal pS2 gene transcription was defined as the C50 value for that compound and used to calculate relative potencies. For comparison, the EC50 value of a compound is the concentration at which the compound elicits an effect that is 50% of its maximal effect. Individual UV filters increased pS2 gene transcription concentration-dependently with C50 values of 0.12 microM, 0.5 microM, 1.9 microM, and 1.0 microM for BP-1, BP-3, 4-MBC and OMC, respectively. Estradiol (E2

  20. Interferometrically stable, enclosed, spinning sample cell for spectroscopic experiments on air-sensitive samples (United States)

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


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

  1. 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


    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.

  2. 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.


    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.)

  3. Molecular evolution and sequence divergence of plant chalcone synthase and chalcone synthase-Like genes. (United States)

    Han, Yingying; Zhao, Wenwen; Wang, Zhicui; Zhu, Jingying; Liu, Qisong


    Plant chalcone synthase (CHS) and CHS-Like (CHSL) proteins are polyketide synthases. In this study, we evaluated the molecular evolution of this gene family using representative types of CHSL genes, including stilbene synthase (STS), 2-pyrone synthase (2-PS), bibenzyl synthase (BBS), acridone synthase (ACS), biphenyl synthase (BIS), benzalacetone synthase, coumaroyl triacetic acid synthase (CTAS), and benzophenone synthase (BPS), along with their CHS homologs from the same species of both angiosperms and gymnosperms. A cDNA-based phylogeny indicated that CHSLs had diverse evolutionary patterns. STS, ACS, and 2-PS clustered with CHSs from the same species (late diverged pattern), while CTAS, BBS, BPS, and BIS were distant from their CHS homologs (early diverged pattern). The amino-acid phylogeny suggested that CHS and CHSL proteins formed clades according to enzyme function. The CHSs and CHSLs from Polygonaceae and Arachis had unique evolutionary histories. Synonymous mutation rates were lower in late diverged CHSLs than in early diverged ones, indicating that gene duplications occurred more recently in late diverged CHSLs than in early diverged ones. Relative rate tests proved that late diverged CHSLs had unequal rates to CHSs from the same species when using fatty acid synthase, which evolved from the common ancestor with the CHS superfamily, as the outgroup, while the early diverged lineages had equal rates. This indicated that late diverged CHSLs experienced more frequent mutation than early diverged CHSLs after gene duplication, allowing obtaining new functions in relatively short period of time.

  4. [Safety verification for reuse of PET and glass bottles]. (United States)

    Hayashi, Eiichi; Imai, Toshio; Niimi, Hiroji


    In order to verify the safety associated with reusing PET and glass bottles, a challenge test was conducted with five surrogate contaminants: 1,1,1-trichloroethane, chlorobenzene, toluene, benzophenone and phenyl cyclohexane. Bottles were filled with a cocktail solution of these contaminants and stored at 50 °C for 7 days, then washed with water and alkaline solutions. Material and migration tests were conducted at each step. The material test results showed that 430-1,440 µg/g of the contaminants were retained after water washing, and that even after washing with a 3.5% NaOH solution, 225-925 µg/g of the contaminants were retained. The migration tests revealed that 0.095-7.35 µg/mL of the contaminants were eluted. Similar tests were conducted with a soft drink ingredient, limonene. The results revealed that 48 µg/g of limonene was retained even after washing with NaOH solution, and that 0.16 µg/mL of limonene was eluted. Conversely, no contaminants were eluted from glass bottles after washing with the NaOH solution. Thus, from the viewpoint of safety and the preservation of content quality, PET bottles are not considered suitable for reuse when compared with glass bottles.

  5. Radiation sterilization of ketoprofen

    Energy Technology Data Exchange (ETDEWEB)

    Katusin-Razem, Branka [Ruder Boskovic Institute, P.O.B 180, Zagreb 10000 (Croatia)]. E-mail:; 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)


    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.

  6. Radiation sterilization of ketoprofen (United States)

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


    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.

  7. 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


    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.

  8. Evaluation of sub-critical water as an extraction fluid for model contaminants from recycled PET for reuse as food packaging material. (United States)

    Santos, Amélia S F; Agnelli, José A M; Manrich, Sati


    Recycling of plastics for food-contact packaging is an important issue and research into meaningful and cost-effective solutions is in progress. In this paper, the use of sub-critical water was evaluated as an alternative way of purifying poly(ethylene terephthalate) (PET) flakes for direct food contact applications. The effects of temperature, pressure and flow rate were assessed on the extraction efficiency of two of the most challenging classes of contaminants (toluene and benzophenone) from PET by sub-critical water using a first-order fractional experimental design. Extraction yield was quantified using GC/FID. The most important parameter was flow rate, indicating that the decrease in sub-critical water polarity with temperature was insufficient to eliminate partition effects. Temperature was also important, but only for the optimization of toluene extraction. These results may be explained by the poor solubility of higher molar mass compounds in sub-critical water compared to lower molar mass compounds under the same conditions, and the small decrease in dielectric constant with temperature under the experimental conditions evaluated. As cleaning efficiency is low and PET is very susceptible to hydrolysis, which limits the use of higher temperatures vis-à-vis physical recycling, the proposed extraction is unsuitable for a standalone super-clean process but may be a step in the process.

  9. Photochemical reaction of 2-(3-benzoylphenyl)propionic acid (ketoprofen) with basic amino acids and dipeptides. (United States)

    Suzuki, Tadashi; Shinoda, Mio; Osanai, Yohei; Isozaki, Tasuku


    Photoreaction of 2-(3-benzoylphenyl)propionic acid (ketoprofen, KP) with basic amino acids (histidine, lysine, and arginine) and dipeptides (carnosine and anserine) including a histidine moiety in phosphate buffer solution (pH 7.4) has been investigated with transient absorption spectroscopy. With UV irradiation KP(-) gave rise to a carbanion through a decarboxylation reaction, and the carbanion easily abstracted a proton from the surrounding molecule to yield a 3-ethylbenzophenone ketyl biradical (EBPH). The dipeptides as well as the basic amino acids were found to accelerate the proton transfer reaction whereas alanine and glycine had no effect on the reaction, revealing that these amino acids having a protonated side chain act as a proton donor. The formation quantum yield of EBPH was estimated to be fairly large by means of an actinometrical method with benzophenone, and the bimolecular reaction rate constant for the proton transfer between the carbanion and the protonated basic amino acids or the protonated dipeptides was successfully determined. It has become apparent that the bimolecular reaction rate constant for the proton transfer depended on the acid dissociation constant for the side chain of the amino acids for the first time. This reaction mechanism was interpreted by difference of the heat of reaction for each basic amino acid based on the thermodynamical consideration. These results strongly suggest that the side chain of the basic amino acid residue in protein should play an important role for photochemistry of KP in vivo.

  10. Surface Modification of Polypropylene Membrane Using Biopolymers with Potential Applications for Metal Ion Removal

    Directory of Open Access Journals (Sweden)

    Omar Alberto Hernández-Aguirre


    Full Text Available This work aims to present the modification of polypropylene (PP membranes using three different biopolymers, chitosan (CHI, potato starch (PS, and cellulose (CEL, in order to obtain three new materials. The modified membranes may be degraded easier than polypropylene ones and could be used as selective membranes for metal ions removal, among other applications. For this purpose, the UV energy induced graft copolymerization reaction among polypropylene membrane, acrylic acid, benzophenone (as photoinitiator, and the biopolymer (CHI, PS, or CEL was conducted. The results of FT-IR-ATR, XRD, TGA, DSC, SEM, BET, and AFM analyses and mechanical properties clearly indicate the successful modification of the membrane surface. The change of surface wettability was monitored by contact angle. The grafting reaction depends on natural polymer, reaction time, and concentration. In order to prove the potential application of the modified membranes, a preliminary study of sorption of metal ion was carried out. For this purpose, the PP-CHI membrane was chosen because of the high hydrophilicity, proportionate to -OH and NH2; these groups could act as ligands of metal ions, provoking the interaction between PP-CHI and M+ (PP-CHI-M+ and therefore the metal ion removal from water.

  11. UV filters are an environmental threat in the Gulf of Mexico: a case study of Texas coastal zones

    Directory of Open Access Journals (Sweden)

    Hamidreza Sharifan


    Full Text Available UV filters are the main ingredients in many cosmetics and personal care products. A significant amount of lipophilic UV filters annually enters the surface water due to large numbers of swimmers and sunbathers. The nature of these compounds cause bioaccumulation in commercial fish, particularly in estuarine areas. Consequently, biomagnification in the food chain will occur. This study estimated the amount of four common UV filters (ethylhexyl methoxycinnamate, EHMC; octocrylene, OC; butyl methoxydibenzoylmethane, BM-DBM; and benzophenone-3, BP3, which may enter surface water in the Gulf of Mexico. Our data analysis was based on the available research data and EPA standards (age classification/human body parts. The results indicated that among the 14 counties in Texas coastal zones, Nueces, with 43 beaches, has a high potential of water contamination through UV filters; EHMC: 477 kg year−1; OC: 318 kg year−1; BM-DBM: 258 kg year−1; and BP by 159 kg year−1. Refugio County, with a minimum number of beaches, indicated the lowest potential of UV filter contamination. The sensitive estuarine areas of Galveston receive a significant amount of UV filters. This article suggests action for protecting Texas estuarine areas and controlling the number of tourists and ecotourism that occurs in sensitive areas of the Gulf of Mexico.

  12. Functions of nucleotide binding subunits in the tonoplast ATPase from Beta vulgaris L

    Energy Technology Data Exchange (ETDEWEB)

    Manolson, M.F.; Poole, R.J.


    Partial purification of NO/sub 3/ sensitive H/sup +/-ATPases from the vacuolar membranes of high plants reveal two prominent polypeptides of approximately 60 and 70 kDa. Both polypeptides appear to contain nucleotide binding sites. The photoactive affinity analog of ATP, BzATP, cannot be hydrolyzed by the tonoplast ATPase but is a potential inhibitor (apparent K/sub I/ = 11 /sup 32/P-BzATP was shown to specifically photolabel the 60 kDa polypeptide. In contrast, Mandala and Taiz have shown the photoincorporation of /sup 32/P-azidoATP to the 70 kDa polypeptide. This sterically different photoaffinity probe can be hydrolyzed although with a low affinity. Azido and benzophenone derivatives of the product, ADP, are currently being examined with respect to their inhibition kinetics of, and their photoincorporation into, the tonoplast ATPase from Beta vulgaris L. Kinetic data will be integrated with patterns of photoincorporation using analogs of both substrate and product, in order to illuminate the functions of the two nucleotide binding subunits.

  13. 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. (United States)

    Cerqueira, Maristela B R; Guilherme, Juliana R; Caldas, Sergiane S; Martins, Manoel L; Zanella, Renato; Primel, Ednei G


    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.

  14. Application of UV-Vis spectrophotometric process for the assessment of indoloacridines as free radical scavenger. (United States)

    Sridharan, Makuteswaran; Prasad, K J Rajendra; Madhumitha, G; Al-Dhabi, Naif Abdullah; Arasu, Mariadhas Valan


    A conventional approach has been used to synthesis Indole fused acridine, 4a-e. In this paper to achieve the target molecule, 4 the reaction was performed via two steps. In step 1, there was a reaction between Carbazolone, 1 and benzophenone, 2 to get dihydroindoloacridine, 3. In step 2, compound, 3 was treated with 5% Palladium/Carbon in the presence of diphenyl ether for 5h to give a dark brown product, 4. The column chromatography was used to purify final product, 4. All the synthesized compounds such as 3 and 4 were characterized by melting point, FTIR, (1)H NMR, and Mass spectra. Further to check the purity of the compounds it was subjected to CHN analyzer. The target molecules such as 3 and 4 were screened for antimicrobial studies against bacteria such as Bacillus subtilis (B. subtilis), Staphylococcus aureus (S. aureus), Klebsiella pneumonia (K. pneumonia), Salmonella typhi (S. typhi); and fungi like Aspergillus niger (A. niger), Aspergillus fumigatus (A. fumigatus). The obtained results clearly proves that the target molecules shown reasonable activity against K. pneumonia and A. niger. Further the compounds were screened for free radical scavenging activity using 2,2-diphenyl-1-picrylhydrazyl (DPPH). The free radical scavenging property was performed using UV-Visible spectroscopy. The results were compared with the standard BHT (Butylated Hydroxy Toluene). Compounds, 4a and 4e were shown higher percentage of inhibition when compare to the standard. The result confirms that further research on indoloacridine will leads effective drug to the market.

  15. Study of UV-curable composite resin of transfer tray for orthodontics

    Institute of Scientific and Technical Information of China (English)

    Lin YANG; Wei WU; Bao-hua XU; Pei-zeng JIA; Jun NIE


    Objectives: the aim of this study was to invest-igate the properties of UV-curable composite resin of transfer tray for indirect bonding system of the lingual brackets. Methods: the conversion of double-bond in the different concentration of UV-initiator was monitored by real time infrared (RTIR). The three-point flexure strength was measured by a universal testing machine. The storage modulus, loss modulus, and loss factor (tan delta) of the resin were measured by a Dynamic Mechanical Analyzer. The cytotoxicity of composite resin was evaluated by the agar covering test. Results: the dou-ble bond conversion exceeded 70% at [benzophe-none] = 0.7 wt.%, [Ethyl 4-dimethylaminobenzoate] = 0.7 wt.% and [2-Hydroxy-2-methyl-1-phenyl propa-non] = 1 wt.%. The mean value of flexural strength came to 122 MPa. The value of storage modulus was 1.04 × 109 MPa at 23℃. The glass transition temperature was 142℃. The toxicity grade was zero at 2 h and one at 24 h. Conclusions: in the preliminary evaluations, we indi-cated that the UV-curable composite resin of transfer tray could satisfy the clinical requirements.

  16. UV-induced Self-initiated Graft Polymerization of Acrylamide onto Poly(ether ether ketone)

    Institute of Scientific and Technical Information of China (English)

    CHEN Rui-chao; SUN Hui; LI Ang; XU Guo-zhi


    Photo-grafting of hydrophilic monomer was used to enhance the hydrophilicity of poly(ether ether ketone)(PEEK) with the aim of extending its applications to biological fields.PEEK sheets were surface modified by grafting of acrylamide(AAm) with ultraviolet(UV) irradiation in the presence or absence of benzophenone(BP).The effects of BP,irradiation time and monomer concentration on the surface wettability of PEEK were investigated.Characterization of modified PEEK using scanning electron microscopy(SEM),energy-disperse spectrometer(EDS) and water contact angle measurements shows that AAm was successfully grafted on PEEK surface both in presence and absence of BP.With the increase in irradiation time and monomer concentration,contact angles decrease to as low as 30°,demonstrating a significant improvement of surface hydrophilicity.In agreement with the decrease in contact angle,under identical conditions,the nitrogen concentration increases,suggesting the increase in grafting degree of the grafting polymerization.This investigation demonstrates a self-initiation of PEEK due to its BP-like structure in the backbone of the polymer.Though the graft polymerization proceeds more readily in the presence of BP,the self-initiated graft polymerization is clearly observed.

  17. Mulifunctional Dendritic Emitter: Aggregation-Induced Emission Enhanced, Thermally Activated Delayed Fluorescent Material for Solution-Processed Multilayered Organic Light-Emitting Diodes (United States)

    Matsuoka, Kenichi; Albrecht, Ken; Yamamoto, Kimihisa; Fujita, Katsuhiko


    Thermally activated delayed fluorescence (TADF) materials emerged as promising light sources in third generation organic light-emitting diodes (OLED). Much effort has been invested for the development of small molecular TADF materials and vacuum process-based efficient TADF-OLEDs. In contrast, a limited number of solution processable high-molecular weight TADF materials toward low cost, large area, and scalable manufacturing of solution processed TADF-OLEDs have been reported so far. In this context, we report benzophenone-core carbazole dendrimers (GnB, n = generation) showing TADF and aggregation-induced emission enhancement (AIEE) properties along with alcohol resistance enabling further solution-based lamination of organic materials. The dendritic structure was found to play an important role for both TADF and AIEE activities in the neat films. By using these multifunctional dendritic emitters as non-doped emissive layers, OLED devices with fully solution processed organic multilayers were successfully fabricated and achieved maximum external quantum efficiency of 5.7%.

  18. Novel thermally cross-linked polyimide membranes for ethanol dehydration via pervaporation

    KAUST Repository

    Xu, Sheng


    © 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.

  19. Biocontrol evaluation of extracts and a major component, clusianone, from Clusia fluminensisPlanch. & Triana againstAedes aegypti

    Directory of Open Access Journals (Sweden)

    Maria C Anholeti


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

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

    Cheng, Hong-Jian; Tang, Hui-Xiang; Shen, Ya-Li; Xia, Nan-Nan; Yin, Wen-Yu; Zhu, Wei; Tang, Xiao-Yan; Ma, Yun-Sheng; Yuan, Rong-Xin


    Solvothermal reactions of Zn(NO3)2·6H2O with 3,6-bis(1-imidazolyl)carbazole (3,6-bmcz) and 1,4-benzenedicarboxylic acid (1,4-H2bdc), p-phenylenediacetic acid (p-H2pda), benzophenone-4,4-dicarboxylic acid (H2bpda) afforded three coordination polymers [Zn(1,4-bdc)(3,6-bmcz)]n (1), {[Zn(p-pda)(3,6-bmcz)]·1.5H2O}n (2) and {[Zn(bpda)(3,6-bmcz)]·0.25H2O}n (3). Complexes 1-3 were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. Complex 1 shows 3D structure with 2D nets inclined polycatenation. Complexes 2 and 3 possess an extended 3D supramolecular architecture based on their respective 2D layers through hydrogen-bonding interactions and the π···π stacking interactions. The solid state luminescent and optical properties of 1-3 at ambient temperature were also investigated. A comparative study on their photocatalytic activity toward the degradation of methylene blue in polluted water was explored.

  1. Electron transfer in N-butylpyridinium tetrafluoroborate ionic liquid by pulse radiolysis

    Institute of Scientific and Technical Information of China (English)

    FU HaiYing; XING ZhaoGuo; CAO XiYan; WU GuoZhong


    The radiolysis behavior of neat pyridinium ionic liquids (ILs) and their aqueous solutions was investigated using nanosecond pulse radiolysis techniques.Radiolysis of the ionic liquids,such as N-butylpyridinium tetrafluoroborate (BuPyBF4),resulted in the formation of solvated electrons and organic radicals.Solvated electrons reacted with the pyridinium moiety to produce a pyridinyl radical,which can transfer electrons to various acceptors.The electron-transfer rate constants of the solvent-derived butylpyridinyl radicals in BuPyBF4 and in several compounds (for example,duroquinone,4,4'-pyridine,benzophenone,and 1,1'-dimethyl-4,4'-bypyridinium dichloride) (k of the order 108 L/(mol s) were lower than those measured in water and in i-PrOH but were significantly higher than the diffusion-controlled rate constants estimated based on viscosity.The electron-transfer rate constants in neat BuPyBF4 were one order of magnitude faster than the diffusion-controlled values.This finding suggests that BuPyBF4 acts not only as solvent but also as active solute,such as in solvent-mediated reactions.These reactions result in electrons reaching their final destinations via intervening pyridinium groups without requiring the diffusion of a specific radical.

  2. Fungicide resistance status in French populations of the wheat eyespot fungi Oculimacula acuformis and Oculimacula yallundae. (United States)

    Leroux, Pierre; Gredt, Michel; Remuson, Florent; Micoud, Annie; Walker, Anne-Sophie


    Eyespot, caused by Oculimacula acuformis and Oculimacula yallundae, is the major foot disease of winter wheat in several European countries, including France. It can be controlled by chemical treatment between tillering and the second node stage. The fungicides used include antimicrotubule toxicants (benzimidazoles), inhibitors of sterol 14α-demethylation (DMIs) or of succinate dehydrogenase (SDHIs), the anilinopyrimidines cyprodinil and the benzophenone metrafenone. Since the early 1980s, a long-term survey has been set up in France to monitor changes in the sensitivity of eyespot populations to fungicides. Resistance to benzimidazoles has become generalised since the early 1990s, in spite of the withdrawal of this class of fungicides. In the DMI group, resistance to triazoles is generalised, whereas no resistance to the triazolinethione prothioconazole has yet developed. Resistance to the imidazole prochloraz evolved successively in O. acuformis and O. yallundae and is now well established. Specific resistance to cyprodinil has also been detected, but its frequency has generally remained low. Finally, since the early 2000s, a few strains of O. yallundae displaying multidrug resistance (MDR) have been detected. These strains display low levels of resistance to prothioconazole and SDHIs, such as boscalid. Knowledge of the spatiotemporal distribution in France of O. acuformis and O. yallundae field strains resistant to fungicides allows resistance management strategies for eyespot fungi in winter wheat to be proposed.

  3. Garcinia subelliptica Merr. (Fukugi): A multipurpose coastal tree with promising medicinal properties. (United States)

    Inoue, Tomomi; Kainuma, Mami; Baba, Karin; Oshiro, Nozomi; Kimura, Norimi; Chan, Eric Wei Chiang


    In this short review, the current knowledge on the botany, ecology, uses, and medicinal properties of the multipurpose Garcinia subelliptica (Fukugi) is updated. As yet, there are no reviews on this indigenous and heritage coastal tree species of the Ryukyu Islands in Japan, which has ethnocultural, ecological, and pharmacological significance. Planted by the Okinawan people some 300 years ago, Fukugi trees serve as windbreaks and accord protection against the destructive typhoons. The species has become a popular ornamental tree, and its bark has been used for dyeing fabrics. It forms part of the food chain for mammals and insects and serves as nesting sites for birds. Endowed with bioactive compounds of benzophenones, xanthones, biflavonoids, and triterpenoids, G. subelliptica possesses anticancer, anti-inflammatory, anti-tyrosinase, trypanocidal, antibacterial, DNA topoisomerase inhibitory, DNA strand scission, choline acetyltransferase enhancing, hypoxia-inducible factor-1 inhibitory, and antiandrogenic activities. Fukugetin and fukugiside are two novel biflavonoids named after the species. The chemical constituents of Fukugi fruits when compared with those of mangosteen yielded interesting contrasts.

  4. A New Benzoyl Compound Isolated from the Endophytic Fungi of Kandis Gajah (Garcinia griffithii and Asam Kandis (Garcinia cowa

    Directory of Open Access Journals (Sweden)

    Elfita Elfita


    Full Text Available Garcinia griffithii and Garcinia cowa belong to the genus Garcinia. The genus Garcinia has been known to be a rich source of secondary metabolites, such as xanthones, benzophenones, flavonoids, steroids, terpenoids, and other phenolic derivatives. Previous investigations of endophytic fungi from G. griffithii revealed the presence of three compounds not found in the host. In order to the continue the phytochemical work on endophytic fungi of G. griffithii, the constituent of the endophytic fungi of G. griffithii was re-examined. In this study, a benzoyl compound similar to that found in the endophytic fungus of G. cowa was observed. The same benzoyl compound was also isolated from the endophytic fungus Acremonium sp of G. griffithii and Aspergillus sp of G. cowa with cultivation of eight weeks in static conditions at room temperature. The culture medium was partitioned using ethyl acetate and evaporated to obtain the concentrated extract. Isolation of compounds was performed using the chromatography method. The chemical structure was proposed on the basis of spectroscopic data, including ultraviolet (UV, infrared (IR, mass spectrometry (MS, proton nuclear magnetic resonance (1H-NMR, carbon nuclear magnetic resonance (13C-NMR, heteronuclear single-quantum correlation spectroscopy (HSQC, heteronuclear multiple-bond correlation spectroscopy (HMBC, and correlation spectroscopy (COSY.

  5. Biphenyl synthase, a novel type III polyketide synthase. (United States)

    Liu, B; Raeth, T; Beuerle, T; Beerhues, L


    Biphenyls and dibenzofurans are the phytoalexins of the Maloideae, a subfamily of the economically important Rosaceae. The carbon skeleton of the two classes of antimicrobial secondary metabolites is formed by biphenyl synthase (BIS). A cDNA encoding this key enzyme was cloned from yeast-extract-treated cell cultures of Sorbus aucuparia. BIS is a novel type III polyketide synthase (PKS) that shares about 60% amino acid sequence identity with other members of the enzyme superfamily. Its preferred starter substrate is benzoyl-CoA that undergoes iterative condensation with three molecules of malonyl-CoA to give 3,5-dihydroxybiphenyl via intramolecular aldol condensation. BIS did not accept CoA-linked cinnamic acids such as 4-coumaroyl-CoA. This substrate, however, was the preferential starter molecule for chalcone synthase (CHS) that was also cloned from S. aucuparia cell cultures. While BIS expression was rapidly, strongly and transiently induced by yeast extract treatment, CHS expression was not. In a phylogenetic tree, BIS grouped together closely with benzophenone synthase (BPS) that also uses benzoyl-CoA as starter molecule but cyclizes the common intermediate via intramolecular Claisen condensation. The molecular characterization of BIS thus contributes to the understanding of the functional diversity and evolution of type III PKSs.

  6. Effects of Brazilian propolis on Leishmania amazonensis

    Directory of Open Access Journals (Sweden)

    Diana Copi Ayres


    Full Text Available Leishmaniasis, an endemic parasitosis that leads to chronic cutaneous, mucocutaneous or visceral lesions, is part of those diseases, which still requires improved control tools. Propolis has shown activities against different bacteria, fungi, and parasites. In this study we investigated the effect of four ethanolic extracts of typified propolis collected in different Brazilian states, on Leishmania amazonensis performing assays with promastigote forms, extracellular amastigotes, and on infected peritoneal macrophages. Ethanolic extracts of all propolis samples (BRG, BRPG, BRP-1, and BRV were capable to reduce parasite load as monitored by the percentage of infected macrophages and the number of intracellular parasites. BRV sample called red propolis, collected in the state of Alagoas, and containing high concentration of prenylated and benzophenones compounds, was the most active extract against L. amazonensis. The anti-Leishmania effect of BRV sample was increased in a concentration and time dependent manner. BRV treatment proved to be non-toxic to macrophage cultures. Since BRV extract at the concentration of 25 µg/ml reduced the parasite load of macrophages while presented no direct toxic to promastigotes and extracellular amastigotes, it was suggested that constituents of propolis intensify the mechanism of macrophage activation leading to killing of L. amazonensis. Our results demonstrate, for the first time, that ethanolic extracts of Brazilian propolis reduce L. amazonensis infection in macrophages, and encourage further studies of this natural compound in animal models of leishmaniasis.

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

    Directory of Open Access Journals (Sweden)

    M. A. El-Sheikh


    Full Text Available 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. Effect of irradiation time and incorporating N, N-methylene diacrylamide (MDA in different concentrations on antibacterial performance before and after repeated washing cycles was studied. S. aureus and E. coli were used to evaluate the antibacterial performance of finished fabrics. The antibacterial performance was directly proportional to the irradiation time and concentration of MDA but inversely proportional to the number of washing cycles. The inhibition zone of S. aureus and E. coli is the same although they are different in the cell wall structure and mode of action due to the nanosize structure formed.

  8. ESR and ring inversion of tetralin-1-yl and ESR of related benzyl radicals

    Energy Technology Data Exchange (ETDEWEB)

    Conradi, M.S.; Zeldes, H.; Livingston, R.


    The tetralin-1-yl radical 1 was generated in solution by hydrogen abstraction from tetralin by photoexcited benzophenone. The proton hyperfine splittings and the g value are reported from -69 to 146/sup 0/C. An alternating line width effect occurs and is ascribed to ring inversion in the saturated portion of the radical. Line widths and amplitudes were analyzed at low and high inversion rates (near -50 and 130/sup 0/C, respectively) to yield values of the ring inversion rate. Arhenius parameters for the inversion are E = 30 kJ/mol +- 12% and log k = 13.1 +- 0.7. Two azimuthal angles which indicate the extent of ring puckering are determined from the proton splittings at -69/sup 0/C. The room temperature hyperfine constants and g values of m- and o-xylyl and ..cap alpha..-methylbenzyl are reported and support the assignment of proton splittings in tetralin-1-yl. The methyl group splittings in m- and o-xylol are smaller than expected from comparison with related radicals. 3 figures, 3 tables.

  9. 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


    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.

  10. Fabrication of protein microarrays for alpha fetoprotein detection by using a rapid photo-immobilization process

    Directory of Open Access Journals (Sweden)

    Sirasa Yodmongkol


    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.

  11. Inhibitors of Testosterone Biosynthetic and Metabolic Activation Enzymes

    Directory of Open Access Journals (Sweden)

    Leping Ye


    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. 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


    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.

  13. BK/TD models for analyzing in vitro impedance data on cytotoxicity. (United States)

    Teng, S; Barcellini-Couget, S; Beaudouin, R; Brochot, C; Desousa, G; Rahmani, R; Pery, A R R


    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.

  14. Simultaneous determination of multiclass emerging contaminants in aquatic plants by ultrasound-assisted matrix solid-phase dispersion and GC-MS. (United States)

    Aznar, Ramón; Albero, Beatriz; Sánchez-Brunete, Consuelo; Miguel, Esther; Martín-Girela, Isabel; Tadeo, José L


    A multiresidue method was developed for the simultaneous determination of 31 emerging contaminants (pharmaceutical compounds, hormones, personal care products, biocides, and flame retardants) in aquatic plants. Analytes were extracted by ultrasound-assisted matrix solid-phase dispersion (UA-MSPD) and determined by gas chromatography-mass spectrometry after sylilation, The method was validated for different aquatic plants (Typha angustifolia, Arundo donax, and Lemna minor) and a semiaquatic cultivated plant (Oryza sativa) with good recoveries at concentrations of 100 and 25 ng g(-1) wet weight, ranging from 70 to 120 %, and low method detection limits (0.3 to 2.2 ng g(-1) wet weight). A significant difference of the chromatographic response was observed for some compounds in neat solvent versus matrix extracts, and therefore, quantification was carried out using matrix-matched standards in order to overcome this matrix effect. Aquatic plants taken from rivers located at three Spanish regions were analyzed, and the compounds detected were parabens, bisphenol A, benzophenone-3, cyfluthrin, and cypermethrin. The levels found ranged from 6 to 25 ng g(-1) wet weight except for cypermethrin that was detected at 235 ng g(-1) wet weight in O. sativa samples.

  15. 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


    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.

  16. Calcium-induced movement of troponin-I relative to actin in skeletal muscle thin filaments. (United States)

    Tao, T; Gong, B J; Leavis, P C


    The role of troponin-I (the inhibitory subunit of troponin) in the regulation by Ca2+ of skeletal muscle contraction was investigated with resonance energy transfer and photo cross-linking techniques. The effect of Ca2+ on the proximity of troponin-I to actin in reconstituted rabbit skeletal thin filaments was determined. The distance between the cysteine residue at position 133 (Cys133) of troponin-I and Cys374 of actin increases by approximately 15 angstroms on binding of Ca2+ to troponin-C. Also, troponin-I labeled at Cys133 with benzophenone-4-maleimide could be photo cross-linked to actin in the absence of Ca2+, but not in its presence. These results suggest that troponin-I is attached to actin in the Ca2(+)-free or relaxed state of muscle, and that it detaches from actin on Ca2+ activation of contraction. Thus, troponin-I may function as a Ca2(+)-dependent molecular switch in regulation of skeletal muscle contraction.

  17. Commercial sunscreen formulations: UVB irradiation stability and effect on UVB irradiation-induced skin oxidative stress and inflammation. (United States)

    Vilela, Fernanda M P; Oliveira, Franciane M; Vicentini, Fabiana T M C; Casagrande, Rubia; Verri, Waldiceu A; Cunha, Thiago M; Fonseca, Maria J V


    Evidence shows that sunscreens undergo degradation processes induced by UV irradiation forming free radicals, which reduces skin protection. In this regard, the biological effects of three commercial sunscreen formulations upon UVB irradiation in the skin were investigated. The three formulations had in common the presence of benzophenone-3 added with octyl methoxycinnamate or octyl salycilate or both, which are regular UV filters in sunscreens. The results show that formulations F1 and F2 presented partial degradation upon UVB irradiation. Formulations F1 and F2 presented higher skin penetration profiles than F3. None of the formulations avoided UVB irradiation-induced GSH depletion, but inhibited reduction of SOD activity, suggesting the tested formulations did not present as a major mechanism inhibiting all UVB irradiation-triggered oxidative stress pathways. The formulations avoided the increase of myeloperoxidase activity and cytokine production (IL-1β and TNF-α), but with different levels of protection in relation to the IL-1β release. Concluding, UVB irradiation can reduce the stability of sunscreens, which in turn, present the undesirable properties of reaching viable skin. Additionally, the same SPF does not mean that different sunscreens will present the same biological effects as SPF is solely based on a skin erythema response. This found opens up perspectives to consider additional studies to reach highly safe sunscreens.

  18. Preparation and characterization of novel thermoset polyimide and polyimide-peo doped with LiCF3SO3

    Directory of Open Access Journals (Sweden)

    M. H. Ugur


    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.

  19. Sensitization and quenching in the conversion of light energy into chemical energy. Progress report, February 1, 1979-January 31, 1980. [Benzylic chlorides

    Energy Technology Data Exchange (ETDEWEB)

    Cristol, S.J.


    Data have been accumulated on the rates of excitation transfer from acetone or acetophenone sensitizers to several benzylic chlorides in acetonitrile-t-butyl alcohol or acetone-t-butyl alcohol and on the lifetimes of the excited triplet intermediates leading to solvolysis products (arylmethyl t-butyl ethers and arylmethanols). Lifetimes were found to be in the 0-2 nsec range. In direct irradiation, in t-butyl alcohol or acetonitrile-t-butyl alcohol, t-butyl ethers are formed from intermediates which are either singlets or are triplets of short lifetimes (0-2 nsec). Long-lived triplets, which do not lead to t-butyl ethers or to other products, but which decay to starting materials, and which arise by intersystem crossing from excited singlet states, were discovered by their ability to isomerize cis-piperylene (Hammond-Lamola quenching). These hidden triplets were shown to be produced as well by excitation transfer from benzophenone. They represent a large fraction of the energy wastage in this system. Work has begun on the preparation of materials for study of optically active benzylic chloride solvolyses, for study of optically active benzylic chloride solvolyses, for study of intramolecular (2 + 2) cycloadditions and for di-..pi..-methane studies, in our attempts to understand the mechanistic details of these important photochemical reactions.

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

    CERN Document Server

    Vlaisavljevich, Bess


    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...

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

    Directory of Open Access Journals (Sweden)

    Maria A. Stander


    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.

  2. 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


    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.

  3. Use of time-of-flight mass spectrometry for large screening of organic pollutants in surface waters and soils from a rice production area in Colombia. (United States)

    Hernández, F; Portolés, T; Ibáñez, M; Bustos-López, M C; Díaz, R; Botero-Coy, A M; Fuentes, C L; Peñuela, G


    The irrigate district of Usosaldaña, an important agricultural area in Colombia mainly devoted to rice crop production, is subjected to an intensive use of pesticides. Monitoring these compounds is necessary to know the impact of phytosanitary products in the different environmental compartments. In this work, surface water and soil samples from different sites of this area have been analyzed by applying an analytical methodology for large screening based on the use of time-of-flight mass spectrometry (TOF MS) hyphenated to liquid chromatography (LC) and gas chromatography (GC). Several pesticides were detected and unequivocally identified, such as the herbicides atrazine, diuron or clomazone. Some of their main metabolites and/or transformation products (TPs) like deethylatrazine (DEA), deisopropylatrazine (DIA) and 3,4-dichloroaniline were also identified in the samples. Among fungicides, carbendazim, azoxystrobin, propiconazole and epoxiconazole were the most frequently detected. Insecticides such as thiacloprid, or p,p'-DDT metabolites (p,p'-DDD and p,p'-DDE) were also found. Thanks to the accurate-mass full-spectrum acquisition in TOF MS it was feasible to widen the number of compounds to be investigated to other families of contaminants. This allowed the detection of emerging contaminants, such as the antioxidant 3,5-di-tertbutyl-4-hydroxy-toluene (BHT), its metabolite 3,5-di-tert-butyl-4-hydroxy-benzaldehyde (BHT-CHO), or the solar filter benzophenone, among others.

  4. Catalytic oxidation of CS2 over atmospheric particles and oxide catalysts

    Institute of Scientific and Technical Information of China (English)

    WANG; Lin


    [1]Carmichael, I., Hug, G. L., Triplet-triplet absorption spectra of organic molecules in condensed phases, J. Phys. Chem. Ref. Data, 1986, 15(1): 1-20.[2]Nikogosyan, D. N., Two-quantum UV photochemistry of nucleic acids: comparison with conventional low-intensity UV photochemistry and radiation chemistry, Int. J. Radiat. Biol., 1990, 57(2): 233-299.[3]Yao, S. D., Sheng, S. G., Cai, J. H. et al., Nanosecond pulse radiolysis studies in China, Radiat. Phys. Chem., 1995, 46:105-109.[4]Baumann, H.. Merckel, C., Timpe, H. -J., The laser versus the lamp: reactivity of the diphenyl ketyl radical in the ground and excited states. Chem. Phys. Lett., 1984, 103(6): 497-502.[5]Barral-Tosh, S., Chattopadhyay, S. K., Das, P. K., A laser flash photolysis study of paraquat reduction by photogenerated aromatic ketyl radicals and carbonyl triplets, J. Phys. Chem., 1984, 88: 1404-1408.[6]Elisei. F., Favaro, G., Ion-forming processes on 248 nm laser excitation of benzophenone in aqueous solution: a time-resolved absorption and conductivity study, J. Photochem. Photobiol. A: Chem., 1991, 59:243-253.

  5. Catalytic performance and structural characterization of ferric oxide and its composite oxides supported gold catalysts for low-temperature CO oxidation

    Institute of Scientific and Technical Information of China (English)

    HAO; Zhengping


    [1]Carmichael, I., Hug, G. L., Triplet-triplet absorption spectra of organic molecules in condensed phases, J. Phys. Chem. Ref. Data, 1986, 15(1): 1-20.[2]Nikogosyan, D. N., Two-quantum UV photochemistry of nucleic acids: comparison with conventional low-intensity UV photochemistry and radiation chemistry, Int. J. Radiat. Biol., 1990, 57(2): 233-299.[3]Yao, S. D., Sheng, S. G., Cai, J. H. et al., Nanosecond pulse radiolysis studies in China, Radiat. Phys. Chem., 1995, 46:105-109.[4]Baumann, H.. Merckel, C., Timpe, H. -J., The laser versus the lamp: reactivity of the diphenyl ketyl radical in the ground and excited states. Chem. Phys. Lett., 1984, 103(6): 497-502.[5]Barral-Tosh, S., Chattopadhyay, S. K., Das, P. K., A laser flash photolysis study of paraquat reduction by photogenerated aromatic ketyl radicals and carbonyl triplets, J. Phys. Chem., 1984, 88: 1404-1408.[6]Elisei. F., Favaro, G., Ion-forming processes on 248 nm laser excitation of benzophenone in aqueous solution: a time-resolved absorption and conductivity study, J. Photochem. Photobiol. A: Chem., 1991, 59:243-253.

  6. 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: [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)


    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.

  7. Hydrothermal Synthesis and Crystal Structure of a New Zero-dimensional Complex: [Zn(H2BPTC)(phen)2]n·3nH2O

    Institute of Scientific and Technical Information of China (English)


    A new metal-organic coordination complex [Zn(H2BPTC)(phen)2]n·3nH2O (BPTC =3,3',4,4'-benzophenone tetracarboxylate, phen = 1,10-phenanthroline) 1 has been obtained from hydrothermal reaction and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. In compound 1, the zinc cation is hexa-coordinated with two carboxylate oxygen atoms from one H2BPTC ligand and four nitrogen atoms from two different phen ligands, showing a slightly distorted octahedral geometry. Crystal data: C41H30N4O12Zn, Mr = 836.06, monoclinic,P21/c, a = 14.2714(9), b = 16.9386(10), c = 15.0151(9) (A),β = 101.3420(10)°, V= 3558.8(4) (A)3, Dc= 1.560 g/cm3,μ(MoKα) = 0.766 mm-1, F(000) = 1720, Z = 4, R = 0.0439 and wR = 0.1157 for 4123observed reflections with I > 2σ(I).

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

    Energy Technology Data Exchange (ETDEWEB)

    Korolkov, Ilya V.; Mashentseva, Anastassiya A. [The L.N. Gumilyov Eurasian National University, Satpayev str., 2, 010008 Astana (Kazakhstan); Institute of Nuclear Physics Republic of Kazakhstan, 050032, Ibragimov str., 1, Almaty (Kazakhstan); Güven, Olgun [Department of Chemistry, Hacettepe University, 06800 Beytepe, Ankara (Turkey); Taltenov, Abzal A. [The L.N. Gumilyov Eurasian National University, Satpayev str., 2, 010008 Astana (Kazakhstan)


    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 (H{sub 2}O{sub 2}/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.

  9. Distribution, variability, and predictors of urinary concentrations of phenols and parabens among pregnant women in Puerto Rico. (United States)

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


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

  10. Green Synthesis of Gold Nanoparticles Using Aqueous Extract of Garcinia mangostana Fruit Peels

    Directory of Open Access Journals (Sweden)

    Kar Xin Lee


    Full Text Available The synthesis of gold nanoparticles (Au-NPs is performed by the reduction of aqueous gold metal ions in contact with the aqueous peel extract of plant, Garcinia mangostana (G. mangostana. An absorption peak of the gold nanoparticles is observed at the range of 540–550 nm using UV-visible spectroscopy. All the diffraction peaks at 2θ = 38.48°, 44.85°, 66.05°, and 78.00° that index to (111, (200, (220, and (311 planes confirm the successful synthesis of Au-NPs. Mostly spherical shape particles with size range of 32.96 ± 5.25 nm are measured using transmission electron microscopy (TEM. From the FTIR results, the peaks obtained are closely related to phenols, flavonoids, benzophenones, and anthocyanins which suggest that they may act as the reducing agent. This method is environmentally safe without the usage of synthetic materials which is highly potential in biomedical applications.

  11. Mechanistic Studies on the Photoallergy Mediated by Fenofibric Acid: Photoreactivity with Serum Albumins. (United States)

    Vayá, Ignacio; Andreu, Inmaculada; Monje, Vicente T; Jiménez, M Consuelo; Miranda, Miguel A


    The photoreactivity of fenofibric acid (FA) in the presence of human and bovine serum albumins (HSA and BSA, respectively) has been investigated by steady-state irradiation, fluorescence, and laser flash photolysis (LFP). Spectroscopic measurements allowed for the determination of a 1:1 stoichiometry for the FA/SA complexes and pointed to a moderate binding of FA to the proteins; by contrast, the FA photoproducts were complexed more efficiently with SAs. Covalent photobinding to the protein, which is directly related to the photoallergic properties of the drug, was detected after long irradiation times and was found to be significantly higher in the case of BSA. Intermolecular FA-amino acid and FA-albumin irradiations resulted in the formation of photoproducts arising from coupling between both moieties, as indicated by mass spectrometric analysis. Mechanistic studies using model drug-amino acid linked systems indicated that the key photochemical step involved in photoallergy is formal hydrogen atom transfer from an amino acid residue to the excited benzophenone chromophore of FA or (more likely) its photoproducts. This results in the formation of caged radical pairs followed by C-C coupling to give covalent photoaducts.

  12. Nuclear Energy Gradients for Internally Contracted Complete Active Space Second-Order Perturbation Theory: Multistate Extensions. (United States)

    Vlaisavljevich, Bess; Shiozaki, Toru


    We report the development of the theory and computer program for analytical nuclear energy gradients for (extended) multistate complete active space perturbation theory (CASPT2) with full internal contraction. The vertical shifts are also considered in this work. This is an extension of the fully internally contracted CASPT2 nuclear gradient program recently developed for a state-specific variant by us [MacLeod and Shiozaki, J. Chem. Phys. 2015, 142, 051103]; in this extension, the so-called λ equation is solved to account for the variation of the multistate CASPT2 energies with respect to the change in the amplitudes obtained in the preceding state-specific CASPT2 calculations, and the Z vector equations are modified accordingly. The program is parallelized using the MPI3 remote memory access protocol that allows us to perform efficient one-sided communication. The optimized geometries of the ground and excited states of a copper corrole and benzophenone are presented as numerical examples. The code is publicly available under the GNU General Public License.

  13. Tunable photonic multilayer sensors from photo-crosslinkable polymers (United States)

    Chiappelli, Maria; Hayward, Ryan


    The fabrication of tunable photonic multilayer sensors from stimuli-responsive, photo-crosslinkable polymers will be described. Benzophenone is covalently incorporated as a pendent photo-crosslinker, allowing for facile preparation of multilayer films by sequential spin-coating and crosslinking processes. Copolymer chemistries and layer thicknesses are selected to provide robust multilayer sensors which can show color changes across nearly the full visible spectrum due to the specific stimulus-responsive nature of the hydrated film stack. We will describe how this approach is extended to alternative sensor designs by tailoring the thickness and chemistry of each layer independently, allowing for the preparation of sensors which depend not only on the shift in wavelength of a reflectance peak, but also on the transition between Bragg mirrors and filters. Device design is optimized by photo-patterning sensor arrays on a single substrate, providing more efficient fabrication time as well as multi-functional sensors. Finally, radiation-sensitive multilayers, designed by choosing polymers which will preferentially degrade or crosslink under ionizing radiation, will also be described.

  14. Photocatalytic degradation of sunscreen active ingredients mediated by nanostructured materials (United States)

    Soto-Vazquez, Loraine

    Water scarcity and pollution are environmental issues with terrible consequences. In recent years several pharmaceutical and personal care products, such as sunscreen active ingredients, have been detected in different water matrices. Its recalcitrant behavior in the environment has caused controversies and generated countless questions about its safety. During this research, we employed an advanced oxidation process (photocatalysis) to degrade sunscreen active ingredients. For this study, we used a 3x3 system, evaluating three photocatalysts and three different contaminants. From the three catalysts employed, two of them were synthesized. ZnO nanoparticles were obtained using zinc acetate dihydrated as the precursor, and TiO2 nanowires were synthesized from titanium tetrachloride precursor. The third catalyst employed (namely, P25) was obtained commercially. The synthesized photocatalysts were characterized in terms of the morphology, elemental composition, crystalline structure, elemental oxidation states, vibrational modes and surface area, using SEM-EDS, XRD, XPS, Raman spectroscopy and BET measurements, respectively. The photocatalysts were employed during the study of the degradation of p-aminobenzoic acid, phenylbenzimidazole sulfonic acid, and benzophenone-4. In all the cases, at least 50% degradation was achieved. P25 showed degradation efficiencies above 90%, and from the nine systems, 7 of them degraded at least 86%.

  15. 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


    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.

  16. The use of molecular probes for the characterization of dispersions of functionalized silica nanoparticles. (United States)

    Arce, Valeria B; Bertolotti, Sonia G; Oliveira, Fernando J V E; Airoldi, Claudio; Gonzalez, Mónica C; Allegretti, Patricia E; Mártire, Daniel O


    Butoxylated silica nanoparticles (BSN) were prepared by esterification of the silanol groups of fumed silica nanoparticles with butanol and characterized by 13C and 29Si NMR and thermogravimetry. The molecular probes benzophenone (BP) and safranine-T were used to investigate the BSN suspensions in water:acetonitrile. Laser flash-photolysis experiments at lambda(exc)=266 nm performed with BSN suspended in acetonitrile:aqueous phosphate buffer supported previous results of our group obtained by time-resolved phosphorescence experiments and showed that only free and adsorbed excited triplet states of BP and diphenylketyl radicals contribute to the signals. The UV-vis spectroscopic and photophysical properties of safranine-T are strongly solvent-dependent. Thus, the analysis of the emission spectra and fluorescence lifetimes yielded information on the localization of this probe molecule in suspensions of BSN and of the bare silica nanoparticles. The values of the equilibrium constant for the adsorption of the ground-state safranine-T on the particles were found to be (9.2+/-0.8)x10(4), (7.2+/-0.8)x10(5), and (3.0+/-0.1)x10(4) for the BSN in 1:1 acetonitrile:water, SiO2 in 1:1 acetonitrile:water, and SiO2 in acetonitrile, respectively.

  17. 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)


    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.

  18. MMA/DVB emulsion surface graft polymerization initiated by UV light. (United States)

    Wang, Yongxin; Yang, Wantai


    Methyl methacrylate/1,2-divinylbenzene (MMA/DVB) in an opaque emulsion were successfully grafted onto the surface of polymeric substrate under the irradiation of UV light with benzophenone (BP) as a photoinitiator that was previously coated on the substrate surface. Monomer conversion, grafting efficiency, and grafting yields were determined by the gravimetric method. ATR-IR, AFM, and TEM were used to characterize the surface composition, to observe the topography of the grafted substrates, and to view inter-film colloid particles formed by cross-linking. The results reveal that, with the opaque MMA/DVB emulsion system and CPP film as substrate, the monomer conversion is in the range of 15-55%, the grafting efficiency is about 80%, the grafting yield reaches 5%, and the thickness of the graft layer can be controlled in the range 0.09-1.5 microm. Images of AFM show that the graft layer is piled up by nanoparticles (about 30-50 nm in diameter), which are linked together and tied to the substrate surface with covalent bonds. A possible model of surface graft polymerization including surface initiating, nucleation, and shish kebab growing is put forward to interpreting the above results.

  19. 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. (United States)

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


    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.

  20. Regioselective trans-cis photoisomerization of m-styrylstilbenes

    Energy Technology Data Exchange (ETDEWEB)

    Ito, Y.; Uozy, Y.; Dote, T.; Ueda, M.; Matsuura, T.


    Trans-cis photoisomerization of m-styrylstilbenes, i.e., 2,4,6-triisopropyl-3'-styrylstilbene (TISS), 2,4,6-trimethyl-3'-styrylstilbene (TMSS), and 3-styrylstilbene (SS), and of stilbenes, i.e., 2,4,6-triisopropylstilbene (TIS), 2,4,6-trimethylstilbene (TMS), and stilbene (S), are studied under direct of benzophenone-sensitized irradiation in hexane. Measurements of quantum yields of isomerization have revealed that although the styrylstilbene molecule bears two styryl groups, the reaction is highly regioselective, depending upon the excitation conditions and reactant structures. For example, isomerization of trans, trans-TISS and trans,cis-TISS occurred either at the 2,4,6-trisubstituted styryl side upon direct excitation or at the unstubstituted styryl side upon sensitized excitation. When the starting material carries an unsubstituted cis-styryl group, the major isomerization always occurred at this moiety by either direct or sensitized excitation, e.g., cis,trans-TISS ..-->.. trans,trans-TISS, cis,cis-TISS ..-->.. trans,cis-TISS, and cis,trans-SS ..-->.. trans,trans-SS. Furthermore, the photoisomerization of cis,cis-SS was found to be one-way. These results are interpreted in terms of the usual energy sink concept: the excited-state energies (E/sub S/ and E/sub T/) of the stilbene chromophores depend on molecular distortion in a subtle manner.

  1. Judd-Ofelt Analysis on Trifluoroacetate Europium Complexes for Liquid Laser Media

    Institute of Scientific and Technical Information of China (English)

    SHE Jiang-bo; LI Dong-dong; GAO Fei; QIAO Ze-bang; LIU Huan-huan; WEI Wei; PENG Bo


    Four europium trifluoroacetate complexes,Eu(CF3COO)3·bpy(bpy=2,2'-bipyridine)(l),Eu(CF3COO)3 ·phen(phen=1,10-phenanthroline)(2),Eu(CF3COO)3·2bp(bp=benzophenone)(3) and Eu(CF3COO)3·2tppo(tppo=triphenyl-phosphine oxide)(4) were synthesized and characterized by elemental analysis,Fourier transform infrared(FTIR) spectroscopy,photoluminescence(PL) spectroscopy and thermogravimetric analysis(TGA).The PL spectra of the complexes at room temperature show the strong typical EU3+ ion red emission,due to the efficient energy "antenna absorption" of ligands and transitions of Eu3+ ion between 5 Do→ 7FJ(J=0-4).The long lifetime and high quantum yield reflect that the multiphonon relaxations by coupling to O—H and C—H vibrations were reduced.According to the photoluminescent spectra,the Judd-Ofelt parameters Ω22 and Ω24 of the complexes were calculated and the radiative properties were also presented.The 5D0 radiative lifetime,quantum yield and the stimulated emission cross-section of the complexes are excellent,which prove that they have promising optical properties for liquid laser.The thermal analyses indicate that they are quite stable to heat.

  2. Cole-Cole law for critical dynamics in glass-forming liquids. (United States)

    Sperl, Matthias


    Within the mode-coupling theory (MCT) for glassy dynamics, the asymptotic low-frequency expansions for the dynamical susceptibilities at critical points are compared to the expansions for the dynamic moduli; this shows that the convergence properties of the two expansions can be quite different. In some parameter regions, the leading-order expansion formula for the modulus describes the solutions of the MCT equations of motion outside the transient regime successfully; at the same time, the leading- and next-to-leading-order expansion formulas for the susceptibility fail. In these cases, one can derive a Cole-Cole law for the susceptibilities; and this law accounts for the dynamics for frequencies below the band of microscopic excitations and above the high-frequency part of the alpha peak. It is shown that this scenario explains the optical-Kerr-effect data measured for salol and benzophenone (BZP). For BZP it is inferred that the depolarized light-scattering spectra exhibit a wing for the alpha peak within the Gigahertz band. This wing results from the crossover of the von Schweidler law part of the alpha peak to the high-frequency part of the Cole-Cole peak; and this crossover can be described quantitatively by the leading-order formulas of MCT for the modulus.

  3. A model assessment of the ability of lake water in Terra Nova Bay, Antarctica, to induce the photochemical degradation of emerging contaminants. (United States)

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


    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.

  4. Kinetics and magnetic field effect in geminate recombination of triplet radical pairs adsorbed onto porous glass studied by laser flash technique (United States)

    Levin, P. P.; Katalnikov, I. V.; Kuzmin, V. A.


    Geminate recombination kinetics of radical pairs (RP) formed by electron or hydrogen atom transfer from triphenylamine, tri(4-bromophenyl)amine, 4-phenylaniline or 4-phenylphenol to triplet 9,10-anthraquinone, benzophenone or 4-bromobenzophenone both adsorbed onto an optically transparent SiO 2 porous glass have been studied, using the laser flash technique with spectrophotometric registration. The kinetics are adequately described by the sum of two exponentials, ascribed to the existence of different kinds of "supercages" on the surface. At the same time, the simplest approximation by only one exponential is fair in many cases, because the contribution of a "slow" exponential is comparatively low and is masked by the slow component because of the decay of the escaped radicals. Introduction of a heavy Br atom leads to the acceleration of the geminate recombination; application of an external magnetic field results in retardation. The heavy-atom effect displays the contribution of the intersystem backwards electron transfer or intersystem recombination in the contact states of a triplet RP owing to the spin-orbit coupling. The magnetic field effect is the result of the significant contribution of the recombination route through the separated RP, where the hyperfine coupling and relaxation mechanisms of the RP spin evolution are active.

  5. The combined effects of matrix stiffness and growth factor immobilization on the bioactivity and differentiation capabilities of adipose-derived stem cells. (United States)

    Banks, Jessica M; Mozdzen, Laura C; Harley, Brendan A C; Bailey, Ryan C


    Biomaterial designs are increasingly incorporating multiple instructive signals to induce a desired cell response. However, many approaches do not allow orthogonal manipulation of immobilized growth factor signals and matrix stiffness. Further, few methods support patterning of biomolecular signals across a biomaterial in a spatially-selective manner. Here, we report a sequential approach employing carbodiimide crosslinking and benzophenone photoimmobilization chemistries to orthogonally modify the stiffness and immobilized growth factor content of a model collagen-GAG (CG) biomaterial. We subsequently examined the singular and combined effects of bone morphogenetic protein (BMP-2), platelet derived growth factor (PDGF-BB), and CG membrane stiffness on the bioactivity and osteogenic/adipogenic lineage-specific gene expression of adipose derived stem cells, an increasingly popular cell source for regenerative medicine studies. We found that the stiffest substrates direct osteogenic lineage commitment of ASCs regardless of the presence or absence of growth factors, while softer substrates require biochemical cues to direct cell fate. We subsequently describe the use of this approach to create overlapping patterns of growth factors across a single substrate. These results highlight the need for versatile approaches to selectively manipulate the biomaterial microenvironment to identify synergies between biochemical and mechanical cues for a range of regenerative medicine applications.

  6. Urinary biomarkers of exposure to 57 xenobiotics and its association with oxidative stress in a population in Jeddah, Saudi Arabia. (United States)

    Asimakopoulos, Alexandros G; Xue, Jingchuan; De Carvalho, Bruno Pereira; Iyer, Archana; Abualnaja, Khalid Omer; Yaghmoor, Soonham Sami; Kumosani, Taha Abdullah; Kannan, Kurunthachalam


    Oxidative stress arises from excessive free radicals in the body and is a trigger for numerous diseases, such as cancer and atherosclerosis. Elevated exposure to environmental chemicals can contribute to oxidative stress. The association between exposure to xenobiotics and oxidative stress, however, has rarely been studied. In this study, urinary concentrations of 57 xenobiotics (antimicrobials, parabens, bisphenols, benzophenones, and phthalates metabolites) were determined in a population from Jeddah, Saudi Arabia, to delineate association with the oxidative stress biomarker, 8-hydroxy-2'-deoxyguanosine (8OHDG). We collected 130 urine samples and analyzed for 57 xenobiotics using liquid chromatography-tandem mass spectrometry (LC/MS/MS) methods. The association between unadjusted and creatinine- or specific gravity-adjusted concentrations of xenobiotics and 8OHDG was examined by Pearson correlations and multiple regression analysis. High concentrations of mCPP (a metabolite of di-n-octyl phthalate; DnOP) and mCMHP (a metabolite of diethylhexyl phthalate; DEHP) were found in urine. In addition, the concentrations of bisphenol S (BPS) were higher than those of bisphenol A (BPA). The concentrations of metabolites of DEHP, phthalic acid, BPA, BPS, and methyl-protocatechuic acid were significantly associated with 8OHDG. This is the first biomonitoring study to report exposure of the Saudi population to a wide range of environmental chemicals and provides evidence that environmental chemical exposures contribute to oxidative stress.

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


    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.

  8. Modified low temperature Czochralski growth of xylenol orange doped benzopheone single crystal for fabricating dual band patch antenna (United States)

    Yadav, Harsh; Sinha, Nidhi; Kumar, Binay


    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.

  9. Phytochemical analysis and antioxidant potential of the leaves of Garcinia travancorica Bedd. (United States)

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


    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).

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

    Directory of Open Access Journals (Sweden)

    Tarek S. Belal


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

  11. Surface modified polypropylene pipette tips packed with a monolithic plug of adsorbent for high-throughput sample preparation. (United States)

    Altun, Zeki; Hjelmström, Anette; Abdel-Rehim, Mohamed; Blomberg, Lars G


    UV-initiated poly(butyl methacrylate-ethylene glycol dimethacrylate) porous polymer monoliths were prepared in situ in polypropylene-based pipette tips for high-throughput sample preparation. Prior to the in situ polymerization, the surface of the PP tips was modified. In this work, two different surface modification approaches were tested for this purpose. First the photoinitiator benzophenone was used to generate radicals at the surface of PP by hydrogen abstraction. In the second modification approach, a thin layer of a polymer was directly grafted to the surface. The effect of surface modification was measured by contact angle measurements of a drop of water at the surface. As a result of the surface modification, scan electron microscopy images indicate a covalent attachment of the monolith to the wall of the pipette tip. Pipette tips modified with 5% BP in methanol and packed with a plug of monolith were further evaluated for high-throughput sample preparation. Using a liquid handling system, the extraction performance of packed pipette tips was tested for the analysis of ropivacaine in plasma samples. The recovery and reproducibility results were in accordance with internationally accepted criteria for qualitative and quantitative analysis of the test substance, ropivacaine.

  12. Evaluation of the photostability of different UV filter combinations in a sunscreen. (United States)

    Gaspar, L R; Maia Campos, P M B G


    Development of photostable sunscreens is extremely important to preserve the UV protective capacity and to prevent the reactive intermediates of photounstable filter substances behaving as photo-oxidants when coming into direct contact with the skin. Thus, the objective of this study was to evaluate the photostability of four different UV filter combinations in a sunscreen by using HPLC analysis and spectrophotometry. The formulations that were investigated included four different UV filter combinations often used in SPF 15 sunscreens. The UV filter combinations were: octyl methoxycinnamate (OMC), benzophenone-3 (BP-3) and octyl salicylate (OS) (formulation 1); OMC, avobenzone (AVB) and 4-methylbenzilidene camphor (MBC) (formulation 2); OMC, BP-3 and octocrylene (OC) (formulation 3); OMC, AVB and OC (formulation 4). In the photostability studies, 40 mg of each formulation were spread onto a glass plate and left to dry before exposure to different UVA/UVB irradiation. Exposed samples were then immersed in isopropanol and the dried film dissolved ultrasonically. The filter components in the resulting solution were quantified by HPLC analysis with detection at 325 nm and by spectrophotometry. In this study, the four UV filter combinations showed different photostability profiles and the best one was formulation 3 (OMC, BP-3 and OC), followed by formulations 4, 1 and 2. In addition, OC improved the photostability of OMC, AVB and BP-3.

  13. A Novel method in Biosynthesis Silver Nanocomposite

    Directory of Open Access Journals (Sweden)

    Ferdos Parsa Mehr


    Full Text Available In this work,Polyacrylaimde grafted carboxymethyl starch (PAAm-g-CMS with different nitrogen contents was prepared using ultra violet /photoinitiator (UV/PI system where the water soluble 4-(trimethylammoniummethyl benzophenone chloride was used as the photoinitiator. PAAm-g-CMS was further utilized to prepare PAAm-g- CMS silver nanoparticles (PAAm-g-CMS-AgNPs composite. The latter was 12prepared using silver nitrate as a precursor and PAAm-g-CMS as both reducing and capping agent under alkaline conditions. The as prepared PAAm-g-CMS-AgNPs composite was characterized by FTIR and by measuring the absorbance of its colloidal solution using UV-vis spectrophotometer. The size and shape of the nanoparticles were measured by TEM. Reproducibility of the synthesis method was also tested. Highest absorbance of the colloidal solution of PAAm-g-CMS-AgNPs was obtained when PAAm-g-CMS (Nitrogen content (% =7.7 concentration of 0.8% (w/v; AgNO3 concentration of 900 ppm; pH 12; temperature 80C for 3h were used. 20 TEM showed round shape nanoparticles with size varies from 1-11 nm.

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

    Directory of Open Access Journals (Sweden)

    M. A. El-Sheikh


    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.

  15. Food contact materials, flavouring substances and smoke flavourings

    Directory of Open Access Journals (Sweden)

    Engel K-H


    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.

  16. [Novel access to indazoles based on palladium-catalyzed amination chemistry]. (United States)

    Inamoto, Kiyofumi


    Two efficient methods to construct the indazole nucleus have been developed, both of which utilize palladium-catalyzed intramolecular carbon-nitrogen bond formation. One is based on intramolecular Buchwald-Hartwig amination reaction of 2-halobenzophenone tosylhydrazones. The catalyst system we developed for this reaction allows the cyclization to proceed under very mild conditions and thus could be applied to a wide range of substrates with acid- or base-sensitive functional groups. Furthermore, this methodology could be applied for the construction of benzoisoxazole ring system. In addition, catalytic C-H activation with palladium followed by intramolecular amination of benzophenone tosylhydrazones was also accomplished with the aid of the catalyst system such as Pd(OAc)(2)/Cu(OAc)(2)/AgOCOCF(3), which gave another route to indazoles. Using this combination, indazoles with various functional groups could be obtained in good to high yields, especially in the case of substrates having electron donating group such as methoxy group on benzene ring. Interesting chemo- and regioselectivity were also observed in this reaction.

  17. Nondestructive chemical functionalization of MWNTs by poly(2-dimethylaminoethyl methacrylate) and their conjugation with CdSe quantum dots: Synthesis, properties, and cytotoxicity studies

    Energy Technology Data Exchange (ETDEWEB)

    Islam, Md. Rafiqul [Department of Imaging System Engineering, Pukyong National University, Busan 608-737 (Korea, Republic of); Energy and Mineral Resources Division, Ministry of Power, Energy and Mineral Resources, Government of the People' s Republic of Bangladesh, Dhaka 1000 (Bangladesh); Bach, Long Giang [Department of Imaging System Engineering, Pukyong National University, Busan 608-737 (Korea, Republic of); Center for Advanced Materials Research, Nguyen Tat Thanh University, Ho Chi Minh (Viet Nam); Vo, Thanh-Sang [Department of Chemistry, Pukyong National University, Busan 608-737 (Korea, Republic of); Center for Advanced Materials Research, Nguyen Tat Thanh University, Ho Chi Minh (Viet Nam); Tran, Thi-Nga [Department of Imaging System Engineering, Pukyong National University, Busan 608-737 (Korea, Republic of); Lim, Kwon Taek, E-mail: [Department of Imaging System Engineering, Pukyong National University, Busan 608-737 (Korea, Republic of)


    Multi-walled carbon nanotubes (MWNTs) were functionalized with poly(2-dimethylaminoethyl methacrylate) (PDMAEMA) in a nondestructive manner by UV-driven surface-initiated reversible addition fragmentation chain transfer (RAFT) polymerization. The RAFT agent having benzophenone groups was initially synthesized, and anchored to MWNTs through UV-triggered photoreaction. The subsequent RAFT polymerization of DMAEMA from the surface of MWNTs afforded PDMAEMA grafted MWNTs (MWNTs-g-PDMAEMA). The successful grafting of PDMAEMA on MWNTs via chemical linkage was confirmed by FT-IR, {sup 1}H NMR, XPS, EDX, TGA, TEM, and SEM analyses. A reversible dispersion phenomenon was observed in an aqueous solution of MWNTs-g-PDMAEMA as induced either by temperature or pH. The CdSe quantum dots (CdSe QDs) were attached to quaternized MWNTs-g-PDMAEMA to produce MWNTs-g-PDMAEMA-MeI/CdSe nanohybrids via electrostatic self-assembly. The formation of the nanohybrids was elucidated by EDS, TEM, and XRD. The cell viability assessment of the nanohybrids suggested their biocompatible character. The photoluminescence spectra of the nanohybrids indicated that the CdSe QDs significantly preserved its optical property after conjugation with MWNTs-g-PDMAEMA.

  18. Phosphine-free synthesis of CdSe quantum dots in a new co-capping ligand system. (United States)

    Wang, Chun; Jiang, Yang; Zhang, Zhongping; Li, Guohua; Chen, Lanlan; Jie, Jiansheng


    High-quality CdSe quantum dots with zinc blende structure were successfully synthesized via a new cheaper, greener phosphine-free route, using environmentally friendly N,N-dimethyl-oleoyl amide as the solvent of Se. The process eliminates trioctylphoshine from the synthesis, using oleic acid (OA) as a primary capping ligand and benzophenone (BP) as a secondary ligand in the noncoordinating solvent. It has been found that the addition of BP can improve the size distribution (below 10%) of as-synthesized CdSe quantum dots greatly, and the nucleation and growth process can also be well-separated. Moreover, a comprehensive examination on the control of particle size and size distribution was performed by systematically varying the BP/OA molar ratio. The phosphine-free route enables us to obtain high-quality CdSe quantum dots with sharp UV-vis absorption peak, size ranging from 2.8 to 6.8 nm, and narrow full width of half-maximum between 27 and 35 nm with purely band-edge luminescence, and without any post-synthesis processing.

  19. Polyimides Derived from Novel Asymmetric Dianhydrides (United States)

    Chuang, Chun-Hua (Inventor)


    This invention relates to the compositions and processes for preparing thermoset and thermoplastic polyimides derived from novel asymmetrical dianhydrides: specifically 2,3,3',4' benzophenone dianhydride (a-BTDA), and 3,4'-(hexafluoroisopropylidene)diphthalic anhydride (a-6FDA). The a-BTDA anhydride is prepared by Suzuki coupling with catalysts from a mixed anhydride of 3,4-dimethylbenzoic acid or 2,3-dimethylbenzoic acid with 2,3-dimethylphenylboronic acid or 3,4-dimethylphenylboronic acid respectively, to form 2,3,3',4'-tetramethylbenzophenone which is oxidized to form 2,3,3',4'-benzophenonetetracarboxylic acid followed by cyclodehydration to obtain a-BTDA. The a-6FDA is prepared by nucleophilic triflouoromethylation of 2,3,3',4'-tetramethylbenzophenone with trifluoromethyltrimethylsilane to form 3,4'-(trifluoromethylmethanol)-bis(o-xylene) which is converted to 3,4'-(hexafluoroisopropylidene-bis(o-xylene). The 3,4'-(hexafluoroisopropylidene)-bis(o-xylene) is oxidized to the corresponding tetraacid followed by cyclodehydration to yield a-6FDA.

  20. Polyimides with pendent ethynyl groups (United States)

    Jensen, Brian J.; Hergenrother, Paul M.; Nwokogu, Godson


    Several new polyimides containing pendent ethynyl groups were prepared and characterized. The new polyimides were prepared from the following novel ethynyl containing diamines; 1,1-bis(p aminophenyl)-1-(p ethynylphenyl) 2,2,2-trifluoroethane, and 1,1-bis(p aminophenyl)-1-(p phenylethynylphenyl)-2,2,2 trifluoroethane, and 1,1-bis(p aminophenyl)-1-(p hexynylphenyl)-2,2,2 trifluoroethane by reacting with either 3,3',4,4' benzophenone tetracarboxylic dianhydride or 2,2-bis(3,4 dicarboxyphenyl) hexafluoropropane dianhydride (6FDA). Inherent viscosities for the polymers ranged from 0.26 to 0.94 dL/g. Three copolymers prepared by reacting 10 mole pct. of one of the ethynyl containing diamines and 90 mole pct. of 2,2-bis-(4-(4 aminophenoxy)phenyl) hexafluoropropane with 6FDA were also prepared and characterized. Inherent viscosities for these copolymers ranged from 1.08 to 1.54 dL/g. Original polyimide glass transition temperatures were approx. 265 C while curing at 300 to 350 C for 1 hr in air increased the Tgs by approx. 10 C. Film properties and thermal stability were also measured for these copolyimides.


    Institute of Scientific and Technical Information of China (English)

    Jin-yan Wang; Gong-xiong Liao; Yuan Song; Shu-de Xiao; Xi-gao Jian


    A series of fluorinated copolyimides containing phthalazinone moieties were prepared from 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA), 3,3'4,4'-benzophenone-tetracarboxylic dianhydride (BPDA) and2-(4-aminophenyl)-4-[4-(4-aminophenoxyl)phenyl]-2,3-phthalazin-1-one (DHPZ-2NH2) for making polymeric optical waveguides. The resulting copolymers containing 0-50 mol% BPDA/DHPZ-2NH2 show good solubility and are soluble in some organic polar aprotic solvents. The copolyimides also present excellent thermal stability. These polymers possess high glass transition temperature higher than 603 K and high decomposition temperature above 742 K determined by differential scanning calorimetry and thermogravimetric analysis, respectively, under a nitrogen atmosphere. Their refractive indices could be controlled by varying the ratio of 6FDA and BPDA in the copolymer from 0.5 to 1.0, and the in-plane refractive indices (nTE) range from 1.6366 to 1.6668 and the out-of-plane refractive indices (nTM) from 1.6024 to 1.6280 at 632.8 nm.The polymers birefringence (0.0342-0.0388) is almost independent of the 6FDA content of copolymer, which indicated that the phthalazinone-containing copolyimides could be suitable to fabricate optical waveguides possessing a low polarization dependent loss (PDL).

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

    DEFF Research Database (Denmark)

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


    of bisphenol A (BPA) and seven other phenols. All analytes were determined using TurboFlow-LC-MS/MS. Two spot, three first morning and three 24-h urine samples were collected from 33 young Danish men over a three months period. Temporal variability was estimated by means of intraclass correlation coefficients...... (ICCs). More than 70% of the urine samples had detectable levels of BPA, triclosan (TCS), benzophenone-3 (BP-3) and sum of 2,4-dichlorophenol and 2,5-dichlorophenol (σDCP). We found low to moderate ICCs for BPA (0.10-0.42) and σDCP (0.39-0.72), whereas the ICCs for BP-3 (0.69-0.80) and TCS (0.......55-0.90) were higher. The ICCs were highest for the two spot urine samples, which were collected approximately 4 days apart, compared with the 24-h urine samples and the first morning urine samples, which were collected approximately 40 days apart. A consequence of the considerable variability in urinary...

  3. Synthesis and Characterization of Sulfonated Poly(Phenylene Containing a Non-Planar Structure and Dibenzoyl Groups

    Directory of Open Access Journals (Sweden)

    Hohyoun Jang


    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.

  4. 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


    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.

  5. Hydrophobic-core PEGylated graft copolymer-stabilized nanoparticles composed of insoluble non-nucleoside reverse transcriptase inhibitors exhibit strong anti-HIV activity. (United States)

    Leporati, Anita; Novikov, Mikhail S; Valuev-Elliston, Vladimir T; Korolev, Sergey P; Khandazhinskaya, Anastasia L; Kochetkov, Sergey N; Gupta, Suresh; Goding, Julian; Bolotin, Elijah; Gottikh, Marina B; Bogdanov, Alexei A


    Benzophenone-uracil (BPU) scaffold-derived candidate compounds are efficient non-nucleoside reverse transcriptase inhibitors (NNRTI) with extremely low solubility in water. We proposed to use hydrophobic core (methoxypolyethylene glycol-polylysine) graft copolymer (HC-PGC) technology for stabilizing nanoparticle-based formulations of BPU NNRTI in water. Co-lyophilization of NNRTI/HC-PGC mixtures resulted in dry powders that could be easily reconstituted with the formation of 150-250 nm stable nanoparticles (NP). The NP and HC-PGC were non-toxic in experiments with TZM-bl reporter cells. Nanoparticles containing selected efficient candidate Z107 NNRTI preserved the ability to inhibit HIV-1 reverse transcriptase polymerase activities with no appreciable change of EC50. The formulation with HC-PGC bearing residues of oleic acid resulted in nanoparticles that were nearly identical in anti-HIV-1 potency when compared to Z107 solutions in DMSO (EC50=7.5±3.8 vs. 8.2±5.1 nM). Therefore, hydrophobic core macromolecular stabilizers form nanoparticles with insoluble NNRTI while preserving the antiviral activity of the drug cargo.

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

    DEFF Research Database (Denmark)

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


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

  7. 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


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Kanetomo, Takuya; Ishida, Takayuki, E-mail: [Department of Engineering Science, The University of Electro-Communications, Tokyo (Japan)


    We synthesized [Ln{sup III}(hfac){sub 3}(H{sub 2}O)(L)] (abbreviated as Ln-L; Ln = Gd, Tb, Eu; L = DTBK (di-t-butyl ketone), BP (benzophenone)), in which the carbonyl oxygen atom was coordinated to the Ln ion center, despite of such bulky substituents. Their crystal structures were determined by means of X-ray diffraction study. Gd-DTBK is completely isomorphous to the di-t-butyl nitroxide derivative and accordingly can be regarded as a model with the ligand spin masked. The ac magnetic susceptibility measurements on Tb-DTBK and -BP showed frequency dependence, characteristic of single-ion magnets. They also displayed photoluminescence in the solid state at room temperature. The quantum yields of the luminescence of Tb-DTBK and -BP (λ{sub ex} = 360 nm) were improved to 57 and 35%, respectively, from that of the starting material [TbI{sup III}(hfac){sub 3}(H{sub 2}O){sub 2}] (28% at λ{sub ex} = 370 nm). Similarly, the quantum yields for Eu-DTBK and -BP were 8 and 15%, respectively, with λ{sub ex} = 400 nm, while that of the starting material [EuI{sup III}(hfac){sub 3}(H{sub 2}O){sub 2}] was 4% at λ{sub ex}=400 nm.

  9. Immunomodulation of Mytilus hemocytes by individual estrogenic chemicals and environmentally relevant mixtures of estrogens: in vitro and in vivo studies. (United States)

    Canesi, Laura; Lorusso, Lucia Cecilia; Ciacci, Caterina; Betti, Michele; Rocchi, Marco; Pojana, Giulio; Marcomini, Antonio


    Endocrine disrupting compounds (EDCs) are almost ubiquitous in the aquatic environment. In the marine bivalve Mytilus the natural estrogen 17beta-estradiol (E2) and different EDCs have been recently demonstrated to affect the function of the immune cells, the hemocytes. The effects were Tamoxifen-sensitive and were mediated by rapid modulation of kinase-mediated transduction pathways. In this work we compared the in vitro effects of individual estrogenic chemicals (E2, EE: 17alpha-ethynyl estradiol; MES: mestranol; NP: nonylphenol; NP1EC: nonylphenol monoethoxylate carboxylate; BPA: bisphenol A; BP: benzophenone) on hemocyte parameters: lysosomal membrane stability (LMS), phagocytosis, lysozyme release. LMS was the most sensitive effect parameter, showing a decreasing trend at increasing concentrations of estrogens. EC50 values obtained from LMS data were utilized to calculate the estradiol equivalency factor (EEF) for each compound; these EEFs allowed for an estimation of the estrogenic potential of a synthetic mixture with a composition very similar to that previously found in waters of the Venice lagoon. Concentrated mixtures significantly affected hemocyte parameters in vitro and the effects were prevented by Tamoxifen. Significant effects of the mixture were also observed in vivo, at longer exposure times and at concentrations comparable with environmental exposure levels. The results indicate that Mytilus immune parameters can be suitably utilized to evaluate the estrogenic potential of environmental samples.

  10. Characterization and quantitation of polyphenolic compounds in bark, kernel, leaves, and peel of mango (Mangifera indica L.). (United States)

    Barreto, Jacqueline C; Trevisan, Maria T S; Hull, William E; Erben, Gerhard; de Brito, Edy S; Pfundstein, Beate; Würtele, Gerd; Spiegelhalder, Bertold; Owen, Robert W


    The contents of secondary plant substances in solvent extracts of various byproducts (barks, kernels, peels, and old and young leaves) in a range of Brazilian mango cultivars were identified and quantitated. The results show that the profiles of secondary plant substances such as xanthone C-glycosides, gallotannins, and benzophenones in different byproducts vary greatly but are fairly consistent across cultivars. The free radical scavenging activity of the solvent extracts was evaluated using a high-performance liquid chromatography-based hypoxanthine/xanthine oxidase assay and revealed dose-dependent antioxidant capacity in all extracts. Four (mangiferin, penta- O-galloyl-glucoside gallic acid, and methyl gallate) of the major phenolic compounds detected were also evaluated in additional in vitro bioassay systems such as oxygen radical absorbance capacity, 2,2-diphenyl-1-picrylhydrazyl, and ferric reducing ability of plasma. Mangiferin in particular, detected at high concentrations in young leaves (Coite = 172 g/kg), in bark (Momika = 107 g/kg), and in old leaves (Itamaraka = 94 g/kg), shows an exceptionally strong antioxidant capacity.

  11. The effect of intermolecular hydrogen bonding on the fluorescence of a bimetallic platinum complex. (United States)

    Zhao, Guang-Jiu; Northrop, Brian H; Han, Ke-Li; Stang, Peter J


    The bimetallic platinum complexes are known as unique building blocks and arewidely utilized in the coordination-driven self-assembly of functionalized supramolecular metallacycles. Hence, photophysical study of the bimetallic platinum complexes will be very helpful for the understanding on the optical properties and further applications of coordination-driven self-assembled supramolecular metallacycles. Herein, we report steady-state and time-resolved spectroscopic experiments as well as quantum chemistry calculations to investigate the significant intermolecular hydrogen bonding effects on the intramolecular charge transfer (ICT) fluorescence of a bimetallic platinum compound 4,4'-bis(trans-Pt(PEt(3))(2)OTf)benzophenone 3 in solution. We demonstrated that the fluorescent state of compound 3 can be assigned as a metal-to-ligand charge transfer (MLCT) state. Moreover, it was observed that the formation of intermolecular hydrogen bonds can effectively lengthen the fluorescence lifetime of 3 in alcoholic solvents compared with that in hexane solvent. At the same time, the electronically excited states of 3 in solution are definitely changed by intermolecular hydrogen bonding interactions. As a consequence, we propose a new fluorescence modulation mechanism by hydrogen bonding to explain different fluorescence emissions of 3 in hydrogen-bonding solvents and nonhydrogen-bonding solvents.

  12. Cyclodextrin/dextran based hydrogels prepared by cross-linking with sodium trimetaphosphate. (United States)

    Wintgens, Véronique; Lorthioir, Cédric; Dubot, Pierre; Sébille, Bernard; Amiel, Catherine


    Novel βCD-based hydrogels have been synthesized using sodium trimetaphosphate (STMP) as non-toxic reagent. Straightforward mixing of βCD with dextran and STMP in basic aqueous media led to hydrogels incorporating dextran chains, phosphate groups and βCD units. The hydrogels have been characterized by swelling measurements, XPS and (31)P NMR. The swelling ratio was correlated to the content in phosphated groups, which give a polyelectrolyte character to these hydrogels. The significant rise of the swelling ratio with the βCD content increase has been attributed to a decrease of the number of phosphate-based crosslinks, the βCD units playing the role of dangling ends in the tridimensional network. Their loading capacity and their release properties have been investigated for methylene blue and benzophenone in order to demonstrate their potentiality for drug delivery. Through different interaction mechanisms, electrostatic and inclusion complex interactions, these compounds are loaded with different efficiencies. The release involves deswelling, diffusion mechanisms and partition equilibrium.

  13. Roles of free radicals in type 1 phototherapeutic agents: aromatic amines, sulfenamides, and sulfenates. (United States)

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


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

  14. Dinuclear Pentacarbonyl Tungsten Complex Bridged by Bis(3,5-dimethylpyrazol- 1- yl ) methane

    Institute of Scientific and Technical Information of China (English)

    赵雪梅; 唐良富; 杨攀; 王积涛


    A new bis (pyrazol-l-yl ) methane ligand, [Ph2(HO)CCH(3,5-Me2Pz)2, Pz=pyrazole] (1), with a bulky substituent on the methine carbon atom has been successfully synthesized by the reaction of bis(3,5- dimethylpyrazol-l-yl ) methyllithinm with benzophenone. Treatment of this ligand with W (CO)6 under UV-irradiation in THF at room temperature afforded a novel dinuclear complex CH2[3,5-Me2PzW(CO)5]2 (2) with loss of the Ph2CO fragment, which was characterized by IR, 1H NMR spectra and elemental analyses as well as the X-ray single crystal diffraction analysis. This compound crystallizes in the orthorhombic space group Pbcn, with a = 1.7690(3) nm, b=1.4460(3) nm, c = 1.2994(2) nm, Z = 4, V = 3.3239(10)nm3, De= 1.775g·cm-3, μ=6.967 mm-l, F (000) = 1672,Rl =0.0414 and wR 2 = 0.0988. Bis (3,5-dimethylpyrazol-l-yl) methane acts as a bridging bidentate ligand in this complex,which links two W (CO)5 fragments. In addition, heating this complex under reflux in 1,2-dimethoxyethane (DME) gives the known chelated mononuclear complex CH2(3,5-Me2Pz)2-W(CO)4 (3).

  15. RMN 13C de chalcones protonées: Factorisation des interactions intramoléculaires (United States)

    Membrey, François; Doucet, Jean-Pierre

    13C study of protonated para, para' disubstituted chalcones XC 6H 4CHCHC(OH) +C 6H 4Y, shows for the chemical shift of the carbenium center important deviations from a strict additivity of Substituent Induced Shifts observed in the corresponding monosubstituted ions. By collecting the experimental data into sub-populations where only one substituent (X or Y) varies—the other remaining fixed—a network of linear homogeneous correlations (δ/δ) is obtained. Their largely variable slopes indicate that the susceptibility of the carbenium site to the perturbations induced by one of the substituent groups depends on the nature of the other substituent group. The definition of 'Intrinsic Substituent Parameters' (derived from the SCS observed, in these ions, on the aromatic para positions) allows to separate the action of a substituent group on the electronic interaction mechanism and the global perturbation detected on the observation site. For a quantitative evaluation of these interactions, a Factorization Model is proposed, where deviations to additivity of the SCS are expressed as a product of the intrinsic parameters of X and Y groups. This model is successfully applied to 13C spectra of protonated chalcones and benzophenones. The parallelism between these intrinsic group effects and the SCS observed in monosubstituted benzenes points out the prime importance in these cationic systems, of π polarisation effects modulating the electron transfer toward the carbenium center within a concerted π-inductive mesomeric action.

  16. Synthesis and testing of ZnO nanoparticles for photo-initiation: experimental observation of two different non-migration initiators for bulk polymerization (United States)

    Schmitt, M.


    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

  17. 分散液液微萃取-在线衍生化-气相色谱-质谱联用法检测环境水样品中紫外吸收剂%Determination of ultraviolet filters in environmental aqueous samples by dispersive liquid-liquid microextraction with online derivatization-gas chromatography-mass spectrometry

    Institute of Scientific and Technical Information of China (English)

    李建; 徐兰英; 薛舒文; 徐丽


    建立了分散液液微萃取( dispersive liquid-liquid microextraction,DLLME )-在线衍生化-气相色谱-质谱( GC-MS)方法,将其用于环境水中6种二苯甲酮类紫外吸收剂( BPs)(二苯甲酮、2,4-二羟基二苯甲酮、2-羟基-4-甲氧基二苯甲酮、4-羟基二苯甲酮、2-羟基-4-辛氧基二苯甲酮、2,2′-二羟基-4,4′-二甲氧基二苯甲酮)的检测。系统优化了在线衍生化的条件(如进样口温度、不分流时间、衍生化试剂用量)以及 DLLME 萃取条件(如萃取剂种类、分散剂种类、萃取剂与分散剂比例、样品体积、样品溶液离子强度及 pH 值)等。在最优的条件下,所考察的6种BPs检出限为0.011~0.15μg/L,重现性( RSD)为0.7%~16.6%。该方法结果准确可靠,操作简单,富集效果好,成本较低,环境友好,在实际样品检测中具有一定的应用前景。%A method of dispersive liquid-liquid microextraction( DLLME)combined with online derivatization-gas chromatography-mass spectrometry( GC-MS)was developed for the determi-nation of benzophenone-type ultraviolet( UV)filers( BPs)in environmental aqueous samples. It is found that the online derivatization was superior to the off-line derivatization with its simplicity,high reaction efficiency and less consumption of potential poisonous reagents. The influential factors for online derivatization,including the temperature of the injection port,the splitless time,the proportion of derivatization reagent and sample solution,were initially opti-mized. In addition,the influential factors for DLLME,including the type of the extractant and dispersing solvent,the proportion of the extractant and the dispersing solvent,the volume of sample solution,the pH and the salt concentration of the sample solution were individually optimized in detail. Under the optimized derivatization and DLLME conditions,the limits of detection for the six BPs, benzophenone, 2

  18. UV/H2O2降解羟苯甲酮反应动力学及影响因素%Degradation of Organic Sunscreens 2-hydroxy-4-methoxybenzophenone by UV/H2O2 Process:Kinetics and Factors

    Institute of Scientific and Technical Information of China (English)

    冯欣欣; 杜尔登; 郭迎庆; 李华杰; 刘翔; 周方


    有机防晒剂随着日常使用不断进入环境中,成为一类新兴污染物。考察了 UV/ H2 O2工艺对典型有机防晒剂羟苯甲酮(BP-3)的水相光化学降解特征,并对 BP-3降解反应的影响因素包括初始 BP-3浓度、 H2 O2浓度、 UV 光强、共存阳离子和阴离子、叔丁醇和腐殖酸投加量等进行了研究。结果表明,BP-3的降解速率常数随初始 BP-3浓度升高而降低,随着H2 O2浓度增大而增高,随着 UV 光强增强而增大;阴离子会在一定程度上降低反应速率,阳离子中 Fe3+会产生类芬顿反应,促进生成•OH,对降解反应有显著的促进作用,投加叔丁醇和腐殖酸皆会抑制降解反应进行。采用每一对数减小级电能输入(EEo )指标对 UV/ H2 O2工艺的电能利用效率进行了评价,Fe3+的加入显著减小了 EEo 。研究不同因素对 UV/ H2 O2工艺降解效果的影响,可对实际工程中采用 UV/ H2 O2去除苯甲酮类有机防晒剂提供参考。%Organic sunscreens continue to enter the environment through people’s daily consumption, and become a kind of emerging contaminants. The photochemical degradation of benzophenone- 3 ( BP- 3) in water by UV/ H2 O2 process was investigated. Several factors, including the initial BP-3 concentration, H2 O2 concentration, UV light intensity, coexisting cations and anions, humic acid and tert-butyl alcohol, were also discussed. The results showed that BP-3 degradation rate constant decreased with increasing initial BP-3 concentration, while increased with increasing H2 O2 dosage and UV intensity. Coexisting anions could reduce the degradation rate, while coexisting ferric ions could stimulate the production of•OH through Fenton-like reaction, further significantly accelerated BP-3 degradation process. The BP-3 degradation would be inhibited by humic acid or tert-butyl alcohol. The electrical energy per order (EEo ) values were also calculated to evaluate the cost of BP- 3 degradation by

  19. 食品接触材料表面印刷油墨中光引发剂的高效液相色谱-串联质谱法检测和迁移研究%Determination and Migration Study of Six Photoinitiators in Printing Inks Used for Food Contact Materials by High Performance Liquid Chromatography Tandem Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    韩伟; 于艳军; 李宁涛; 王利兵


    A method based on migration tests using food simulants and ultra high performance liquid chromatography-photo diode array detector (UPLC-PDA) coupled with tandem mass spectroscopy (MS/MS) was developed for the detection of migration levels of six photoinitiators, benzophenone (BP), 4-methyl benzophenone (MBP), 1-Hydroxycyclohexyl phenyl ketone (Irgacure 184), 2-isopro-pylthioxanthone (ITX), ethyl 4-(N,N-dimethylamino)benzoate (EDAB), and 2-Ethylhexyl 4-dime-thylaminobenzoate (EHDAB) from food contact materials. Approximately 65% ethanol solution and w-hexane were selected as the food simulants. Under optimized conditions (migration at 5 ℃ and 40 ℃ for 240 h), the linearity of the analytical method ranged from 0. 1 to 1000 μg/L, method detection limit (MDL) ranged from 0. 002 to 0. 19 μg/dm2, recoveries were in the range from 63. 2% to 98. 8%. Fifty samples were tested by using the current method. The analytical results demonstrated that MBP was a general additive in printing ink with migration levels of 0. 055 - 3. 43 μg/dm2; EHDAB was always detectable in company with ITX, while BP was detectable only in one sample, with the highest level of 4. 02 μg/dm2.%采用食品模拟物进行迁移实验,结合高效液相色谱-紫外检测器(UPLC-PDA)和串联质谱(UPLC-MS/MS)技术,建立了食品接触材料印刷油墨中光引发剂BP(二苯甲酮)、MBP(4-甲基二苯甲酮)、Irgacure 184(1-羟基环己基苯基丙酮)、ITX(2-异丙基硫杂蒽酮)、EDAB(对二甲氨基苯甲酸乙酯)和EHDAB(对二甲氨基苯甲酸异辛酯)的快速测定方法.以65%乙醇和正己烷为食品模拟物,在5℃和40℃下迁移240 h.模拟液经浓缩、净化和过滤后直接进样分析.本方法的线性范围为0.1~1000 μg/L;检出限为0.002~0.19 μg/dm2;加标同收率为63.2%~98.8%.采用PDA初筛,MS/MS定量的方式对50余种样品中PIs的种类和含量进行了测定.结果表明:MBP在5个样品中被检出,其迁移水平为0.055~3

  20. Environmental occurrence and risk of organic UV filters and stabilizers in multiple matrices in Norway. (United States)

    Langford, Katherine H; Reid, Malcolm J; Fjeld, Eirik; Øxnevad, Sigurd; Thomas, Kevin V


    Eight organic UV filters and stabilizers were quantitatively determined in wastewater sludge and effluent, landfill leachate, sediments, and marine and freshwater biota. Crab, prawn and cod from Oslofjord, and perch, whitefish and burbot from Lake Mjøsa were selected in order to evaluate the potential for trophic accumulation. All of the cod livers analysed were contaminated with at least 1 UV filter, and a maximum concentration of almost 12 μg/g wet weight for octocrylene (OC) was measured in one individual. 80% of the cod livers contained OC, and approximately 50% of cod liver and prawn samples contained benzophenone (BP3). Lower concentrations and detection frequencies were observed in freshwater species and the data of most interest is the 4 individual whitefish that contained both BP3 and ethylhexylmethoxycinnamate (EHMC) with maximum concentrations of almost 200 ng/g wet weight. The data shows a difference in the loads of UV filters entering receiving water dependent on the extent of wastewater treatment. Primary screening alone is insufficient for the removal of selected UV filters (BP3, Padimate, EHMC, OC, UV-234, UV-327, UV-328, UV-329). Likely due in part to the hydrophobic nature of the majority of the UV filters studied, particulate loading and organic carbon content appear to be related to concentrations of UV filters in landfill leachate and an order of magnitude difference in these parameters correlates with an order of magnitude difference in the effluent concentrations of selected UV filters (Fig. 2). From the data, it is possible that under certain low flow conditions selected organic UV filters may pose a risk to surface waters but under the present conditions the risk is low, but some UV filters will potentially accumulate through the trophic food chain.

  1. Acute and chronic toxicity of four frequently used UV filter substances for Desmodesmus subspicatus and Daphnia magna. (United States)

    Sieratowicz, Agnes; Kaiser, Dominic; Behr, Maximilian; Oetken, Matthias; Oehlmann, Jörg


    As a consequence of growing public concern about UV radiation effects on human health chemical and physical UV filters are increasingly used in personal care and other products. The release of these lipophilic and often persistent compounds into surface waters may pose a risk for aquatic organisms. The aim of the study was to determine effects of four frequently used UV filters on primary aquatic producers and consumers, the green alga Desmodesmus subspicatus and the crustacean Daphnia magna. Exposure to benzophenone 3 (BP3), ethylhexyl methoxycinnamate (EHMC), 3-benzylidene camphor (3-BC) and 3-(4'-methylbenzylidene)-camphor (4-MBC) resulted in growth inhibition of D. subspicatus with 72 h IC(10) values of 0.56 mg/L (BP 3), 0.24 mg/L (EHMC), 0.27 mg/L (3-BC) and 0.21 mg/L (4-MBC). EC(50) concentrations in the acute test with D. magna were 1.67, 0.57, 3.61 and 0.80 mg/L for BP3, EHMC, 3-BC and 4-MBC, respectively. Chronic exposure of D. magna resulted in NOECs of 0.04 mg/L (EHMC) and 0.1 mg/L (3-BC and 4-MBC). BP 3 showed no effects on neonate production or the length of adults. Rapid dissipation of these substances from the water phase was observed indicating the need for more frequent test medium renewal in chronic tests or the use of flow-through test systems.

  2. Molecularly imprinted polymer grafted to porous polyethylene frits: a new selective solid-phase extraction format. (United States)

    Barahona, Francisco; Turiel, Esther; Martín-Esteban, Antonio


    In this paper, a novel format for selective solid-phase extraction based on a molecularly imprinted polymer (MIP) is described. A small amount of MIP has been synthesized within the pores of commercial polyethylene (PE) frits and attached to its surface using benzophenone (BP), a photo-initiator capable to start the polymerisation from the surface of the support material. Key properties affecting the obtainment of a proper polymeric layer, such as polymerisation time and kind of cross-linker were optimised. The developed imprinted material has been applied as a selective sorbent for cleaning extracts of thiabendazole (TBZ), as model compound, from citrus samples. The use of different solvents for loading the analyte in the imprinted frits was investigated, as well as the binding capacity of the imprinted polymer. Imprinted frits showed good selectivity when loads were performed using toluene and a linear relationship was obtained for the target analyte up to 1000 ng of loaded analyte. Prepared composite material was applied to the SPE of TBZ in real samples extracts, showing an impressive clean-up ability. Calibrations showed good linearity in the concentration range of 0.05-5.00 μg g(-1), referred to the original solid sample, and the regression coefficients obtained were greater than 0.996. The calculated detection limit was 0.016 μg g(-1), low enough to satisfactory analysis of TBZ in real samples. RSDs at different spiking levels ranged below 15% in all the cases and imprinted frits were reusable without loss in their performance.

  3. Serum and urine concentrations of flunitrazepam and metabolites, after a single oral dose, by immunoassay and GC-MS. (United States)

    Snyder, H; Schwenzer, K S; Pearlman, R; McNally, A J; Tsilimidos, M; Salamone, S J; Brenneisen, R; ElSohly, M A; Feng, S


    A clinical study was conducted to assess the ability of commercially available immunoassays to detect flunitrazepam (FNP) in plasma and urine samples and to compare the results with those obtained by gas chromatography-mass spectrometry (GC-MS). The clinical study consisted of four individuals (two male and two female) who had taken a single 2-mg dose of FNP. Serum was collected over a 48-h period and urine was collected over a 72-h period. The serum and urine samples were analyzed by the COBAS INTEGRA Serum Benzodiazepines assay (SBENZ), the TDx serum and urine Benzodiazepines assay, and GC-MS. The GC-MS procedure was developed for analysis of FNP and metabolites in plasma and urine using an acid hydrolysis step resulting in the formation of specific benzophenones corresponding to FNP and its metabolites. The relative sensitivities of the assays for the detection of FNP and metabolites in serum and urine were GC-MS > SBENZ > TDx. The immunoassay results for serum samples showed peak concentrations of FNP metabolites at 8 h after FNP ingestion for three individuals and at about 1 h for the fourth individual. The GC-MS, SBENZ, and TDx urine immunoassays detected drug above the stated limit of detection (LOD) in 44, 41, and 35 serial FNP urine samples, respectively. FNP metabolites were detected in urine samples with all three assays for up to 72 h after a 2-mg dose. The improved detection rate with the SBENZ assay as compared to the TDx assay is likely explained by its higher cross-reactivity with the major metabolite, 7-amino-flunitrazepam (7-amino-FNP), and its lower LOD.

  4. Bespoke contrast-matched diblock copolymer nanoparticles enable the rational design of highly transparent Pickering double emulsions† †Electronic supplementary information (ESI) available: GPC chromatograms, additional transmission electron micrographs, digital photographs, visible absorption spectra and laser diffraction data, further optical and fluorescence micrographs. See DOI: 10.1039/c6nr03856e Click here for additional data file. (United States)

    Thompson, Kate L.; Derry, Matthew J.; Warren, Nicholas J.; Ratcliffe, Liam P. D.; Williams, Clive N.; Brown, Steven L.


    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

  5. People with diabetes, respiratory, liver or mental disorders, higher urinary antimony, bisphenol A, or pesticides had higher food insecurity: USA NHANES, 2005-2006. (United States)

    Shiue, Ivy


    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.

  6. 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: [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)


    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. Inhibition of Saccharomyces cerevisiae Pdr5p by a natural compound extracted from Brazilian Red Propolis

    Directory of Open Access Journals (Sweden)

    Cinzia Lotti


    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

  8. Biodegradation of Crystal Violet by Agrobacterium radiobacter

    Institute of Scientific and Technical Information of China (English)

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


    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% NH4Cl 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 rag/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.

  9. 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)


    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.

  10. Development of palm oil-based UV-curable epoxy acrylate and urethane acrylate resins for wood coating application (United States)

    Tajau, Rida; Ibrahim, Mohammad Izzat; Yunus, Nurulhuda Mohd; Mahmood, Mohd Hilmi; Salleh, Mek Zah; Salleh, Nik Ghazali Nik


    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.

  11. Flow cytometric assay to assess short-term effects of personal care products on the marine microalga Tetraselmis suecica. (United States)

    Seoane, Marta; Esperanza, Marta; Rioboo, Carmen; Herrero, Concepción; Cid, Ángeles


    Large quantities of personal care products (PCPs) are used daily and many of their chemical ingredients are subsequently released into marine environments. Cultures of the marine microalga Tetraselmis suecica were exposed for 24 h to three emerging compounds included in the main classes of PCPs: the UV filter benzophenone-3 (BP-3), the disinfectant triclosan (TCS) and the fragrance tonalide (AHTN). Concentrations tested, expressed as cellular quota (pg cell(-1)), ranged from 5 to 40 for BP-3, from 2 to 16 for TCS and from 1.2 to 2.4 for AHTN. A small cytometric panel was carried out to evaluate key cytotoxicity biomarkers including inherent cell properties, growth and metabolic activity and cytoplasmic membrane properties. BP-3 caused a significant increase in growth rate, metabolic activity and chlorophyll a fluorescence from 10 pg cell(-1). However, growth and esterase activity decreased in cells exposed to all TCS and AHTN concentrations, except the lowest ones. Also these two compounds provoked a significant swelling of cells, more pronounced in the case of TCS-exposed cells. Although all treated cells remained viable, changes in membrane potential were observed. BP-3 and AHTN caused a significant depolarization of cells from 10 to 1.6 pg cell(-1), respectively; however all TCS concentrations assayed caused a noticeable hyperpolarization of cells. Metabolic activity and cytoplasmic membrane potential were the most sensitive parameters. It can be concluded that the toxicological model used and the toxicological parameters evaluated are suitable to assess the toxicity of these emerging contaminants.

  12. Associations between urinary phenol and paraben concentrations and markers of oxidative stress and inflammation among pregnant women in Puerto Rico. (United States)

    Watkins, Deborah J; Ferguson, Kelly K; Anzalota Del Toro, Liza V; Alshawabkeh, Akram N; Cordero, José F; Meeker, John D


    Phenols and parabens are used in a multitude of consumer products resulting in ubiquitous human exposure. Animal and in vitro studies suggest that exposure to these compounds may be related to a number of adverse health outcomes, as well as potential mediators such as oxidative stress and inflammation. We examined urinary phenol (bisphenol A (BPA), triclosan (TCS), benzophenone-3 (BP-3), 2,4-dichlorophenol (24-DCP), 2,5-dichlorophenol (25-DCP)) and paraben (butyl paraben (B-PB), methyl paraben (M-PB), propyl paraben (P-PB)) concentrations measured three times during pregnancy in relation to markers of oxidative stress and inflammation among participants in the Puerto Rico Testsite for Exploring Contamination Threats (PROTECT) project. Serum markers of inflammation (c-reactive protein (CRP), IL-1β, IL-6, IL-10, and tumor necrosis factor-α (TNF-α)) were measured twice during pregnancy (n=105 subjects, 187 measurements) and urinary markers of oxidative stress (8-hydroxydeoxyguanosine (OHdG) and isoprostane) were measured three times during pregnancy (n=54 subjects, 146 measurements). We used linear mixed models to assess relationships between natural log-transformed exposure and outcome biomarkers while accounting for within individual correlation across study visits. After adjustment for urinary specific gravity, study visit, maternal pre-pregnancy BMI, and maternal education, an interquartile range (IQR) increase in urinary BPA was associated with 21% higher OHdG (p=0.001) and 29% higher isoprostane (p=0.0002), indicating increased oxidative stress. The adjusted increase in isoprostane per IQR increase in marker of exposure was 17% for BP-3, 27% for B-PB, and 20% for P-PB (all pparabens, and TCS during pregnancy may be related to oxidative stress and inflammation, potential mechanisms by which exposure to these compounds may influence birth outcomes and other adverse health effects, but additional research is needed.

  13. 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: [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)


    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.

  14. A photoreducible copper(II)-tren complex of practical value: generation of a highly reactive click catalyst. (United States)

    Harmand, Lydie; Lambert, Romain; Scarpantonio, Luca; McClenaghan, Nathan D; Lastécouères, Dominique; Vincent, Jean-Marc


    A detailed study on the photoreduction of the copper(II) precatalyst 1 to generate a highly reactive cuprous species for the copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) click reaction is presented. For the photoactive catalyst described herein, the activation is driven by a photoinduced electron transfer (PET) process harnessing a benzophenone-like ketoprofenate chromophore as a photosensitizer, which is equally the counterion. The solvent is shown to play a major role in the Cu(II) to Cu(I) reduction process as the final electron source, and the influence of the solvent nature on the photoreduction efficiency has been studied. Particular attention was paid to the use of water as a potential solvent, aqueous media being particularly appealing for CuAAC processes. The ability to solubilize the copper-tren complexes in water through the formation of inclusion complexes with β-CDs is demonstrated. Data is also provided on the fate of the copper(I)-tren catalytic species when reacting with O2, O2 being used to switch off the catalysis. These data show that partial oxidation of the secondary benzylamine groups of the ligand to benzylimines occurs. Preliminary results show that when prolonged irradiation times are employed a Cu(I) to Cu(0) over-reduction process takes place, leading to the formation of copper nanoparticles (NPs). Finally, the main objective of this work being the development of photoactivable catalysts of practical value for the CuAAC, the catalytic, photolatent, and recycling properties of 1 in water and organic solvents are reported.

  15. Endocrine disrupting chemicals and other substances of concern in food contact materials: an updated review of exposure, effect and risk assessment. (United States)

    Muncke, Jane


    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.

  16. Photoyellowing inhibition of bleached high yield pulps using novel water-soluble UV screens. (United States)

    Argyropoulos, D S; Halevy, P; Peng, P


    To address the deficiencies of benzophenone UV screens for preventing brightness reversion in high yield mechanical papers, we synthesized a new series of such materials with enhanced water solubility and compatibility with the lignocellulosic substrate. A series of 2,4-dihydroxybenzophenones (DHB) were synthesized containing various Mannich bases at the C3 position of one of its rings. They possess the UV-screening ability of o-hydroxylbenzophenones, and they also contain tertiary nitrogen atoms that may function as radical scavengers. Aqueous solutions of the hydrochloride salt of 3-(dimethylaminomethylene)-2,4-dihydroxylbenzophenone (1), when applied on bleached chemithermomechanical pulp (CTMP) sheets, were significantly more efficient in preventing photoyellowing than the original DHB applied on the sheets from ethanol-water solutions. This confirmed our original hypothesis that increasing the compatibility of the UV screen with the lignocellulosic matrix would increase its efficiency in preventing photoyellowing. Compound 1, however, was found to be somewhat more effective than its hydrochloride salt toward preventing photoyellowing. This was attributed to the synergistic action of the free tertiary aminic center attached on the molecule with its UV-screening ability. To comprehend further the various parameters that influence the photoyellowing inhibition performance of these compounds and DHB with bleached CTMP pulp fibers, a series of handsheets were prepared at different pH. The interactions of the protonated compound 1 with pulp fibers were then evaluated by studying their kinetics of absorption and desorption to and from the fiber matrix. This part of our study found that the adsorption of protonated Mannich derivatives of DHB onto pulp is most likely governed by a cation-exchange mechanism involving the cationic amine group with the sulfonic and carboxylic acid groups located on the surface of the fibers. The pH the paper sheet was made from was also

  17. Endocrine disruptors in food contact materials; is there a health threat? (United States)

    Cwiek-Ludwicka, Kazimiera; Ludwicki, Jan K


    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.

  18. Exploring the flexible chemistry of 4-fluoro-3-nitrophenyl azide for biomolecule immobilization and bioconjugation. (United States)

    Kumar, Saroj; Kumar, Dileep; Ahirwar, Rajesh; Nahar, Pradip


    Bioconjugation and functionalization of polymer surfaces are two major tasks in materials chemistry which are accomplished using a variety of coupling agents. Immobilization of biomolecules onto polymer surfaces and the construction of bioconjugates are essential requirements of many biochemical assays and chemical syntheses. Different linkers with a variety of functional groups are used for these purposes. Among them, the benzophenones, aryldiazirines, and arylazides represent the most commonly used photolinker to produce the desired chemical linkage upon their photo-irradiation. In this review, we describe the versatile applications of 4-fluoro-3-nitrophenyl azide, one of the oldest photolinkers used for photoaffinity labeling in the late 1960s. Surprisingly, this photolinker, historically known as 1-fluoro-2-nitro-4-azidobenzene (FNAB), has remained unexplored for a long time because of apprehension that FNAB forms ring-expanded dehydroazepine as a major product and hence cannot activate an inert polymer. The first evidence of photochemical activation of an inert surface by FNAB through nitrene insertion reaction was reported in 2001, and the FNAB-activated surface was found to conjugate a biomolecule without any catalyst, reagent, or modification. FNAB has distinct advantages over perfluorophenyl azide derivatives, which are contemporary nitrene-generating photolinkers, because of its simple, single-step preparation and ease of thermochemical and photochemical reactions with versatile polymers and biomolecules. Covering these aspects, the present review highlights the flexible chemistry of FNAB and its applications in the field of surface engineering, immobilization of biomolecules such as antibodies, enzymes, cells, carbohydrates, oligonucleotides, and DNA aptamers, and rapid diagnostics. Graphical Abstract An overview of the FNAB-engineered activated polymer surfaces for covalent ligation of versatile biomolecules.

  19. Formation of hybrid films from perylenediimide-labeled core-shell silica-polymer nanoparticles. (United States)

    Ribeiro, Tânia; Fedorov, Aleksander; Baleizão, Carlos; Farinha, José Paulo S


    We prepared water-dispersible core-shell nanoparticles with a perylenediimide-labeled silica core and a poly(butyl methacrylate) shell, for application in photoactive high performance coatings. Films cast from water dispersions of the core-shell nanoparticles are flexible and transparent, featuring homogeneously dispersed silica nanoparticles, and exhibiting fluorescence under appropriate excitation. We characterized the film formation process using nanoparticles where the polymer shell has been labeled with either a non-fluorescent N-benzophenone derivative (NBen) or a fluorescent phenanthrene derivative (PheBMA). We used Förster resonance energy transfer (FRET) from PheBMA to NBen to follow the interparticle interdiffusion of the polymer anchored to the silica surface that occurs after the dried dispersions are annealing above the glass transition temperature of the polymer. By calculating the evolution of the FRET quantum efficiency with annealing time, we could estimate the approximate fraction of mixing (fm) between polymer from neighbor particles, and from this, the apparent diffusion coefficients (Dapp) for this process. For long annealing times, the limiting values of fm are slightly lower than for films of pure PBMA particles at similar temperatures (go up to 80% of total possible mixing). The corresponding diffusion coefficients are also very similar to those reported for films of pure PBMA, indicating that the fact that the polymer chains are anchored to the silica particles does not significantly hinder the diffusion process during the initial part of the mixing process. From the temperature dependence of the diffusion coefficients, we found an effective activation energy for diffusion of Ea=38 kcal/mol, very similar to the value obtained for particles of the same polymer without the silica core. With these results, we show that, although the polymer is grafted to the silica surface, polymer interdiffusion during film formation is not significantly

  20. Use of stable isotope probing to assess the fate of emerging contaminants degraded by white-rot fungus. (United States)

    Badia-Fabregat, Marina; Rosell, Mònica; Caminal, Glòria; Vicent, Teresa; Marco-Urrea, Ernest


    The widespread of emerging contaminants in the environment and their potential impact on humans is a matter of concern. White-rot fungi are cosmopolitan organisms able to remove a wide range of pharmaceuticals and personal care products (PPCP) through cometabolism (i.e. laccases and peroxidases) or detoxification mechanisms (i.e. cytochrome P450 system). However, the use of PPCP as carbon source for these organisms is largely unexplored. Here, we used carbon stable isotope tracer experiments to assess the fate of anti-inflammatory diclofenac (DCF) and UV filter benzophenone-3 (BP3) during degradation by Trametes versicolor. The comparison between carbon isotopic composition of emitted carbon dioxide from 13C-labelled DCF ([acetophenyl ring-13C6]-DCF) and 13C-BP3 ([phenyl-13C6]-BP3) versus their 12C-homologue compounds showed mineralization of about 45% and 10% of the 13C contained in their respective molecules after 9 days of incubation. The carbon isotopic composition of the bulk biomass and the application of amino acid-stable isotope probing (SIP) allowed distinguishing between incorporation of 13C from BP3 into amino acids, which implies the use of this emerging contaminant as carbon source, and major intracellular accumulation of 13C from DCF without implying the transformation of its labelled phenyl ring into anabolic products. A mass balance of 13C in different compartments over time provided a comprehensive picture of the fate of DCF and BP3 across their different transformation processes. This is the first report assessing biodegradation of PPCP by SIP techniques and the use of emerging contaminants as carbon source for amino acid biosynthesis.

  1. Urinary excretion of phthalate metabolites, phenols and parabens in rural and urban Danish mother-child pairs. (United States)

    Frederiksen, Hanne; Nielsen, Jeanette Kolstrup Søgaard; Mørck, Thit Aarøe; Hansen, Pernille Winton; Jensen, Janne Fangel; Nielsen, Ole; Andersson, Anna-Maria; Knudsen, Lisbeth E


    Some phthalates, parabens and phenols have shown adverse endocrine disrupting effects in animal studies and are also suspected to be involved in human reproductive problems. However, knowledge about exposure sources and biomonitoring data in different subsets of populations are still scarce. Thus, in this study first morning urine samples were collected from 6 to 11 years Danish children and their mothers. The content of seven parabens, nine phenols and metabolites of eight different phthalates were analysed by LC-MS/MS. Two parabens, six phenols and metabolites from six phthalate diesters were measurable in more than 50%, 75% and 90% of the participants, respectively. Thus the children and their mothers were generally exposed simultaneously to a range of phthalates, phenols and parabens. In general, the levels were low but for several of the compounds extreme creatinine adjusted concentrations 100-500-fold higher than the median level were seen in some participants. Children were significantly higher exposed to bisphenol A (BPA) and some of the phthalates (DiBP, DnBP, BBzP, DEHP and DiNP) than their mothers, whereas mothers were higher exposed to compounds related to cosmetics and personal care products such as parabens (MeP, EtP and n-PrP), benzophenone-3, triclosan and diethyl phthalate. However, a very high correlation between mothers and their children was observed for all chemicals. A high individual exposure to one chemical was often associated with a high exposure to other of the chemicals and the possibility of combination effects of multiple simultaneous exposures cannot be excluded.

  2. Divide and Conquer May Not Be the Optimal Approach to Retain the Desirable Estrogenic Attributes of the Cyclopia Nutraceutical Extract, SM6Met.

    Directory of Open Access Journals (Sweden)

    M Mortimer

    Full Text Available The genus Cyclopia, an indigenous South African fynbos plant used to prepare honeybush tea, contains phytoestrogenic compounds. An extract from C. subternata, SM6Met, displays three desirable estrogenic attributes for future development of a phytoestrogenic nutraceutical, namely, ERα antagonism, ERβ agonism, and also antagonism of E2-induced breast cancer cell proliferation. Activity-guided fractionation of SM6Met was used in an attempt to isolate and identify compounds conferring the desirable estrogenic profile to SM6Met. Initial liquid-liquid fractionation of SM6Met yielded a polar fraction (PF and a non-polar fraction (NPF, with the desirable estrogenic attributes retained in the NPF. Subsequent high performance counter-current chromatography (HPCCC fractionation of the NPF yielded three fractions (F1-F3. Interestingly, the fractions revealed separation of the previously demonstrated positive estrogenic attributes of the NPF into separate fractions, with F1 and F2 acting as ERα antagonists, only F2 inducing antagonism of E2-induced breast cancer cell proliferation and only F3 retaining robust ERβ agonist activity. In terms of major polyphenols, quantitative HPLC and liquid chromatography tandem mass spectrometry (LC-MS/MS indicated that HPCCC fractionation resulted in a divergence of polyphenolic classes, with F1 emerging as the dihydrochalcone-rich fraction and F2 as the flavanone- and benzophenone-rich fraction, while the xanthones, flavones and phenolic acids were retained in F3. F3 was re-engineered into F3R by reassembling the major polyphenols identified in the fraction. F3R could, however, not replicate the effect of F3. In conclusion, although activity-guided fractionation results suggest that retention of all the desirable estrogenic attributes of the original SM6Met in one fraction is not an attainable goal, fractionation is a useful tool to enhance specific desirable estrogenic attributes.

  3. Iriflophenone-3-C-glucoside from Cyclopia genistoides: isolation and quantitative comparison of antioxidant capacity with mangiferin and isomangiferin using on-line HPLC antioxidant assays. (United States)

    Malherbe, Christiaan J; Willenburg, Elize; de Beer, Dalene; Bonnet, Susan L; van der Westhuizen, Jan H; Joubert, Elizabeth


    The benzophenone, iriflophenone-3-C-glucoside, was isolated from Cyclopia genistoides using a combination of fluid-fluid extraction, high performance counter-current chromatography (HPCCC) and semi-preparative high performance liquid chromatography (HPLC). The microplate oxygen radical absorbance capacity (ORAC) assay, with fluorescein as probe, was adapted for use in an on-line HPLC configuration. The method was validated using a mixture of authentic standards including iriflophenone-3-C-glucoside, and the xanthones, mangiferin and isomangiferin. Trolox (6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid) was included in the mixture for calculation of Trolox equivalent antioxidant capacity (TEAC) values. Using the on-line HPLC-ORAC assay, as well as 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS(+)) on-line assays, the antioxidant activity of iriflophenone-3-C-glucoside and isomangiferin was demonstrated for the first time. Iriflophenone-3-C-glucoside presented no radical scavenging ability against DPPH, but scavenged ABTS(+) and peroxyl radicals (TEACABTS of 1.04 and TEACORAC of 3.61). Isomangiferin showed slightly lower antioxidant capacity than mangiferin against DPPH (TEACDPPH of 0.57 vs. 0.62), but higher capacity against ABTS(+) (TEACABTS of 1.82 vs. 1.67) and peroxyl radical (TEACORAC of 4.14 vs. 3.69) than mangiferin. The on-line HPLC-ORAC assay was shown to be more sensitive for radical scavengers, but at the same time less selective for rapid radical scavengers than the DPPH assay.

  4. 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. (United States)

    Tay, Pei Yin; Tan, Chin Ping; Abas, Faridah; Yim, Hip Seng; Ho, Chun Wai


    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 (pantioxidant 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.

  5. Integrated comparative metabolite profiling via MS and NMR techniques for Senna drug quality control analysis. (United States)

    Farag, Mohamed A; Porzel, Andrea; Mahrous, Engy A; El-Massry, Mo'men M; Wessjohann, Ludger A


    Senna alexandrina Mill (Cassia acutifolia and Cassia angustifolia) are used for the laxative medicine Senna. Leaves and pods from two geographically different sources were distinguished from each other via proton nuclear magnetic resonance (1H-NMR) and ultra performance liquid chromatography-mass spectrometry (UPLC-MS) analysis. Under optimized conditions, we were able to simultaneously quantify and identify 107 metabolites including 21 anthraquinones, 24 bianthrones (including sennosides), 5 acetophenones, 25 C/O-flavonoid conjugates, 5 xanthones, 3 naphthalenes, 2 further phenolics, and 9 fatty acids. Principal component analysis (PCA) and hierarchical clustering analysis (HCA) were used to define both similarities and differences among samples. For sample classification based on tissue type (leaf and pod), both UPLC-MS and NMR were found to be more effective in separation than on geographical origin. Results reveal that the amounts of the major classes of bioactives in Senna, i.e., flavonoids and sennosides, varied significantly among organs. Leaves contained more flavonoids and ω-3 fatty acids but fewer benzophenone derivatives than pods. In contrast, pods were more enriched in bianthrones (sennosides). PCA analysis was found to be equally effective in predicting the origin of the commercial Senna preparation using NMR and/or UPLC-MS datasets. Furthermore, a selection of six so far uninvestigated Senna species were analyzed by UPLC-MS. Results revealed that the Senna alata leaf in terms of secondary metabolite composition is the most closely related species to S. alexandrina Mill, showing the highest levels of the anthraquinone "rhein" and flavonoid conjugates. To the best of our knowledge, this study provides the first approach utilizing both UPLC-MS and NMR to reveal secondary metabolite compositional differences among Senna species.

  6. 含羟基活性基团的聚酰亚胺制备和表征%Preparation and Properties of Polyimides from Diamino Containing Hydroxyl Group, 4,4′-Diamino-4″-Hydroxytriphenylmethan

    Institute of Scientific and Technical Information of China (English)

    路庆华; 李梅; 陶萍; 莫海燕; 魏少华; 王宗光


    合成了一种4,4′-二氨基-4″-羟基三苯甲烷的二胺单体,用该单体分别和芳香性二酐、酯环二酐以及含氟二酐制备了三种含羟基聚酰亚胺,并对其溶解性能和热性能进行了初步研究.发现含羟基二胺单体和含氟二酐生成的聚酰亚胺能溶解在极性非质子溶剂中,且显示出良好的耐热性能,这种聚酰亚胺可通过羟基引入功能基团制备功能性聚酰亚胺.%4,4′-diamino-4″-hydroxyphenyl-triphenylmethan was synthesized and polyhydroxyimides (PHI) based on this diamine and benzophenone-3,3′4,4′-tetracarboxylic acid dianhydride (BTDA), 1,2,4-tricarboxy-3-carboxymethylcyclopentane(TCAAH), hexafluoroisopropylidene 2,2-bis(phthalic acid anhydride) (6FDA) were prepared by solution polycondensation followed by thermal cyclization in refluxing xylene. PHI from 6FDA and DHTM is soluble in aprotonic polar organic solvents such as N-methyl 2-pyrrolidone, N,N-dimethyl acetamide, it has glass transition temperature of 248°C and thermal decomposition temperature above 500°C.

  7. Multi-residue analysis of 36 priority and emerging pollutants in marine echinoderms (Holothuria tubulosa) and marine sediments by solid-liquid extraction followed by dispersive solid phase extraction and liquid chromatography-tandem mass spectrometry analysis. (United States)

    Martín, J; Zafra-Gómez, A; Hidalgo, F; Ibáñez-Yuste, A J; Alonso, E; Vilchez, J L


    Marine echinoderms are filter-feeding invertebrates widely distributed along the coasts, and which are therefore extensively exposed to anthropogenic xenobiotics. They can serve as good sentinels for monitoring a large variety of contaminants in marine ecosystems. In this context, a multi-residue analytical method has been validated and applied to Holothuria tubulosa specimens and marine sediments for the determination of 36 organic compounds, which belong to some of the most problematic groups of emerging and priority pollutants (perfluoroalkyl compounds, estrogens, parabens, benzophenones, plasticizers, surfactants, brominated flame retardants and alkylphenols). Lyophilization of samples prior to solvent extraction and clean-up of extracts with C18, followed by liquid chromatography-tandem mass spectrometry analysis, is proposed. A Box-Behnken design was used for optimization of the most influential variables affecting the extraction and clean-up steps. For validation, matrix-matched calibration and recovery assay were applied. Linearity (% r(2)) higher than 99%, recoveries between 80% and 114% (except in LAS and NP1EO), RSD (precision) lower than 15% and limits of quantification between 0.03 and 12.5ngg(-1) dry weight (d.w.) were achieved. The method was applied to nine samples of Holothuria collected along the coast of Granada (Spain), and to marine sediments around the animals. The results demonstrated high bioaccumulation of certain pollutants. A total of 25 out of the 36 studied compounds were quantified, being surfactants, alkylphenols, perfluoroalkyl compounds, triclocarban and parabens the most frequently detected. Nonylphenol was found in the highest concentration (340 and 323ngg(-1) d.w. in sediment and Holothuria samples, respectively).

  8. Garcinol Upregulates GABAA and GAD65 Expression, Modulates BDNF-TrkB Pathway to Reduce Seizures in Pentylenetetrazole (PTZ)-Induced Epilepsy (United States)

    Hao, Fang; Jia, Li-Hua; Li, Xiao-Wan; Zhang, Ying-Rui; Liu, Xue-Wu


    Background Epilepsy is the most predominant neurological disorder characterized by recurrent seizures. Despite treatment with antiepileptic drugs, epilepsy still is a challenge to treat, due to the associated adverse effects of the drugs. Previous investigations have shown critical roles of BDNF-TrkB signalling and expression of glutamic acid decarboxylase 65 (GAD65) and GABAA in the brain during epilepsy. Thus, drugs that could modulate BDNF-TrkB signal and expression of GAD65 and GABAA could aid in therapy. Recent experimental data have focussed on plant-derived compounds in treatments. Garcinol (camboginol), is a polyisoprenylated benzophenone derived from the fruit of Garcinia indica. We investigated the effects of garcinol in pentylenetetrazole (PTZ)-induced epileptic models. Material/Methods Seizure scores were measured in epilepsy kindled mice. Neuronal degeneration and apoptosis were assessed by Nissl staining, TUNEL assay, and Fluoro-Jade B staining. Immunohistochemistry was performed to evaluate cleaved caspase-3 expressions. Expression of BDNF, TrkB, GABAA, GAD65, Bad, Bcl-2, Bcl-xL, and Bax were determined by western blots. Results Significantly reduced seizure scores and mortality rates were observed with pretreatment with garcinol. Elevated expression of apoptotic proteins and caspase-3 in kindled mice were effectively downregulated by garcinol. Epileptogenic mice presented increased BDNF and TrkB with considerably decreased GABAA and GAD65 expression. Garcinol significantly enhanced GABAA and GAD65 while it suppressed BDNF and TrkB. Garcinol enhanced the performance of mice in Morris water maze tests. Conclusions Garcinol exerts neuroprotective effects via supressing apoptosis and modulating BDNF-TrkB signalling and GAD65/GABAA expressions and also enhanced cognition and memory of the mice. PMID:27855137

  9. A comprehensive scientific overview of Garcinia cambogia. (United States)

    Semwal, Ruchi Badoni; Semwal, Deepak Kumar; Vermaak, Ilze; Viljoen, Alvaro


    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

  10. 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.


    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

  11. The effects of binary UV filter mixtures on the midge Chironomus riparius. (United States)

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


    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.

  12. Development of a thyroperoxidase inhibition assay for high-throughput screening. (United States)

    Paul, Katie B; Hedge, Joan M; Rotroff, Daniel M; Hornung, Michael W; Crofton, Kevin M; Simmons, Steven O


    High-throughput screening (HTPS) assays to detect inhibitors of thyroperoxidase (TPO), the enzymatic catalyst for thyroid hormone (TH) synthesis, are not currently available. Herein, we describe the development of a HTPS TPO inhibition assay. Rat thyroid microsomes and a fluorescent peroxidase substrate, Amplex UltraRed (AUR), were employed in an end-point assay for comparison to the existing kinetic guaiacol (GUA) oxidation assay. Following optimization of assay metrics, including Z', dynamic range, and activity, using methimazole (MMI), the assay was tested with a 21-chemical training set. The potency of MMI-induced TPO inhibition was greater with AUR compared to GUA. The dynamic range and Z' score with MMI were as follows: 127-fold and 0.62 for the GUA assay, 18-fold and 0.86 for the 96-well AUR assay, and 11.5-fold and 0.93 for the 384-well AUR assay. The 384-well AUR assay drastically reduced animal use, requiring one-tenth of the rat thyroid microsomal protein needed for the GUA 96-well format assay. Fourteen chemicals inhibited TPO, with a relative potency ranking of MMI > ethylene thiourea > 6-propylthiouracil > 2,2',4,4'-tetrahydroxy-benzophenone > 2-mercaptobenzothiazole > 3-amino-1,2,4-triazole > genistein > 4-propoxyphenol > sulfamethazine > daidzein > 4-nonylphenol > triclosan > iopanoic acid > resorcinol. These data demonstrate the capacity of this assay to detect diverse TPO inhibitors. Seven chemicals acted as negatives: 2-hydroxy-4-methoxybenzophenone, dibutylphthalate, diethylhexylphthalate, diethylphthalate, 3,5-dimethylpyrazole-1-methanol, methyl 2-methyl-benzoate, and sodium perchlorate. This assay could be used to screen large numbers of chemicals as an integral component of a tiered TH-disruptor screening approach.

  13. A novel photo-grafting of acrylamide onto carboxymethyl starch. 1. Utilization of CMS-g-PAAm in easy care finishing of cotton fabrics. (United States)

    El-Sheikh, Manal A


    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.

  14. 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


    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.

  15. 梯度引发自由基聚合体系(Ⅰ)——基原法合成超高分子量聚合物%Graduation Initiating Radical Polymerization(Ⅰ) ——Synthesis of Hyper-high Molecular Weight Polymers by Free Radical Sources

    Institute of Scientific and Technical Information of China (English)

    杨万泰; 刘涛; 尹梅贞


    There are presently two ways to realize “controlled/living radical polymerization”: one is by a reversible termination or reversible chain transfer to make active polymer chains continuously propagate; the other is by a physical method to suppress chain termination and to prolong radical lifetime. Here we report a new method called Graduation Initiating Radical Polymerization System for realizing “controlled/living radical polymerization”. Its principle and experimental setup are as follows: firstly, initiatable groups(i.e. peroxide groups) were introduced onto the polymer substrates like LDPE film by photo-oxidation reaction; secondly, the films carried peroxide groups were put and fixed to the bottom of polymerization bottle containing monomer and solvent. Afterwards, they were made to produce radicals(by heating or reductive agent), and finally the system polymerization was initiated. Once these radicals are produced on the surface of these films, they will undergo three different processes: terminating by combination, diffusing to monomer solution and taking in monomers(polymerizing). The reactive diffusion makes this system produce “two graduation”: one is the graduation of radical concentration(i.e. the farther away from the surface of the film, the lower radical concentration); the other is the length-graduation of living chains, \\{i.e.\\} the farther away from the surface of the film the longer the propagating chains. By this way, we could obtain a polymerization field where the radical concentration is very low and there are no primary free radicals approximately, which are benefit to realize “controlled/living radical polymerization”. This communication reports the first experimental results based on the above idea: with benzophenone(BP) as photo-catalyst and peroxide groups introduced on the LDPE surface in a concentration 10-8 mol/cm2; by these peroxided films as the sources of free radicals, polyacrylamide and polyacrylic acid were

  16. Dealing with the ubiquity of phthalates in the laboratory when determining plasticizers by gas chromatography/mass spectrometry and PARAFAC. (United States)

    Oca, M L; Rubio, L; Sarabia, L A; Ortiz, M C


    Determining plasticizers and other additives migrated from plastic materials becomes a hard task when these substances are already present in the laboratory environment. This work dealt with this drawback in the multiresidue determination of four plasticizers (2,6-di-tert-butyl-4-methyl-phenol (BHT), diisobutyl phthalate (DiBP), bis(2-ethylhexyl) adipate (DEHA) and diisononyl phthalate (DiNP)) and a UV stabilizer (benzophenone (BP)) by gas chromatography/mass spectrometry (GC/MS) using DiBP-d4 as internal standard. The ubiquity of DiBP by a non-constant leaching process in the laboratory was detected, which could not guarantee the achievement of a trustworthy quantification. To handle this, the assessment of the level of DiBP in solvent blanks having fixed the probabilities of false non-compliance (α) and false compliance (β) at 0.01 was performed. On the other hand, another special case was that of DiNP, in whose chromatogram finger peaks appear because of an array of possible C9 isomers. PARAFAC, used for the identification and quantification of all the substances, is a useful chemometric tool that enabled a more reliable determination of this analyte since no peak areas were considered but chromatographic and spectral loadings. Since phthalates may migrate from rubber latex items, an evaluation of the existence of matrix effects on the determination of the five analytes was conducted prior to an extraction with hexane from a dummy for infants. As matrix effects were present, the quantification of the compounds under study was performed following the standard addition method using PARAFAC sample loadings as response variable. As a result, the presence of BHT was confirmed, being its concentration equal to 37.87μgL(-1). Calibrations based on PARAFAC yielded the following values for the decision limit (CCα): 1.16μgL(-1) for BHT, 1.34μgL(-1) for BP, 1.84μgL(-1) for DEHA and 51.42μgL(-1) for DiNP(for α=0.05 and two replicates).

  17. Functional materials from self-assembled bis-urea macrocycles. (United States)

    Shimizu, Linda S; Salpage, Sahan R; Korous, Arthur A


    -methyl-cyclopentenone, while larger hosts bind and facilitate the photodimerization of coumarin. When the host framework incorporates benzophenone, a triplet sensitizer, UV-irradiation in the presence of oxygen efficiently generates singlet oxygen. Complexes of this host were employed to influence the selectivity of photooxidations of 2-methyl-2-butene and cumene with singlet oxygen. Small systematic changes in the channel and bound reactants should enable systematic evaluation of the effects of channel dimensions, guest dimensions, and channel-guest interactions on the processes of absorption, diffusion, and reaction of guests within these nanochannels. Such studies could help in the development of new materials for separations, gas storage, and catalysis.

  18. Direct evidence that scorpion α-toxins (site-3 modulate sodium channel inactivation by hindrance of voltage-sensor movements.

    Directory of Open Access Journals (Sweden)

    Zhongming Ma

    Full Text Available The position of the voltage-sensing transmembrane segment, S4, in voltage-gated ion channels as a function of voltage remains incompletely elucidated. Site-3 toxins bind primarily to the extracellular loops connecting transmembrane helical segments S1-S2 and S3-S4 in Domain 4 (D4 and S5-S6 in Domain 1 (D1 and slow fast-inactivation of voltage-gated sodium channels. As S4 of the human skeletal muscle voltage-gated sodium channel, hNav1.4, moves in response to depolarization from the resting to the inactivated state, two D4S4 reporters (R2C and R3C, Arg1451Cys and Arg1454Cys, respectively move from internal to external positions as deduced by reactivity to internally or externally applied sulfhydryl group reagents, methane thiosulfonates (MTS. The changes in reporter reactivity, when cycling rapidly between hyperpolarized and depolarized voltages, enabled determination of the positions of the D4 voltage-sensor and of its rate of movement. Scorpion α-toxin binding impedes D4S4 segment movement during inactivation since the modification rates of R3C in hNav1.4 with methanethiosulfonate (CH3SO2SCH2CH2R, where R = -N(CH33 (+ trimethylammonium, MTSET and benzophenone-4-carboxamidocysteine methanethiosulfonate (BPMTS were slowed ~10-fold in toxin-modified channels. Based upon the different size, hydrophobicity and charge of the two reagents it is unlikely that the change in reactivity is due to direct or indirect blockage of access of this site to reagent in the presence of toxin (Tx, but rather is the result of inability of this segment to move outward to the normal extent and at the normal rate in the toxin-modified channel. Measurements of availability of R3C to internally applied reagent show decreased access (slower rates of thiol reaction providing further evidence for encumbered D4S4 movement in the presence of toxins consistent with the assignment of at least part of the toxin binding site to the region of D4S4 region of the voltage


    Directory of Open Access Journals (Sweden)

    Vivi Lisdawati


    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

  20. Synthesis of a mononuclear, non-square-planar chromium(ii) bis(alkoxide) complex and its reactivity toward organic carbonyls and CO2. (United States)

    Yousif, Maryam; Cabelof, Alyssa C; Martin, Philip D; Lord, Richard L; Groysman, Stanislav


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ozáez, Irene; Morcillo, Gloria; Martínez-Guitarte, José-Luis, E-mail:


    Organic ultraviolet (UV) filters are used in a wide variety of products, including cosmetics, to prevent damage from UV light in tissues and industrial materials. Their extensive use has raised concerns about potential adverse effects in human health and aquatic ecosystems that accumulate these pollutants. To increase sun radiation protection, UV filters are commonly used in mixtures. Here, we studied the toxicity of binary mixtures of 4-methylbenzylidene camphor (4MBC), octyl-methoxycinnamate (OMC), and benzophenone-3 (BP-3), by evaluating the larval mortality of Chironomus riparius. Also molecular endpoints have been analyzed, including alterations in the expression levels of a gene related with the endocrine system (EcR, ecdysone receptor) and a gene related with the stress response (hsp70, heat shock protein 70). The results showed that the mortality caused by binary mixtures was similar to that observed for each compound alone; however, some differences in LC50 were observed between groups. Gene expression analysis showed that EcR mRNA levels increased in the presence of 0.1 mg/L 4MBC but returned to normal levels after exposure to mixtures of 4MBC with 0.1, 1, and 10 mg/L of BP-3 or OMC. In contrast, the hsp70 mRNA levels increased after exposure to the combinations tested of 4MBC and BP-3 or OMC mixtures. These data suggest that 4MBC, BP-3, and OMC may have antagonist effects on EcR gene transcription and a synergistic effect on hsp70 gene activation. This is the first experimental study to show the complex patterned effects of UV filter mixtures on invertebrates. The data suggest that the interactions within these chemicals mixtures are complex and show diverse effects on various endpoints. - Highlights: • Chironomus riparius is sensitive to UV filter binary mixtures. • UV filters binary mixtures show antagonism on survival of 4th instar larvae. • BP-3 and OMC antagonize the stimulatory effect of 4MBC on EcR gene. • 4MBC, OMC, and BP-3 induce hsp70

  2. Evaluating the potential for recycling all PET bottles into new food packaging. (United States)

    Begley, T H; McNeal, T P; Biles, J E; Paquette, K E


    To evaluate the feasibility of recycling all PET bottles into food packaging, realistic estimates of the maximum concentration of contaminants that might be expected in the polymer are needed. To estimate the maximum concentration of a contaminant that might be in PET from the storage of non-food substances, sorption experiments into two types of PET were performed. These test materials were 0.8mm thick amorphous PET (a relative sink for contaminants) and commercial PET bottle wall. Using a commercial shampoo containing 1% lindane (C6H6Cl6), the test materials were stored in contact with the shampoo at 20 and 40 degrees C for 231 days. This commercial shampoo also represents an extreme case because it contains 7% acetone, a solvent which swells PET, further enhancing sorption of chemicals. Additional sorption experiments into PET were performed by preparing solutions of 10% toluene in Miglyol (a fractionated coconut oil), 10% benzophenone in Miglyol, 5% 2-butoxyethoxy ethanol (2-BE) in 50/50 water/ethanol, and 10% methyl stearate in heptane. Sorption data from the shampoo into PET illustrate Fickian behaviour. Specifically, the amount of sorption at room temperature is approximately40 times less than that at 40 degrees C. The amount of lindane sorbed into PET from the shampoo after 231 days was 0.1 and 3.7 mgdm(-2) at 20 and 40 degrees C respectively. These values correspond to 28 and 765 mg kg(-1) on a mass/mass basis. All sorptions are within the ranges measured and published by other authors using surrogate contamination testing schemes. Additionally, actual bottles from recycle bins were analysed for the amout of contamination. Results are discussed in terms of potential consumer exposure to non-food contaminants in food containers made of recycled PET and in relation to the surrogate testing methods recommended by the Food and Drug Administration (FDA) for determining the compatibility of a PET recycling process to produce containers suitable for food

  3. Removal of micro pollutants using activated biochars and powdered activated carbon in water (United States)

    Kim, E.; Jung, C.; Han, J.; Son, A.; Yoon, Y.


    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

  4. 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

  5. Reducing Phthalate, Paraben, and Phenol Exposure from Personal Care Products in Adolescent Girls: Findings from the HERMOSA Intervention Study (United States)

    Harley, Kim G.; Kogut, Katherine; Madrigal, Daniel S.; Cardenas, Maritza; Vera, Irene A.; Meza-Alfaro, Gonzalo; She, Jianwen; Gavin, Qi; Zahedi, Rana; Bradman, Asa; Eskenazi, Brenda; Parra, Kimberly L.


    Background: Personal care products are a source of exposure to potentially endocrine-disrupting chemicals such as phthalates, parabens, triclosan, and benzophenone-3 (BP-3) for adolescent girls. Methods: We enrolled 100 Latina girls in a youth-led, community-based participatory research intervention study to determine whether using personal care products whose labels stated they did not contain these chemicals for 3 days could lower urinary concentrations. Pre- and postintervention urine samples were analyzed for phthalate metabolites, parabens, triclosan, and BP-3 using high-performance liquid chromatography/tandem mass spectrometry. Results: Urinary concentrations of mono-ethyl phthalate (MEP) decreased by 27.4% (95% CI: –39.3, –13.2) on average over the 3-day intervention; no significant changes were seen in urinary concentrations of mono-n-butyl phthalate (MnBP) and mono-isobutyl phthalate (MiBP). Methyl and propyl paraben concentrations decreased by 43.9% (95% CI: –61.3, –18.8) and 45.4% (95% CI: –63.7, –17.9), respectively. Unexpectedly, concentrations of ethyl and butyl paraben concentrations increased, although concentrations were low overall and not detected in almost half the samples. Triclosan concentrations decreased by 35.7% (95% CI: –53.3, –11.6), and BP-3 concentrations decreased by 36.0% (95% CI: –51.0, –16.4). Discussion: This study demonstrates that techniques available to consumers, such as choosing personal care products that are labeled to be free of phthalates, parabens, triclosan, and BP-3, can reduce personal exposure to possible endocrine-disrupting chemicals. Involving youth in the design and implementation of the study was key to recruitment, retention, compliance, and acceptability of the intervention. Citation: Harley KG, Kogut K, Madrigal DS, Cardenas M, Vera IA, Meza-Alfaro G, She J, Gavin Q, Zahedi R, Bradman A, Eskenazi B, Parra KL. 2016. Reducing phthalate, paraben, and phenol exposure from personal care

  6. Accumulation of 19 environmental phenolic and xenobiotic heterocyclic aromatic compounds in human adipose tissue. (United States)

    Wang, Lei; Asimakopoulos, Alexandros G; Kannan, Kurunthachalam


    The extensive use of environmental phenols (e.g., bisphenol A) and heterocyclic aromatic compounds (e.g., benzothiazole) in consumer products as well as widespread exposure of humans to these compounds have been well documented. Biomonitoring studies have used urinary measurements to assess exposures, based on the assumption that these chemicals are metabolized and eliminated in urine. Despite the fact that some of these chemicals are moderately lipophilic, the extent of their accumulation in adipose fat tissues has not been convincingly demonstrated. In this study, human adipose fat samples (N=20) collected from New York City, USA, were analyzed for the presence of environmental phenols, including bisphenol A (BPA), benzophenone-3 (BP-3), triclosan (TCS), and parabens, as well as heterocyclic aromatic compounds, including benzotriazole (BTR), benzothiazole (BTH), and their derivatives. BPA and TCS were frequently detected in adipose tissues at concentrations (geometric mean [GM]: 3.95ng/g wet wt for BPA and 7.21ng/g wet wt for TCS) similar to or below the values reported for human urine. High concentrations of BP-3 were found in human adipose tissues (GM: 43.4; maximum: 4940ng/g wet wt) and a positive correlation between BP-3 concentrations and donor's age was observed. The metabolite of parabens, p-hydroxybenzoic acid (p-HB), also was found at elevated levels (GM: 4160; max.: 17,400ng/g wet wt) and a positive correlation between donor's age and sum concentration of parabens and p-HB were found. The GM concentrations of BTR and BTH in human adipose tissues were below 1ng/g, although the methylated forms of BTR (i.e., TTR and XTR) and the hydrated form of BTH (i.e., 2-OH-BTH) were frequently detected in adipose samples, indicating widespread exposure to these compounds. Our results suggest that adipose tissue is an important repository for BP-3 and parabens, including p-HB, in the human body.

  7. Bisphenol A and other phenols in urine from Danish children and adolescents analyzed by isotope diluted TurboFlow-LC-MS/MS. (United States)

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


    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

  8. Cationic methyl complexes of the rare-earth metals: an experimental and computational study on synthesis, structure, and reactivity. (United States)

    Kramer, Mathias U; Robert, Dominique; Arndt, Stefan; Zeimentz, Peter M; Spaniol, Thomas P; Yahia, Ahmed; Maron, Laurent; Eisenstein, Odile; Okuda, Jun


    Synthesis, structure, and reactivity of two families of rare-earth metal complexes containing discrete methyl cations [LnMe(2-x)(thf)n]((1+x)+) (x = 0, 1; thf = tetrahydrofuran) have been studied. As a synthetic equivalent for the elusive trimethyl complex [LnMe3], lithium methylates of the approximate composition [Li3LnMe6(thf)n] were prepared by treating rare-earth metal trichlorides [LnCl3(thf)n] with 6 equiv of methyllithium in diethyl ether. Heteronuclear complexes of the formula [Li3Ln2Me9L(n)] (Ln = Sc, Y, Tb; L = Et2O, thf) were isolated by crystallization from diethyl ether. Single crystal X-ray diffraction studies revealed a heterometallic aggregate of composition [Li3Ln2Me9(thf)n(Et2O)m] with a [LiLn2Me9](2-) core (Ln = Sc, Y, Tb). When tris(tetramethylaluminate) [Ln(AlMe4)3] (Ln = Y, Lu) was reacted with less than 1 equiv of [NR3H][BPh4], the dimethyl cations [LnMe2(thf)n][BPh4] were obtained. The coordination number as well as cis/trans isomer preference was studied by crystallographic and computational methods. Dicationic methyl complexes of the rare-earth metals of the formula [LnMe(thf)n][BAr4]2 (Ln = Sc, Y, La-Nd, Sm, Gd-Lu; Ar = Ph, C6H4F-4) were synthesized, by protonolysis of either the ate complex [Li3LnMe6(thf)n] (Ln = Sc, Y, Gd-Lu) or the tris(tetramethylaluminate) [Ln(AlMe4)3] (Ln = La-Nd, Sm, Dy, Gd) with ammonium borates [NR3H][BAr4] in thf. The number of coordinated thf ligands varied from n = 5 (Ln = Sc, Tm) to n = 6 (Ln = La, Y, Sm, Dy, Ho). The configuration of representative examples was determined by X-ray diffraction studies and confirmed by density-functional theory calculations. The highly polarized bonding between the methyl group and the rare-earth metal center results in the reactivity pattern dominated by the carbanionic character and the pronounced Lewis acidity: The dicationic methyl complex [YMe(thf)6](2+) inserted benzophenone as an electrophile to give the alkoxy complex [Y(OCMePh2)(thf)5](2+). Nucleophilic addition of

  9. 紫外光接枝丙烯酸改性废胶粉工艺优化及其复合材料的力学性能%Process Optimization of UV-induced Photografting Acrylic Acid onto Waste Rubber Powder and Mechanical Property of the Composite

    Institute of Scientific and Technical Information of China (English)

    丁国新; 夏明; 张智敏; 王彬


    The surface of waste rubber powder (WRP) grafted with acrylic acid (APt) was performed under the inducing of ultraviolet (UV) using benzophenone (BP) as photosensitizer. The fabrication parameters were optimized via orthogonal method. The modified WRP/natural rubber (NR) composites were fabricated. The surface morphology and structures of WRP before and after modified, and the effects of WRP content on the mechanical properties of WRP/NR composites were studied. Results show that the highest grafting degree of 3. 38% was gained in the optimized condition with 10wt% AA, 9wt % BP, 150μm grain size of WRP and 4 min of illumination time. The rougher surface of modified WRP was observed when compared with the unmodified samples. The tensile strength and Shore A hardness were increased first, and then decreased with the content of modified WRP increased, and the peak values (27. 28 MPa and 69.2 HSA, respectively) were obtained when 10wt% WRP added.%以丙烯酸为接枝单体,二苯甲酮为光敏剂,在紫外光的引发下对废胶粉进行表面接枝,用正交方法对改性工艺进行了优化,制备了改性废胶粉/天然橡胶复合材料,表征了改性前后废胶粉的表面形貌和结构,考察了其加入量对复合材料力学性能的影响。结果表明:当丙烯酸和二苯甲酮与废胶粉的质量比分别为10%和9%,废胶粉粒径为150μm和光照时间为4min时,为最佳工艺条件,此时接枝率最高,达3.38%;接枝改性后的废胶粉表面粗糙度增加;随改性废胶粉含量的增加,复合材料的拉伸强度和邵氏A硬度先增大后降低,并在质量分数10%时达到最大值,分别为27.28MPa和69.2HSA。

  10. Optimisation of an analytical method and results from the inter-laboratory comparison of the migration of regulated substances from food packaging into the new mandatory European Union simulant for dry foodstuffs. (United States)

    Jakubowska, Natalia; Beldì, Giorgia; Peychès Bach, Aurélie; Simoneau, Catherine


    This paper presents the outcome of the development, optimisation and validation at European Union level of an analytical method for using poly(2,6-diphenyl phenylene oxide--PPPO), which is stipulated in Regulation (EU) No. 10/2011, as food simulant E for testing specific migration from plastics into dry foodstuffs. Two methods for fortifying respectively PPPO and a low-density polyethylene (LDPE) film with surrogate substances that are relevant to food contact were developed. A protocol for cleaning the PPPO and an efficient analytical method were developed for the quantification of butylhydroxytoluene (BHT), benzophenone (BP), diisobutylphthalate (DiBP), bis(2-ethylhexyl) adipate (DEHA) and 1,2-cyclohexanedicarboxylic acid, diisononyl ester (DINCH) from PPPO. A protocol for a migration test from plastics using small migration cells was also developed. The method was validated by an inter-laboratory comparison (ILC) with 16 national reference laboratories for food contact materials in the European Union. This allowed for the first time data to be obtained on the precision and laboratory performance of both migration and quantification. The results showed that the validation ILC was successful even when taking into account the complexity of the exercise. The results showed that the method performance was 7-9% repeatability standard deviation (rSD) for most substances (regardless of concentration), with 12% rSD for the high level of BHT and for DiBP at very low levels. The reproducibility standard deviation results for the 16 European Union laboratories were in the range of 20-30% for the quantification from PPPO (for the three levels of concentrations of the five substances) and 15-40% from migration experiments from the fortified plastic at 60°C for 10 days and subsequent quantification. Considering the lack of data previously available in the literature, this work has demonstrated that the validation of a method is possible both for migration from a film and for

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

    Energy Technology Data Exchange (ETDEWEB)

    Wishart, J.F.


    , 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.

  12. Occurrence of organic wastewater and other contaminants in cave streams in northeastern Oklahoma and northwestern Arkansas (United States)

    Bidwell, Joseph R.; Becker, C.; Hensley, S.; Stark, R.; Meyer, M.T.


    The prevalence of organic wastewater compounds in surface waters of the United States has been reported in a number of recent studies. In karstic areas, surface contaminants might be transported to groundwater and, ultimately, cave ecosystems, where they might impact resident biota. In this study, polar organic chemical integrative samplers (POCISs) and semipermeable membrane devices (SPMDs) were deployed in six caves and two surface-water sites located within the Ozark Plateau of northeastern Oklahoma and northwestern Arkansas in order to detect potential chemical contaminants in these systems. All caves sampled were known to contain populations of the threatened Ozark cavefish (Amblyopsis rosae). The surface-water site in Oklahoma was downstream from the outfall of a municipal wastewater treatment plant and a previous study indicated a hydrologic link between this stream and one of the caves. A total of 83 chemicals were detected in the POCIS and SPMD extracts from the surface-water and cave sites. Of these, 55 chemicals were detected in the caves. Regardless of the sampler used, more compounds were detected in the Oklahoma surface-water site than in the Arkansas site or the caves. The organic wastewater chemicals with the greatest mass measured in the sampler extracts included sterols (cholesterol and ??-sitosterol), plasticizers [diethylhexylphthalate and tris (2-butoxyethyl) phosphate], the herbicide bromacil, and the fragrance indole. Sampler extracts from most of the cave sites did not contain many wastewater contaminants, although extracts from samplers in the Oklahoma surfacewater site and the cave hydrologically linked to it had similar levels of diethylhexyphthalate and common detections of carbamazapine, sulfamethoxazole, benzophenone, N-diethyl-3-methylbenzamide (DEET), and octophenol monoethoxylate. Further evaluation of this system is warranted due to potential ongoing transport of wastewaterassociated chemicals into the cave. Halogenated organics

  13. Separation of chemical constituents from three plant medicines by counter-current chromatography using a three-phase solvent system at a novel ratio. (United States)

    Wu, Xiaoyi; Chao, Zhimao; Wang, Chun; Yu, Li


    A solvent system of n-hexane, methyl acetate, acetonitrile, and water at a novel volume ratio of 4:3:4:4 forms three layers, i.e. upper phase (UP), middle phase (MP), and lower phase (LP), with a volume ratio of 1:1.20:1.42 at room temperature (25°C). All three two-phases from this three-phase solvent system were successfully used to separate some chemical constituents from three plant medicines with counter-current chromatography (CCC). Eight coumarins (B1-B8) were obtained from petroleum ether extract of fresh roots of Angelica dahurica (Baizhi) with a stationary phase of UP and a mobile phase of LP. Six diarylheptanoids (L1-L6) were obtained from petroleum ether extract of dried rhizomes of Alpinia officinarum (Liangjiang) with a stationary phase of UP and a mobile phase of MP. Three chemical constituents (Z1-Z3) were obtained from ethyl acetate extract of fresh rhizomes of Anemarrhena asphodeloides (Zhimu) with a stationary phase of MP and a mobile phase of LP. Preparative HPLC was used for further purification if necessary. Seventeen chemical constituents were identified as oxypeucedanin hydrate (B1), byakangelicin (B2), byakangelicol (B3), bergapten (B4), oxypeucedanin (B5), imperatorin (B6), phellopterin (B7), isoimperatorin (B8), 5-hydroxy-7-(4-hydroxy-3-methoxyphenyl)-1-phenyl-3-heptanone (L1), 7-(4-hydroxy-3-methoxyphenyl)-1-phenyl-4E-en-3-heptanone (L2), 5-hydroxy-1,7-diphenyl-3-heptanone (L3), 1,7-diphenyl-4E-en-3-heptanone (L4), 5-hydroxy-1,7-diphenyl-4E,6E-dien-3-heptanone (L5), isomers of 1,7-diphenyl-3,5-heptandione and 5-hydroxy-1,7-diphenyl-4E-en-3-heptanone (L6), mangiferin (Z1), timosaponin A-III (Z2), and 2,6,4'-trihydroxy-4-methoxy-benzophenone (Z3) by means of MS, (1)H and (13)C NMR studies. Five compounds of B3, L3, L5, L6, and Z3 were isolated by CCC for the first time.

  14. Photoaffinity antigens for human γδ T cells1 (United States)

    Sarikonda, Ghanashyam; Wang, Hong; Puan, Kia-Joo; Liu, Xiao-hui; Lee, Hoi K.; Song, Yongcheng; Distefano, Mark D.; Oldfield, Eric; Prestwich, Glenn D.; Morita, Craig T.


    Vγ2Vδ2 T cells comprise the major subset of peripheral blood γ δ T cells in humans and expand during infections by recognizing small, nonpeptide prenyl pyrophosphates. These molecules include (E)-4-hydroxy-3-methyl-but-2-enyl-pyrophosphate (HMBPP), a microbial isoprenoid intermediate, and isopentenyl pyrophosphate (IPP), an endogenous isoprenoid intermediate. Recognition of these nonpeptide antigens is mediated by the Vγ2Vδ2 T cell antigen receptor (TCR). Several findings suggest that prenyl pyrophosphates are presented by an antigen presenting molecule: contact between T cells and APCs is required; the antigens do not bind the Vγ2Vδ2 TCR directly; and antigen recognition is abrogated by TCR mutations in CDRs distant from the putative antigen recognition site. Identification of the putative antigen presenting molecule, however, has been hindered by the inability to achieve stable association of nonpeptide prenyl pyrophosphate antigens with the presenting molecule. In this study, we show that photoaffinity analogs of HMBPP, meta/para-benzophenone-(methylene)-prenyl pyrophosphates (m/p-BZ-(C)-C5-OPP), can cross-link to the surface of tumor cell lines and be presented as antigens to γ δ T cells. Mutant tumor cell lines lacking MHC class I, MHC class II, β2-microglobulin, and CD1, as well as tumor cell lines from a variety of tissues and individuals, will all crosslink to and present m-BZ-C5-OPP. Finally, pulsing of BZ-(C)-C5-OPP is inhibited by IPP and an inactive analog, suggesting that they bind to the same molecule. Taken together, these results suggest that nonpeptide antigens are presented by a novel antigen presenting molecule that is widely distributed, non-polymorphic, but not classical MHC class I, MHC class II, or CD1. This is an author-produced version of a manuscript accepted for publication in The Journal of Immunology (The JI). The American Association of Immunologists, Inc. (AAI), publisher of The JI, holds the copyright to this manuscript

  15. Multiple hormonal activities of UV filters and comparison of in vivo and in vitro estrogenic activity of ethyl-4-aminobenzoate in fish. (United States)

    Kunz, Petra Y; Fent, Karl


    UV filters have been detected in surface water, wastewater and fish, and some of them are estrogenic in fish. At present, little is known about their additional hormonal activities in different hormonal receptor systems despite their increasing use and environmental persistence. Besides estrogenic activity, UV filters may have additional activities, both agonistic and antagonistic in aquatic organisms. In our study, we investigate a series of UV filters for multiple hormonal activities in vitro in human receptor systems and evaluate the predictive value of these findings for the activity in fish in vitro and in vivo. First we systematically analysed the estrogenic, antiestrogenic, androgenic, and antiandrogenic activity of 18 UV filters and one metabolite in vitro at non-cytotoxic concentrations with recombinant yeast systems carrying either a human estrogen (hERalpha) or androgen receptor (hAR). All 19 compounds elicited hormonal activities, surprisingly most of them multiple activities. We found 10 UV-filters having agonistic effects towards the hERalpha. Surprisingly, we identified for the first time six UV filters with androgenic activities and many of them having pronounced antiestrogenic and antiandrogenic activities. As much as 17 compounds inhibited 4,5-dihydrotestosterone activity in the hAR assay, while 14 compounds inhibited estradiol activity in the hERalpha assay, indicating antiandrogenic and antiestrogenic activity, respectively. In particular, the antiandrogenic activities of phenyl- and benzyl salicylate, benzophenone-1 and -2, and of 4-hydroxybenzophenone were higher than that of flutamide, a known hAR antagonist. In a second series of experiments, we investigated the predictive power of the hERalpha assay for aquatic organisms by further investigating the estrogenic UV filter ethyl 4-aminobenzoate (Et-PABA) in vitro and in vivo in fish. Et-PABA showed estrogenic activity in a recombinant yeast system carrying the rainbow trout estrogen receptor

  16. Removal of micropollutants from aerobically treated grey water via ozone and activated carbon. (United States)

    Hernández-Leal, L; Temmink, H; Zeeman, G; Buisman, C J N


    Ozonation and adsorption onto activated carbon were tested for the removal micropollutants of personal care products from aerobically treated grey water. MilliQ water spiked with micropollutants (100-1600 μgL(-1)) was ozonated at a dosing rate of 1.22. In 45 min, this effectively removed (>99%): Four parabens, bisphenol-A, hexylcinnamic aldehyde, 4-methylbenzylidene-camphor (4MBC), benzophenone-3 (BP3), triclosan, galaxolide and ethylhexyl methoxycinnamate. After 60 min, the removal efficiency of benzalkonium chloride was 98%, tonalide and nonylphenol 95%, octocrylene 92% and 2-phenyl-5-benzimidazolesulfonic acid (PBSA) 84%. Ozonation of aerobically treated grey water at an applied ozone dose of 15 mgL(-1), reduced the concentrations of octocrylene, nonylphenol, triclosan, galaxolide, tonalide and 4-methylbenzylidene-camphor to below limits of quantification, with removal efficiencies of at least 79%. Complete adsorption of all studied micropollutants onto powdered activated carbon (PAC) was observed in batch tests with milliQ water spiked with 100-1600 μgL(-1) at a PAC dose of 1.25 gL(-1) and a contact time of 5 min. Three granular activated carbon (GAC) column experiments were operated to treat aerobically treated grey water. The operation of a GAC column with aerobically treated grey water spiked with micropollutants in the range of 0.1-10 μgL(-1) at a flow of 0.5 bed volumes (BV)h(-1) showed micropollutant removal efficiencies higher than 72%. During the operation time of 1728 BV, no breakthrough of TOC or micropollutants was observed. Removal of micropollutants from aerobically treated grey water was tested in a GAC column at a flow of 2 BVh(-1). Bisphenol-A, triclosan, tonalide, BP3, galaxolide, nonylphenol and PBSA were effectively removed even after a stable TOC breakthrough of 65% had been reached. After spiking the aerobically treated effluent with micropollutants to concentrations of 10-100 μgL(-1), efficient removal to below limits of quantification

  17. Leaching of plastic polymers by plastic vials used for storing homoeopathic medicines: A preliminary study

    Directory of Open Access Journals (Sweden)

    Neeraj Gupta


    Full Text Available Background: In Homoeopathy, plastic containers/vials are used for the storing/dispensing of ethanol-based medicines instead of glass. Various studies have suggested that plastic components that leach out in stored substances tend to cause contamination and may produce adverse effects in living systems. The present study was aimed to find out chemical composition and leaching behaviour of commonly used plastic vials (PVs if any during the storage of ethanol-based homoeopathic medicines in optimal environment. Material and Methods: The experiments were conducted on two sample sets of PVs. Chemical properties of PV were assessed by Fourier Transform Infrared Attenuated Total Reflectance (FTIR-ATR spectroscopy. PV were cut separately [sample-1 (S-1 and sample-2 (S-2] and immersed in Homoeopathic Grade Ethanol (HGE in conical flask and stored for 7 days at ambient temperature (25° ± 5C with constant rotary shaking. After 7 days, S-1 and S-2 of PV in Homoeopathic Grade Ethanol (HGE were decanted and filtered. Aliquots (A1 and A2 were analysed by proton nuclear magnetic resonance spectroscopy (H 1 NMR. The spectral graph obtained by FTIR-ATR spectroscopy for PV compositions and spectral graph obtained by H 1 NMR spectroscopy for PV ethanol aliquots were examined for PVs material and PV leaching effect in HGE. Results: FTIR-ATR spectra showed that PV are made up of two types of polyolefin′s compounds i.e. Low Density Polyethylene (LDPE and Linear Low Density Polyethylene (LLDPE. Aliquots of PV in HGE showed the presence benzophenone and its methyl derivative, heat and light stabiliser (2, 2, 6, 6-tetramethylpiperidine and amino derivative, antioxidant (4, 4′- thiobis and 2-tertbutyl-5-methylphenol and plasticizer bis 2-Diethylhexyl phthalate (DEHP or Dioctyl phthalate (DOP. Results of study suggest that PVs leach out plastic polymers in HGE. Conclusion: This preliminary experiment suggests that it is not safe to use LDPE/LLDPE plastic for storing

  18. Reactivity of the uranium(IV) carbene complex [U(BIPM(TMS))(Cl)(μ-Cl)₂Li(THF)₂] (BIPM(TMS) = {C(PPh₂NSiMe₃)₂}) towards carbonyl and heteroallene substrates: metallo-Wittig, adduct formation, C-F bond activation, and [2 + 2]-cycloaddition reactions. (United States)

    Cooper, Oliver J; Mills, David P; Lewis, William; Blake, Alexander J; Liddle, Stephen T


    The reactivity of the uranium(IV) carbene complex [U(BIPM(TMS))(Cl)(μ-Cl)2Li(THF)2] (1, BIPM(TMS) = {C(PPh2NSiMe3)2}) towards carbonyl and heteroallene substrates is reported. Reaction of 1 with benzophenone proceeds to give the metallo-Wittig terminal alkene product Ph2C=C(PPh2NSiMe3)2 (2); the likely "UOCl2" byproduct could not be isolated. Addition of the bulky ketone PhCOBu(t) to 1 resulted in loss of LiCl, coordination of the ketone, and dimerisation to give [U(BIPM(TMS))(Cl)(μ-Cl){OC(Ph)(Bu(t))}]2 (3). The reaction of 1 with coumarin resulted in ring opening of the cyclic ester and a metallo-Wittig-type reaction to afford [U{BIPM(TMS)[C(O)(CHCHC6H4O-2)]-κ(3)-N,O,O'}(Cl)2(THF)] (4) where the enolate product remains coordinated to uranium. The reaction of PhCOF with 1 resulted in C-F bond activation and oxidation resulting in isolation of [U(O)2(Cl)2(μ-Cl)2{(μ-LiDME)OC(Ph)=C(PPh2NSiMe3)(PPh2NHSiMe3)}2] (5) along with [U(Cl)2(F)2(py)4] (6). The reactions of 1 with tert-butylisocyanate or dicyclohexylcarbodiimide resulted in the isolation of the [2 + 2]-cycloaddition products [U{BIPM(TMS)[C(NBu(t)){OLi(THF)2(μ-Cl)Li(THF)3}]-κ(4)-C,N,N',N''}(Cl)3] (7) and [U{BIPM(TMS)[C(NCy)2]-κ(4)-C,N,N',N''}(Cl)(μ-Cl)2Li(THF)2] (8). Complexes 2-8 have been variously characterised by single crystal X-ray diffraction, multi-nuclear NMR and FTIR spectroscopies, Evans method solution magnetic moments, variable temperature SQUID magnetometry, and elemental analyses.

  19. Bespoke contrast-matched diblock copolymer nanoparticles enable the rational design of highly transparent Pickering double emulsions (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.


    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

  20. Alkylphenols, Other Endocrine-Active Chemicals, and Fish Responses in Three Streams in Minnesota - Study Design and Data, February-September 2007 (United States)

    Lee, Kathy E.; Schoenfuss, Heiko L.; Jahns, Nathan D.; Brown, Greg K.; Barber, Larry B.


    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

  1. Migration measurement and modelling from poly(ethylene terephthalate) (PET) into soft drinks and fruit juices in comparison with food simulants. (United States)

    Franz, R; Welle, F


    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

  2. Effects of garcinol on the radiosensitivity of human cervical cancer Hela cells%garcinol对宫颈癌Hela细胞放射敏感性影响的研究

    Institute of Scientific and Technical Information of China (English)

    孙玲娣; 王侠; 张艳; 章龙珍


    目的:研究多聚异戊二烯基苯甲酮( garcinol )对宫颈癌Hela细胞株放射敏感性的影响。方法不同浓度garcinol作用于人宫颈癌Hela细胞12、24、48 h,CCK-8法检测garcinol对Hela细胞增殖活性的影响,并计算出24 h时的20%和50%的药物抑制浓度( IC20和IC50)值;克隆形成实验检测20μmol/L garcinol对Hela 细胞放射敏感性的影响;反转录PCR法和Western blot法检测Hela细胞内环氧化酶-2(cyclooxygenase -2, COX-2)在mRNA水平和蛋白表达水平的变化。结果 garcinol抑制宫颈癌Hela细胞的生长,并且有明显的时间-剂量依赖性;通过单击多靶模型计算放射生物学参数,经20μmol/L garcinol处理24 h的 Hela细胞,与单纯照射组相比,放射敏感性增加(t=6.69,P<0.05),放射增敏比(SER)为1.26;经20μmol/L garcinol 处理24 h的Hela细胞,COX-2的蛋白表达水平下降(P<0.05),而COX-2 mRNA水平无明显变化(P>0.05)。结论 garcinol 可以增加宫颈癌Hela细胞的放射敏感性,这可能与其降低Hela细胞中COX-2的蛋白表达水平有关。%Objective To investigate the effects of polyisoprenylated benzophenone ( garcino ) on the radiosensitivity of human cervical cancer Hela cells .Methods Hela cells were exposed to different concentrations of garcinol for 12 , 24 and 48 hours.The proliferative rate of the cells was detected by CCK -8 assay, while the values of IC20 and IC50 were calculated after 24 hours of incubation .Clonogenic survival assay was adopted to evaluate the effects of 20μmol/L garci-nol on the radiosensitivity of Hela cells .The levels of COX -2 mRNA and protein were measured by RT -PCR and Western blotting , respectively .Results Garcinol could inhibit the growth of Hela cells in time -and dose -dependent ways.Incubation with 20μmol/L garcinol for 24 house stimulated the radiosensitivity of the cells (t=6.69, P0.05 ) .Conclusion Garcinol can enhance

  3. Application of carbon dioxide towards the development of smart materials, green reaction schemes and metallic nanoparticle synthesis (United States)

    Mohammed, Fiaz S.

    energy consumption due to a separate deprotection reaction. To solve this dilemma, the reversible protection of amines using CO2 induced carbamates was demonstrated in chapter 3; by reducing n-alkyl benzophenone imine and n-phenyl, nalkylurea yields by up to 67% compared to non-protected amines. The applicability of this chemistry to these classes of nucleophilic substitution reactions and has significant potential to alter the way we approach amine protection in organic synthesis. Another research area that has grown popularity over the last decade is the development of metallic nanoparticles, specifically gold nanoparticles (GNPs), due to their size and shape dependent optical and catalytic properties. Chapter 4 of this dissertation demonstrates the successful application of polyethylene imine (PEI) in the synthesis of cationic GNPs, which are of significant interest for biomedical applications. In this work, we investigated the effect of pH, PEI concentration and reduction method on the size and stability of amine-stabilized gold and silver nanoparticles. Furthermore the potential of carbon dioxide as a stabilizing aid through reversible carbamate formation was explored, leading to a decrease in particle size at ambient temperature along with an increase in stability. In summary, this work has demonstrated the great potential of employing the reversible reaction of carbon dioxide with primary and secondary amines as an effective and greener alternative to conventional methods in a diversity of fields that include "smart" materials, organic chemistry, and functional nanomaterials.

  4. Flavonoids of Lonchocarpus montanus A.M.G. Azevedo and biological activity

    Directory of Open Access Journals (Sweden)

    Aderbal F. Magalhães


    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

  5. Water quality and possible sources of nitrate in the Cimarron Terrace Aquifer, Oklahoma, 2003 (United States)

    Masoner, Jason R.; Mashburn, Shana L.


    detected, 11 compounds were from household chemicals, 3 compounds were hydrocarbons, 2 compounds were industrial chemicals, 2 compounds were pesticides, 1 compound was of animal source, and 1 compound was a detergent compound. The most frequently detected wastewater compound was phenol, which was detected in 23 wells. N,N-diethyl-meta-toluamide (DEET) was detected in water samples from 5 wells. Benzophenone, ethanol- 2-butoxy-phosphate, and tributylphosphate were detected in water samples from 3 wells. Fertilizer was determined to be the possible source of nitrate in samples from 13 of 45 wells sampled, with a15N values ranging from 0.43 to 3.46 permil. The possible source of nitrate for samples from the greatest number of wells (22 wells) was from mixed sources of nitrate from fertilizer, septic or manure, or natural sources. Mixed nitrate sources had a 15N values ranging from 0.25 to 9.83 permil. Septic or manure was determined as the possible source of nitrate in samples from 2 wells. Natural sources were determined to be the possible source of nitrate in samples from 7 wells, with a 15N values ranging from 0.83 to 9.44 permil.

  6. Cloning, expression and functional identification of a type Ⅲ polyketide synthase gene from Huperzia serrata%千层塔中Ⅲ型聚酮合酶基因的克隆、表达与功能鉴定

    Institute of Scientific and Technical Information of China (English)

    叶金翠; 张萍; 孙洁胤; 郭潮潭; 陈国神; 阿部郁朗; 野口博司


    Ⅲ型聚酮合酶是以合成聚酮类化合物为主的一类重要生物合成酶.本文利用逆转录聚合酶链反应从中草药千层塔新鲜嫩叶中扩增聚酮合酶基因,得到一个Ⅲ型聚酮合酶全长cDNA.该基因全长1 212 bp,编码404个氨基酸.与已知的其他植物来源的聚酮合酶氨基酸序列有约50%~66%的同源性.cDNA经双酶切后克隆至pQE81L,并导入大肠杆菌(E.coli) M15中表达,产生大量带寡聚组氨酸标记的重组酶,重组酶分子质量大小约为46.4 kDa.酶活性鉴定研究表明,该重组酶可催化芳香族底物、脂肪族底物生成系列非天然聚酮产物,尤其是其可催化N-甲基邻氨基苯甲酰CoA和丙二酰CoA生成1,3-二羟基-N-甲基-吖啶酮,吖啶酮生物碱一直被认为只能由吖啶酮合酶合成.该工作为研究千层塔中Ⅲ型聚酮合酶在天然药物石杉碱甲生物合成中的作用奠定基础.%A Cdna encoding novel type III polyketide synthase (PKS) was cloned and sequenced from young leaves of Chinese club moss Huperzia serrata (Thunb.) Trev. By RT-PCR using degenerated primers based on the conserved sequences of known CHSs, and named as H. Serrata PKS2. The terminal sequences of Cdna were obtained by the 3'- and 5'-RACE method. The full-length Cdna ofH, serrata PKS2 contained a 1 212 bp open reading frame encoding a 46.4 kDa protein with 404 amino acids. The deduced amino acid sequence of H. Serrata PKS2 showed 50%-66% identities to those of other chalcone synthase super family enzymes of plant origin. The recombinant H. Serrata PKS2 was functionally expressed in Escherichia coli with an additional hexahistidine tag at the N-terminus and showed unusually versatile catalytic potency to produce various aromatic tetraketides, including chalcones, benzophenones, phloroglucinols, and acridones. In particular, the enzyme accepted bulky starter substrates N-methylanthraniloyl-CoA, and carried out three condensations with malonyl-CoA to produce 1

  7. Protective effects of sunscreen cream on soldiers in sea training%VICHY防晒霜对1550例官兵夏季海训防晒效果观察

    Institute of Scientific and Technical Information of China (English)

    张华; 雷永红; 梁秀丽


    Objective To investigale the proleclive effects of sunscreen cream of VICHY on PLA soldiers in summer swimming. Methods ( 1) An 8 week, blinded, randomized study was conducted in 1550 PLA soldiers during summer swimming training Lo evaluale the efficacy of the sunscreen cream. The sunscreen cream was applied randomly to the face, arms, shoulder, and back of volunteer soldiers at 2 hours lime intervals in experimental groups everyday( n = 800) . Subjects used a sun protection factor ( SPF) 30 of sunscreen cream containing 5% benzophenone -3, octyl methoxycinnamale, and tilanium dioxide. On the contrary, the control group applied placebo of cream emulsions. The IL - 6 level of peripheral blood of PLA soldiers in summer swimming training was assessed by ELIASA. The results were analyzed by comparing the occurrence of sunburn by Tukey test. Results The all accumulated cases were 1550, including 850 for experimental group, 700 for control group. The sun burn occurred in 54(6. 35% ) in experimental group, and 273 (39. 0% ) in control group on first week in sea training. Tukey test showed that there was significant difference in the percentage of subjects with improvement between experimental groups and control group ( P < 0. 01), IL-6 level was elevated in the 2-5 days. Conclusions Use of the sunscreen cream of VICHY provides a good proleclive effecls of sunscreen for sea training in PLA soldiers.%目的 观察VICHY防晒霜对官兵海上游泳训练预防日晒伤的效果.方法 采取整体抽样、随机双盲的方法,分别对不同单位海上游泳训练的官兵进行防晒效果的比较观察.每批次均设观察组和对照组,观察组(n=850)每次下海游泳训练前将防晒霜涂抹在颈项及肩背部,训练2 h上岸休息时追加涂抹1次;对照组(n=700)基本不进行处理.观察组防晒效果观察:比较训练期内观察组和对照组日晒伤的发病率及其晒伤程度.同时,采集晒伤战士的血样(n=100),ELISA

  8. 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.


    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

  9. 苯乙烯-丁二烯-苯乙烯嵌段共聚物负载Pt催化肉桂醛制备肉桂醇的研究%Selective Hydrogenation of Cinnamaldehyde over Pt-Supported Styrene-Butadiene-Styrene Block Copolymer

    Institute of Scientific and Technical Information of China (English)

    曹云苹; 张爱清


    用紫外光交联的方法制备不同交联度的苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)负载Pt的催化膜并探讨其对肉桂醛选择性加氢制备肉桂醇的催化效果.其中催化剂Pt纳米簇用微波法制备,XRD测其平均粒径为3.7 nm.膜载催化剂的负载量、光交联剂三羟甲基丙烷三丙烯酸酯(TMPTA)和光引发剂二苯甲酮(BP)的用量均为3%.用色谱-质谱联用、XRD、紫外分光光度计对膜载催化剂和反应产物进行了表征,结果表明,随着交联度的增加,肉桂醇的催化选择性先增后减,紫外光光照80s时,负载膜交联度23.63%,肉桂醛转化率为91.46,肉桂醇选择性80.98%.质谱分析表明交联度大于30%后,催化产物中开始有膜分解产生的小分子杂质出现,并随交联度的进一步增大而增多;显微镜检测同时说明此时膜结构发生变化,造成肉桂醇选择性的降低.%Photocrosslinked styrene-butadiene-styrene block copolymer (SBS) membrane supported nano platinum catalysts was prepared and their catalytic activity on the selective hydrogenation of cinnamaldehyde was investigated.The platinum nanoclusters with an average diameter of ca 3.7 nm were obtained by reaction of H2PtCl6 with polyols, assisted by microwave irradiation (MW).The SBS membrane was loaded with 3.0 wt% of Pt, benzophenone (BP) and 1,1,1-trimethylolpropane triacrylate (TMPTA), respectively, and varing crosslinking ratios were achieved by adjusting the radiation time.The hydrogenation products were investigated by gas chromatography and mass spectrometry (GC-MS) and UV techniques.As the crosslinking ratio increases, the selectivity for cinnamyl alcohol first increases and reaches 80.98% at a crosslinking ratio of 23.63%, and then decreases.Decomposition products of the SBS meambrane itself begin to appear as the radiaton time is over 30 min (corresponding to a crossling ratio of sightly above 30%).The deterioration of the membrane structure is also evidenced

  10. Evaluation of Emerging Contaminants of Concern at the South District Wastewater Treatment Plant Based on Seasonal Events, Miami-Dade County, Florida, 2004 (United States)

    Lietz, Arthur C.; Meyer, Michael T.


    effluent pump, -100 to 17 percent at the reuse train, -100 to -40 percent at the chlorine dioxide unit, and -100 to -14 percent at the ultraviolet pilot unit on October 20, 2004. Samples were tested for detection of household and industrial (organic) wastewater compounds, pharmaceutical compounds, antibiotic compounds, and hormones in influent. Two 'known' endocrine disrupting compounds?17 beta-estradiol (E2) and diethoxynonylphenol? and four 'suspected' endocrine-disrupting compounds?1,4-dichlorobenzene, benzophenone, tris(2-chloroethyl) phosphate, and tris(dichloroisopropyl) phosphate?were detected during these sampling events. Phenanthrene and indole showed the greatest concentration ranges and highest concentrations for the organic wastewater compounds. Acetaminophen showed the greatest concentration range and highest concentration, and warfarin showed the smallest concentration range for the pharmaceutical compounds. Sulfamethoxazole (a sulfonamide) showed the greatest concentration range and highest concentration, and sulfathiozole (also a sulfonamide) showed the smallest concentration range for the antibiotic compounds. Two hormones, 17 beta-estradiol (E2) and estrone (E1), were detected in influent. Samples were also tested for detection of organic wastewater compounds, pharmaceutical compounds, antibiotic compounds, and hormones in effluent. Indole showed the greatest concentration range and highest concentration, and triphenyl phosphate showed the smallest concentration range for the organic wastewater compounds. Dehydronifedipine showed the greatest concentration range and highest concentration, and warfarin had the smallest concentration range for the pharmaceutical compounds. Anhydro-erythromycin (a macrolide degradation product) showed the greatest concentration range, and sulfadiazine (a sulfonamide) and tetracycline showed the lowest concentration ranges for the antibiotic compounds. One hormone, 17 beta-estradiol (E2), was det

  11. The stalk region of the Escherichia coli ATP synthase. Tyrosine 205 of the gamma subunit is in the interface between the F1 and F0 parts and can interact with both the epsilon and c oligomer. (United States)

    Watts, S D; Tang, C; Capaldi, R A


    The soluble portion of the Escherichia coli F1F0 ATP synthase (ECF1) and E. coli F1F0 ATP synthase (ECF1F0) have been isolated from a novel mutant gammaY205C. ECF1 isolated from this mutant had an ATPase activity 3.5-fold higher than that of wild-type enzyme and could be activated further by maleimide modification of the introduced cysteine. This effect was not seen in ECF1F0. The mutation partly disrupts the F1 to F0 interaction, as indicated by a reduced efficiency of proton pumping. ECF1 containing the mutation gammaY205C was bound to the membrane-bound portion of the E. coli F1F0 ATP synthase (ECF0) isolated from mutants cA39C, cQ42C, cP43C, and cD44C to reconstitute hybrid enzymes. Cu2+ treatment or reaction with 5,5'-dithio-bis(2-nitro-benzoic acid) induced disulfide bond formation between the Cys at gamma position 205 and a Cys residue at positions 42, 43, or 44 in the c subunit but not at position 39. Using Cu2+ treatment, this covalent cross-linking was obtained in yields as high as 95% in the hybrid ECF1 gammaY205C/cQ42C and in ECF1F0 isolated from the double mutant of the same composition. The covalent linkage of the gamma to a c subunit had little effect on ATPase activity. However, ATP hydrolysis-linked proton translocation was lost, by modification of both gamma Cys-205 and c Cys-42 by bulky reagents such as 5,5'-dithio-bis (2-nitro-benzoic acid) or benzophenone-4-maleimide. In both ECF1 and ECF1F0 containing a Cys at gamma 205 and a Cys in the epsilon subunit (at position 38 or 43), cross-linking of the gamma to the epsilon subunit was induced in high yield by Cu2+. No cross-linking was observed in hybrid enzymes in which the Cys was at position 10, 65, or 108 of the epsilon subunit. Cross-linking of gamma to epsilon had only a minimal effect on ATP hydrolysis. The reactivity of the Cys at gamma 205 showed a nucleotide dependence of reactivity to maleimides in both ECF1 and ECF1F0, which was lost in ECF1 when the epsilon subunit was removed. Our

  12. Photostability and efficacy studies of topical formulations containing UV-filters combination and vitamins A, C and E. (United States)

    Gaspar, L R; Campos, P M B G Maia


    It is already known that the photostability of a sunscreen is important for its performance on human skin. On the other hand, there are many formulations besides sunscreens containing combinations of UV-filters and daily use active substances with other claims like hydration and anti-aging effects. Vitamins A, C and E are frequently added in these kinds of products and it is not known if the UV-filters have some influence on the hydration and anti-aging effects of these vitamins on the skin as well as on their stability mainly when photounstable UV-filters like avobenzone and octyl methoxycinnamate are present in the formulation. Thus, the aim of this study was to evaluate the influence of two different UV-filters combinations, a photostable and a photounstable one, on the photostability as well as on the efficacy of a formulation containing vitamin A, C and E derivatives. The formulations that were investigated contained or not (vehicle: formulation 1) a combination of 0.6 % (w/w) vitamin A palmitate (1,700,000 UI/g), 2 % (w/w) vitamin E acetate and 2% (w/w) ascorbyl tetraisopalmitate (formulation 2) supplemented with a photounstable UV filter combination octyl methoxycinnamate (OMC), avobenzone (AVB) and 4-methylbenzilidene camphor (MBC) (formulation 3) or with a photostable UV filter combination OMC, benzophenone-3 (BP-3) and octocrylene (OC) (formulation 4). In the photostability studies, all formulations were spread onto a glass plate and exposed to UVA/UVB irradiation. The filter components and vitamins were quantified by HPLC analysis with detection at 325 and 235 nm and by spectrophotometry. To simulate the effects of these formulations daily use, all of them (formulations 1-4) were applied on the dorsum of hairless mice, which were submitted to a controlled light-dark cycle (and were not irradiated), once a day for 5 days. Transepidermal water loss (TEWL), water content of the stratum corneum and viscoelastic properties of the skin were analyzed by using

  13. Groundwater-quality characteristics for the Wyoming Groundwater-Quality Monitoring Network, November 2009 through September 2012 (United States)

    Boughton, Gregory K.


    , manganese, boron, and selenium exceeded WDEQ Class II agriculture groundwater standards in some samples. Measurements of pH and concentrations of sulfate, dissolved solids, aluminum, boron, and selenium exceeded WDEQ Class III livestock groundwater standards in some samples. The concentrations of dissolved solids in two samples exceeded the WDEQ Class IV industry groundwater standard. Measurements of pH and concentrations of dissolved solids, aluminum, iron, manganese, and selenium exceeded WDEQ Class special (A) fish and aquatic life groundwater standards in some samples. Stable isotopes of hydrogen and oxygen measured in water samples were compared to the Global Meteoric Water Line and Local Meteoric Water Lines. Results indicated that recharge to all of the wells was derived from precipitation and that the water has undergone some fractionation, possibly because of evaporation. Concentrations of organic compounds did not exceed any State or Federal water-quality standards. Few volatile organic compounds were detected in samples, whereas gasoline range organics, diesel range organics, and methane were detected most frequently. Concentrations of wastewater compounds did not exceed any State or Federal water-quality standards. The compounds N,N-diethyl-meta-toluamide (DEET), benzophenone, and phenanthrene were detected most frequently. Bacteria samples were collected, processed, incubated, and enumerated in the field or at the U.S. Geological Survey Wyoming-Montana Water Science Center. Total coliforms and Escherichia coli were detected in some samples.

  14. Isolation,identification,degradation characteristics and pathway of a pyrethroid-degrading bacterial strain%一株拟除虫菊酯农药降解菌的分离鉴定及其降解特性与途径

    Institute of Scientific and Technical Information of China (English)

    陈少华; 罗建军; 胡美英; 赖开平; 耿鹏; 肖盈


    A bacterial strain named P-01 was newly isolated by enrichment culture from the activated sludge in the wastewater of a pyrethroid-manufacturer in Zhongshan.Based on the morphology,physio-biochemical characteristics,and 16S rDNA sequence analysis,strain P-01 was temporarily identified as Achromobacter sp.P-01.Response surface methodology(RSM) was used to optimize degradation conditions.The optimal conditions for biodegradation were obtained as follows:31.4℃,pH 7.6 and inoculum biomass 0.4 g · L-1.Under the optimal degradation conditions,strain P-01 could effectively degrade deltamethrin,fenvalerate,beta-cypermethrin,beta-cyfluthrin and cyhalothrin with degradation rates of 98.9%,92.2%,91.0%,85.1% and 77.3%,respectively,within 7 days of incubation.Strain P-01 not only could utilize deltamethrin as the sole carbon source and energy for growth in mineral salt medium(MSM),but also could tolerate and efficiently degrade high concentrations of deltamethrin(100~500 mg · L-1).Furthermore,the degradation reaction followed first-order kinetics and half lives(T1/2) were 1.3,1.8,2.0,2.5 and 3.0 d,respectively.Studies on the degradation pathway showed that deltamethrin was degraded by hydrolysis of the carboxylester linkage to yield alpha-hydroxy-3-phenoxy-benzeneacetonitrile and 3-phenoxy benzaldehyde,and then the intermediates were further degraded by oxygenolysis to form 2-hydroxy-4-methoxy benzophenone and 1,2-benzenedicarboxylic acid,mono ester,finally resulting in complete detoxification.%采用富集培养法,从拟除虫菊酯农药厂废水排放口的活性污泥中分离到1株菊酯农药高效降解菌P-01.经形态、生理生化特征及16S rDNA序列分析,初步鉴定其为无色杆菌属(Achromobacter sp.).响应曲面法优化菌株P-01的降解条件,其降解最优条件为31.4℃、初始pH7.6和接种量0.4g·L-1,在此条件下,该菌株培养7d对50mg·L-1溴氰菊酯、氰戊菊酯、高效氯氰菊酯、高效氟

  15. Synthesis and application of functional branched macromolecules: From site isolation and energy harvesting to catalysis (United States)

    Hecht, Stefan

    polymers is described in Chapters 3, 4, and 5. Among the key findings of these chapters are: the important role of core size and structure for encapsulation, the superior ability of the dendrimer backbone to serve as an insulating shell and energy harvesting building block, as well as the practical and versatile use of dendritic initiators to generate functional star polymers with a high degree of site isolation. Following a short description of hyperbranched porphyrin architectures having multiple active sites (Chapter 6), the encapsulation of benzophenone-based singlet oxygen sensitizers at the core of a regular dendritic micelle is described in Chapter 7. The utilized amphiphilic design leads to the first example of light-driven catalysis within dendrimers. In the context of light-harvesting dendrimers, this finding represents the unique opportunity to convert the excitation energy that is funneled to the core into chemical energy, thereby truly mimicking natural photosynthesis. The design of first systems capable of combining light harvesting and excited state catalysis is outlined in Chapter 8. Finally, Chapter 9 illustrates an alternative, more practical approach towards light-harvesting photocatalytic polymers involving the use of monolithic materials.

  16. 黑附球菌抗紫外线保护剂的筛选%Screening of ultraviolet protectants for Epicoccum purpurascens

    Institute of Scientific and Technical Information of China (English)

    夏丽琴; 王亚南; 周岱超; 王树桐; 张瑜; 胡同乐; 曹克强


    In order to reduce the impact of UV on conidia of Epicoccum purpurascens strain XF1 and improve the biological activity of conidia in the field,the protective efficiency of ultraviolet protectant (UVP) combinations of 6 UV-absorbers and 4 light stabilizers against UV for conidia of E. purpurascens strain XF1 was tested in laboratory. The results showed that the protective efficiency of different UVP combinations was different, combinations of benzotriazole and hexamethyl phosphorus triamide (a3bl), and combinations of oxybenzone and hexamethyl phosphorus triamide ( a4bl and a5bl) ,were confirmed to be more effective than the other UV-protectants, with protective efficiency over 90% after 40 min exposure to UV light (at λ253.7N,) ,while that of combinations of salicylic acid benzyl ester and hexamethyl phosphorus triamide (albl) was only about 37. 12% . UVP combinations without protective efficiency included combinations of salicylic acid benzyl esters and light stabilizer 770,benzotriazole and light stabilizer 770,benzophenones and light stabilizer 770 (alb2,a3b2,a4b2, a5b2). The appropriate solvent combination was V( solvent n-hexane): V( peanut oil) =1:1 for (a3bl, a4bl,a5bl). For the three UVP complexes selected, the effective concentration of a4bl and a5bl should be higher than 7.5 mg/mL,while that of a3bl should be higher than 10 mg/mL. After 90 min and 180 min exposure of conidia to UV light (at λ253.7N,) , the protective efficiency of the three selective UVP combinations were over 88% and 63% Respectively.%为减少紫外线对黑附球菌Epicoccum purpurascens分生孢子的影响,提高分生孢子在田间的生物活性,在室内检测了6种紫外线吸收剂和4种光稳定剂之间的不同组合(复合型抗紫外线保护剂)对黑附球菌XF1菌株分生孢子抗紫外线的保护作用.结果表明:不同复合型抗紫外线保护剂对XF1分生孢子的保护效率差异较大,其中苯并三唑类与六甲基磷酰三胺的组合(a3b1)及苯

  17. A Development of Rapid, Practical and Selective Process for Preparation of Z-Oximes

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Bo Ram; Sung, Gi Hyeon; Yoon, Yongjin [Gyeongsang National Univ., Jinju (Korea, Republic of); Kim, Jeumjong [Electronic and Telecommunications Research Institute, Daejeon (Korea, Republic of)


    Table 1, compound 1a was treated with hydroxylamine hydrochloride in the presence of potassium carbonate in refluxing 1,4-dioxane to afford the corresponding ketoxime 2a in excellent yield. Acetophenone oxime (2a) was also obtained by the use of ethanol or methanol as the solvent at room temperature or at reflux temperature in excellent yields (Entries 9-12 in Table 1), whereas the side reaction was detected for the reaction of 1a with hydroxylamine hydrochloride in the presence of potassium carbonate in refluxing water. According to our preliminary results, we selected the methanol as the solvent due to short reaction time and low price. As shown in Table 2, aliphatic and aromatic ketones except for benzophenone (1f) were rapidly and selectively converted to the corresponding Z-oximes in good yields. Also, various types of aromatic aldehydes 1g. with electron donating and withdrawing groups were rapidly and selectively converted to the corresponding Zaldoximes in good to excellent yields. In our condition, the oximation of aldehydes is more Z-selective than the oximation of ketones. In order to evaluate the utility of industrial process, we examined the one mole scale reaction. Treatment of one mole acetophenone (1a) and benzaldehyde (1g) with hydroxylamine hydrochloride and potassium carbonate in methanol afforded the corresponding oximes 2a (E/Z ratio = 15:85, 92%) and 2g (E/Z ratio = 10:90, 92%). The structures of the oximes were established by IR and NMR. In the case of ketoximes, we distinguished two isomers by using the carbon chemical shifts of C=NOH, that is, the chemical shifts of the Z-isomer are detected higher field than the chemical shifts of the E-isomer. In the case of aldoximes, E/Z-isomers were distinguished by using the proton chemical shifts of HC=N for aldoximes, that is, the proton chemical shifts of the Z-isomer are detected lower field than the chemical shifts of the E-isomer. In summury, we have demonstrated the rapid and convenient oximation of