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Sample records for benzoquinones

  1. Reactivity measurement in estimation of benzoquinone and benzoquinone derivatives' allergenicity.

    Science.gov (United States)

    Mbiya, Wilbes; Chipinda, Itai; Simoyi, Reuben H; Siegel, Paul D

    2016-01-01

    Benzoquinone (BQ) and benzoquinone derivatives (BQD) are used in the production of dyes and cosmetics. While BQ, an extreme skin sensitizer, is an electrophile known to covalently modify proteins via Michael Addition (MA) reaction whilst halogen substituted BQD undergo nucleophilic vinylic substitution (SNV) mechanism onto amine and thiol moieties on proteins, the allergenic effects of adding substituents on BQ have not been reported. The effects of inserting substituents on the BQ ring has not been studied in animal assays. However, mandated reduction/elimination of animals used in cosmetics testing in Europe has led to an increased need for alternatives for the prediction of skin sensitization potential. Electron withdrawing and electron donating substituents on BQ were assessed for effects on BQ reactivity toward nitrobenzene thiol (NBT). The NBT binding studies demonstrated that addition of EWG to BQ as exemplified by the chlorine substituted BQDs increased reactivity while addition of EDG as in the methyl substituted BQDs reduced reactivity. BQ and BQD skin allerginicity was evaluated in the murine local lymph node assay (LLNA). BQD with electron withdrawing groups had the highest chemical potency followed by unsubstituted BQ and the least potent were the BQD with electron donating groups. The BQD results demonstrate the impact of inductive effects on both BQ reactivity and allergenicity, and suggest the potential utility of chemical reactivity data for electrophilic allergen identification and potency ranking. PMID:26612505

  2. Two new ortho benzoquinones from Uncaria rhynchophylla.

    Science.gov (United States)

    Zhang, Qian; Chen, Lei; Hu, Le-Jian; Liu, Wen-Yuan; Feng, Feng; Qu, Wei

    2016-03-01

    The present study was designed to determine the chemical constituents of the stems and hooks of Uncaria rhynchophylla. The chemical constituents were isolated and purified from CH2Cl2 fraction by chromatography. Their structures were elucidated by spectroscopic analyses. Their cytotoxicity was tested using MTT method. Two new ortho benzoquinones, 3-diethylamino-5-methoxy-1, 2-benzoquinone (1) and 3-ethylamino-5-methoxy-1, 2-benzoquinone (2), together with a known compound isorhynchophyllic acid (3) were isolated from U. rhynchophylla. These compounds were evaluated for their cytotoxicity against cancer cells A549, HepG2 and A2780. Compounds 1 and 2 were new ortho benzoquinones and showed weak antiproliferative activities on A549, HepG2 and A2780 cells. Compound 3 significantly inhibited the proliferation of A549, HepG2 and A2780 cells with IC50 values being 5.8, 12.8 and 11.8 µmol·L(-1), respectively. PMID:27025371

  3. Regioselectivity of conjugate additions to monoalkyl-1,4-benzoquinones

    OpenAIRE

    SNEZANA TRIFUNOVIC; MIROSLAV J. GASIC; MARIO ZLATOVIC; IRENA NOVAKOVIC; DUSAN SLADIC; TATJANA BOZIC

    2002-01-01

    The regioselectivity of the reaction of conjugate addition of thiols, amines, methanol and hydrogen chloride with the monoalkyl-1,4-benzoquinones avarone and 2-tert-butyl-1,4-benzoquinone was investigated. It was shown that the regioselectivity of the reaction is influenced by the electrophilicity of position 5 in unprotonated 2-alkylquinones, the increased electrophilicity of position 6 in acidic medium, and by the acidity of the intermediate hydroquinones.

  4. Regioselectivity of conjugate additions to monoalkyl-1,4-benzoquinones

    Directory of Open Access Journals (Sweden)

    SNEZANA TRIFUNOVIC

    2002-09-01

    Full Text Available The regioselectivity of the reaction of conjugate addition of thiols, amines, methanol and hydrogen chloride with the monoalkyl-1,4-benzoquinones avarone and 2-tert-butyl-1,4-benzoquinone was investigated. It was shown that the regioselectivity of the reaction is influenced by the electrophilicity of position 5 in unprotonated 2-alkylquinones, the increased electrophilicity of position 6 in acidic medium, and by the acidity of the intermediate hydroquinones.

  5. On the {sup 1}H NMR spectra of 2-substituted benzoquinones

    Energy Technology Data Exchange (ETDEWEB)

    Tedeschi, E.; Rezende, D.B. [Universidade de Sao Paulo (USP), SP (Brazil). Inst. de Quimica; Arruda Campos, I.P. de, E-mail: ipdacamp@uol.com.br [Universidade Paulista, Sao Paulo, SP (Brazil). Inst. de Ciencias Exatas e Tecnologia. Programa de Pos-Graduacao em Engenharia de Producao

    2009-07-01

    The novel complete analysis of the {sup 1}H NMR spectra of six monosubstituted benzoquinones is reported herein, together with a brief but complete review of the scanty previously published data on benzoquinone and its monosubstituded derivatives. (author)

  6. Activity of 1,4-Benzoquinones Against Formosan Subterranean Termites, Coptotermes formosanus

    Science.gov (United States)

    A large number of naturally occurring and synthetic benzoquinones were evaluated for activity against the Formosan subterranean termite, Coptotermes formosanus, with potential use in termite control. Among these bioactive naturally occurring benzoquinones are 2-methyl-5-isopropyl-1,4-benzoquinone, ...

  7. Synthesis and properties of fluorous benzoquinones and their application in deprotection of silyl ethers.

    Science.gov (United States)

    Matsubara, Hiroshi; Maegawa, Takahiko; Kita, Yasuaki; Yokoji, Takato; Nomoto, Akihiro

    2014-08-01

    1,4-Benzoquinone derivatives bearing trifluoromethyl, perfluorobutyl and perfluorohexyl groups were prepared and employed in the deprotection of silyl ethers. The fluorous character of these compounds was examined by measuring the partition coefficient between the fluorous and organic solvents. The benzoquinone derivatives showed significant fluorous character, indicating that they can be recovered from the reaction mixtures using a fluorous/organic biphasic system. The oxidising ability of the fluorous benzoquinones was estimated by cyclic voltammetry, and these compounds were found to be strong oxidisers. The fluorous benzoquinones were utilised in the oxidative desilylation of silyl ethers to afford the deprotected alcohols in high yield. In addition, the reduced fluorous benzoquinones were recovered from the reaction mixtures in good yields using a fluorous/organic biphasic system. PMID:24937383

  8. Analysis of benzoquinone decomposition in solution plasma process

    International Nuclear Information System (INIS)

    The decomposition of p-benzoquinone (p-BQ) in Solution Plasma Processing (SPP) was analyzed by Coherent Anti-Stokes Raman Spectroscopy (CARS) by monitoring the change of the anti-Stokes signal intensity of the vibrational transitions of the molecule, during and after SPP. Just in the beginning of the SPP treatment, the CARS signal intensities of the ring vibrational molecular transitions increased under the influence of the electric field of plasma. The results show that plasma influences the p-BQ molecules in two ways: (i) plasma produces a polarization and an orientation of the molecules in the local electric field of plasma and (ii) the gas phase plasma supplies, in the liquid phase, hydrogen and hydroxyl radicals, which reduce or oxidize the molecules, respectively, generating different carboxylic acids. The decomposition of p-BQ after SPP was confirmed by UV-visible absorption spectroscopy and liquid chromatography

  9. A cytotoxic meroterpenoid benzoquinone from roots of Cordia globosa.

    Science.gov (United States)

    Alencar de Menezes, Jane Eire; Lemos, Telma Leda; Pessoa, Otília Deusdênia; Braz-Filho, Raimundo; Montenegro, Raquel C; Wilke, Diego Veras; Costa-Lotufo, Letícia V; Pessoa, Cláudia; de Moraes, Manoel Odorico; Silveira, Edilberto R

    2005-01-01

    (1a S*,1b S*,7a S*,8a S*)-4,5-Dimethoxy-1a,7a-dimethyl-1,1a,1b,2,7, 7a,8,8a-octahydrocyclopropa cyclopenta[1,2-b]naphthalene-3,6-dione (1), a new meroterpenoid benzoquinone, and microphyllaquinone (2), a known naphthoquinone, have been isolated from roots of Cordia globosa. Both structure determinations were performed by conventional spectroscopic methods, including inverse detection NMR techniques, and by comparison with data from the literature for related compounds. Compound 1 displayed considerable cytotoxic activity against several cancer cell lines with IC50 values in the range of 1.2 to 5.0 microg/mL. The cytotoxic activity seemed to be related to DNA synthesis inhibition, as revealed by the reduction of 5-bromo-2'-deoxyuridine incorporation, and apoptosis induction, as indicated by the acridine orange/ethidium bromide assay and morphological changes after 24 h of incubation on leukemic cells.

  10. Dihydroxybenzene/benzoquinone-containing polymers: organic redox polymers

    Energy Technology Data Exchange (ETDEWEB)

    Moulay, S. [Universite de Blida, Lab. de Chimie-Physique Macromoleculaire, Institut de Chimie Industrielle (Algeria)

    2000-08-01

    Polymers containing hydroquinone, catechol or their corresponding benzoquinones are a special class of redox polymers. Three pathways of their syntheses are possible: condensation polymerization of suitable monomers, addition polymerization of vinyl monomers containing redox moiety, and chemical attachment of redox unit onto pre-made polymeric matrix. A range of functionalized matrices have been employed such as polyethers, polyesters, polycarbonates, polyurethanes, polyamides and others. Protection of their phenolic functionality has conducted to chemically interesting redox polymer precursors. The presence of a redox moiety coupled with the extant functionalization of the polymer matrix makes the materials very valuable, of wide properties and consequently of vast applicability. For instance, in the oil field, some polymers such as carboxy-methyl-cellulose (CMC) are often applied as to bring about a viscosity improvement and therefore to facilitate the oil drilling. In this regard, Patel evaluated sulfo-alkylated polymeric catechol, namely sulfo-methylated and sulfo-ethylated resins. Indeed, polymeric catechol chemically modified as such exhibited a marked ability to control the viscosity, the gel strength, as well as the filtrate loss of aqueous oil drilling fluids.

  11. Benzoquinones as inhibitors of botulinum neurotoxin serotype A.

    Science.gov (United States)

    Bremer, Paul T; Hixon, Mark S; Janda, Kim D

    2014-08-01

    Although botulinum neurotoxin serotype A (BoNT/A) is known for its use in cosmetics, it causes a potentially fatal illness, botulism, and can be used as a bioterror weapon. Many compounds have been developed that inhibit the BoNTA zinc-metalloprotease light chain (LC), however, none of these inhibitors have advanced to clinical trials. In this study, a fragment-based approach was implemented to develop novel covalent inhibitors of BoNT/A LC. First, electrophilic fragments were screened against BoNT/A LC, and benzoquinone (BQ) derivatives were found to be active. In kinetic studies, BQ compounds acted as irreversible inhibitors that presumably covalently modify cysteine 165 of BoNT/A LC. Although most BQ derivatives were highly reactive toward glutathione in vitro, a few compounds such as natural product naphthazarin displayed low thiol reactivity and good BoNT/A inhibition. In order to increase the potency of the BQ fragment, computational docking studies were employed to elucidate a scaffold that could bind to sites adjacent to Cys165 while positioning a BQ fragment at Cys165 for covalent modification; 2-amino-N-arylacetamides met these criteria and when linked to BQ displayed at least a 20-fold increase in activity to low μM IC₅₀ values. Unlike BQ alone, the linked-BQ compounds demonstrated only weak irreversible inhibition and therefore acted mainly as non-covalent inhibitors. Further kinetic studies revealed a mutual exclusivity of BQ covalent inactivation and competitive inhibitor binding to sites adjacent to Cys165, refuting the viability of the current strategy for developing more potent irreversible BoNT/A inhibitors. The highlights of this study include the discovery of BQ compounds as irreversible BoNT/A inhibitors and the rational design of low μM IC50 competitive inhibitors that depend on the BQ moiety for activity. PMID:24984937

  12. Chemical defense in harvestmen (arachnida, opiliones): do benzoquinone secretions deter invertebrate and vertebrate predators?

    Science.gov (United States)

    Machado, Glauco; Carrera, Patricia C; Pomini, Armando M; Marsaioli, Anita J

    2005-11-01

    Two alkylated 1,4-benzoquinones were identified from the defensive secretion produced by the neotropical harvestman Goniosoma longipes (Gonyleptidae). They were characterized as 2,3-dimethyl-1,4-benzoquinone and 2-ethyl-3-methyl-1,4-benzoquinone. We tested the effectiveness of these benzoquinone secretions against several predator types, including invertebrates and vertebrates. Different predators were exposed to the harvestmen's gland secretion or to distilled water in laboratory bioassays. Our results indicate that secretions containing the 1,4-benzoquinones released by G. longipes can be an effective defense against predation, and that the effectiveness of the secretion is dependent on the predator type. The scent gland secretion repelled seven ant species, two species of large wandering spiders, and one frog species, but was not an effective defense against an opossum. Our study also demonstrates that the scent gland secretion of G. longipes can work as a chemical shield preventing the approach of three large predatory ants for at least 10 min. The chemical shield may protect the harvestman against successive attacks of the same ant worker and also allow the harvestman to flee before massive ant recruitment. Our data support the suggestion that chemical defenses may increase survival with some but not all potential predators. This variation in defense effectiveness may result from many interacting factors, including the attack strategy, size, learning ability, and physiology of the predators, as well as the chemical nature of the defensive compounds, type of emission, and amount of effluent released by the prey. PMID:16273426

  13. Occurrence and formation of chloro- and bromo-benzoquinones during drinking water disinfection.

    Science.gov (United States)

    Zhao, Yuli; Anichina, Janna; Lu, Xiufen; Bull, Richard J; Krasner, Stuart W; Hrudey, Steve E; Li, Xing-Fang

    2012-09-15

    Consumption of chlorinated drinking water has shown somewhat consistent association with increased risk of bladder cancer in a series of epidemiological studies, but plausible causative agents have not been identified. Halobenzoquinones (HBQs) have been recently predicted as putative disinfection byproducts (DBPs) that might be of toxicological relevance. This study reports the occurrence frequencies and concentrations of HBQs in plant effluents from nine drinking water treatment plants in the USA and Canada, where four common disinfection methods, chlorination, chloramination, chlorination with chloramination, and ozonation with chloramination, are used. In total, 16 water samples were collected and analyzed for eight HBQs: 2,6-dichloro-1,4-benzoquinone (2,6-DCBQ), 2,6-dibromo-1,4-benzoquinone (2,6-DBBQ), 2,6-dichloro-3-methyl-1,4-benzoquinone (2,6-DC-3-MBQ), 2,3,6-trichloro-1,4-benzoquinone (2,3,6-TriCBQ), 2,5-dibromo-1,4-benzoquinone (2,5-DBBQ), 2,3-dibromo-5,6-dimethyl-1,4-benzoquinone (2,3-DB-5,6-DM-BQ), tetrabromo-1,4-benzoquinone (TetraB-1,4-BQ), and tetrabromo-1,2-benzoquinone (TetraB-1,2-BQ). Of these, 2,6-DCBQ, 2,6-DBBQ, 2,6-DC-3-MBQ and 2,3,6-TriCBQ were detected in 16, 11, 6, and 3 of the 16 samples with the method detection limit (DL) of 1.0, 0.5, 0.9 and 1.5 ng/L, respectively, using a solid phase extraction and high performance liquid chromatography-tandem mass spectrometry method. The concentrations were in the ranges of 4.5-274.5 ng/L for 2,6-DCBQ, below DL to 37.9 ng/L for 2,6-DBBQ, below DL to 6.5 ng/L for 2,6-DC-3-MBQ, and below DL to 9.1 ng/L for 2,3,6-TriCBQ. These authentic samples show DCBQ and DBBQ as the most abundant and frequently detectable HBQs. In addition, laboratory controlled experiments were performed to examine the formation of HBQs and their subsequent stability toward hydrolysis when the disinfectants, chlorine, chloramine, or ozone followed by chloramines, reacted with phenol (a known precursor) under various conditions

  14. Synthesis and Biological Evaluation of 2,5-Bis(alkylamino-1,4-benzoquinones

    Directory of Open Access Journals (Sweden)

    Cláudia Pessoa

    2010-08-01

    Full Text Available A series of twelve 2,5-bis(alkylamino-1,4-benzoquinones were prepared in yields ranging from 9–58% via the reaction between p-benzoquinone and various amines. The structures of the synthesized compounds were confirmed by IR, 1H- and 13C-NMR and MS analyses. The phytotoxicity of the 2,5-bis(alkylamino-1,4-benzoquinones was evaluated against two crop species, Cucumis sativus and Sorgum bicolor, at 1.0 × 10-3 mol/L. In general, the quinones displayed inhibitory effects on the dicotyledonous species C. sativus (7–74%. On the other hand stimulatory effects were observed on S. bicolor (monocotyledonous. Similar results were observed in the biological assays carried out with the weed species Ipomoea grandifolia (dicotyledonous and Brachiaria decumbens (monocotyledonous. In addition, the cytotoxicity of the 2,5-bis(alkylamino-1,4-benzoquinones was assayed against HL-60 (leukemia, MDA-MB-435 (melanoma, SF-295 (brain and HCT-8 (colon human cancer cell lines and human peripheral blood mononuclear cells (PBMC, as representatives of healthy cells, using a MTT and an Alamar Blue assay. Compound 12 was the most active, displaying cytotoxicity against all cancer cell lines tested.

  15. Study of the Residual Linewidth of the Level-Anti-Crossing Signal in p-Benzoquinone

    NARCIS (Netherlands)

    Lichtenbelt, Jan H.; Wiersma, Douwe A.

    1978-01-01

    The linewidth of the level-anti-crossing (LAC) signal in p-benzoquinone has been examined using optical detection of magnetic resonance between states in the avoided crossing region. The results are used to separate the homogeneous (due to hyperfine coupling) from the inhomogeneous (due to disorder)

  16. The benzoquinone-mediated electrochemical microbial biosensor for water biotoxicity assay

    International Nuclear Information System (INIS)

    Graphical abstract: The mediator can participate in microorganism respiration, accept the electrons from respiratory chains, and therefore be reduced by microorganism. The re-oxidization currents of mediators on electrode can reflect the microbial activity, and when respiration is suppressed by toxicants, it can be detected by the resulting change of currents. Unlike other biotoxicity tests, which record the toxic effect after a fixed time for incubation of biocomponents and toxicants, this mediated whole cell biosensor can provide a real-time monitor of the microbial activity during the measurement. -- Abstract: A simple mediated microbial biosensor providing real-time monitoring of water quality and evaluation of biotoxicity was fabricated by entrapping Escherichia coli (E. coli) cells in gelatin on glassy carbon electrode with benzoquinone as the redox mediator. The biotoxicity assay was based on the respiratory activity of E. coli cells estimated by the oxidation current of microbially reduced benzoquinone. The neutrality and lipophilicity rendered benzoquinone better efficiency than ferricyanide in mediated microbial reactions. After the optimization of preparation conditions, the prepared microbial biosensors have measured several common toxicants with different concentrations. In addition, the biotoxicity of binary mixtures of heavy metals and wastewater were investigated. The fabricated biosensor exhibited good repeatability and stability in the biotoxicity measurements

  17. Photoinduced energy and electron transfer in rubrene-benzoquinone and rubrene-porphyrin systems

    KAUST Repository

    Khan, Jafar Iqbal

    2014-11-01

    Excited-state electron and energy transfer from singlet excited rubrene (Ru) to benzoquinone (BQ) and tetra-(4-aminophenyl) porphyrin (TAPP) were investigated by steady-state absorption and emission, time-resolved transient absorption, and femtosecond (fs)-nanosecond (ns) fluorescence spectroscopy. The low reduction potential of BQ provides the high probability of electron transfer from the excited Ru to BQ. Steady-state and time-resolved results confirm such an excited electron transfer scenario. On the other hand, strong spectral overlap between the emission of Ru and absorption of TAPP suggests that energy transfer is a possible deactivation pathway of the Ru excited state.

  18. Structural and optical properties of langmuir-blodgett films of the electron acceptor 2-octadecylthio-1,4-benzoquinone

    DEFF Research Database (Denmark)

    Bjørnholm, T.; Larsen, N. B.; Christensen, Finn Erland;

    1993-01-01

    The electron acceptor 2-octadecylthio-1,4-benzoquinone forms stable monolayers at air/water interfaces. Transfer to hydrophobic substrates yields Y-type Langmuir-Blodgett films. By studies of multilayers using X-ray diffraction and spectroscopy with polarized light a structure model is obtained...

  19. Alkylresorcinol Synthases Expressed in Sorghum Bicolor Root Hairs Play an Essential Role in the Biosynthesis of the Allelopathic Benzoquinone Sorgoleone

    Science.gov (United States)

    Sorghum bicolor is considered to be an allelopathic crop species, producing phytotoxins such as the lipid benzoquinone sorgoleone, which likely accounts for many of the allelopathic properties of Sorghum spp. Current evidence suggests that sorgoleone biosynthesis occurs exclusively in root hair cel...

  20. Synthesis, characterization of N-, S-, O-substituted naphthoand benzoquinones and a structural study

    Indian Academy of Sciences (India)

    Cemil Ibis; Nahide Gulsah Deniz

    2012-05-01

    The new series of N-, S-, O-substituted 1,4-naphthoquinone and S-, O-substituted 1,4-benzoquinone compounds were synthesized via vinylic substitution. Compounds 3 and 4 were synthesized from the reaction of 1 with 2. Compounds 6, 7 and 8 were synthesized from reaction of 1 with 5. Compounds 10 and 11 were obtained from the reaction of 1 with 9. Compounds 13 and 14 were synthesized from the reaction of 1 with 12. Compounds 16 and 17 were obtained from the reaction of 15 with 2. Photochemical and electrochemical properties of N-, S-, O-substituted quninone compounds were determined by using fluorescence spectroscopy and cyclic voltammetry. Crystal structure of 2-(7-sulphanyl-4-methyl-coumarinyl)-3-(1-ethoxy)-1,4-naphthoquinone 13 was determined by X-ray diffraction method.

  1. High-pressure polymorphism of the electrochemically active organic molecule tetrahydroxy-p-benzoquinone

    Science.gov (United States)

    Ciezak-Jenkins, Jennifer A.

    2016-09-01

    The structural and chemical response of tetrahydroxy-p-benzoquinone to isothermal compression to near 20 GPa have been studied using powder x-ray diffraction and vibrational spectroscopy. Compression beyond 11.5 GPa resulted in the appearance of several new peaks in the x-ray patterns, changes in the peak distribution and intensities, as well as the disappearance of features observed at lower pressures, which when coupled with concomitant changes in the infrared spectrum are indicative of a phase transition. Further analysis of the infrared spectra suggest this phase transition results in an increase in the anharmonicity of the system. Raman spectroscopic experiments indicate the high-pressure phase to be highly photosensitive and easily polymerized.

  2. Neopetrosiquinones A and B, Sesquiterpene Benzoquinones Isolated from the Deep-water Sponge Neopetrosia cf. proxima

    Science.gov (United States)

    Winder, Priscilla L.; Baker, Heather L.; Linley, Patricia; Guzmán, Esther; Pomponi, Shirley A.; Diaz, M. Cristina; Reed, John K.; Wright, Amy E.

    2011-01-01

    Two new marine-derived sesquiterpene benzoquinones which we designate as neopetrosiquinone A (1) and B (2), have been isolated from a deep-water sponge of the family Petrosiidae. The structures were elucidated on the basis of their spectroscopic data. Compounds 1 and 2 inhibit the in vitro proliferation of the DLD-1 human colorectal adenocarcinoma cell line with IC50 values of 3.7 and 9.8 μM, respectively, and the PANC-1 human pancreatic carcinoma cell line with IC50 values of 6.1 and 13.8 μM, respectively. Neopetrosiquinone A (1) also inhibited the in vitro proliferation of the AsPC-1 human pancreatic carcinoma cell line with an IC50 value of 6.1 μM. The compounds are structurally related to alisiaquinone A, cyclozonarone and xestoquinone. PMID:22014756

  3. One-pot non-enzymatic formation of firefly luciferin in a neutral buffer from p-benzoquinone and cysteine.

    Science.gov (United States)

    Kanie, Shusei; Nishikawa, Toshio; Ojika, Makoto; Oba, Yuichi

    2016-01-01

    Firefly luciferin, the substrate for the bioluminescence reaction of luminous beetles, possesses a benzothiazole ring, which is rare in nature. Here, we demonstrate a novel one-pot reaction to give firefly luciferin in a neutral buffer from p-benzoquinone and cysteine without any synthetic reagents or enzymes. The formation of firefly luciferin was low in yield in various neutral buffers, whereas it was inhibited or completely prevented in acidic or basic buffers, in organic solvents, or under a nitrogen atmosphere. Labelling analysis of the firefly luciferin using stable isotopic cysteines showed that the benzothiazole ring was formed via the decarboxylation and carbon-sulfur bond rearrangement of cysteine. These findings imply that the biosynthesis of firefly luciferin can be developed/evolved from the non-enzymatic production of firefly luciferin using common primary biosynthetic units, p-benzoquinone and cysteine. PMID:27098929

  4. Synthesis by-products from the Wacker oxidation of safrole in methanol using rho-benzoquinone and palladium chloride.

    Science.gov (United States)

    Cox, M; Klass, G

    2006-12-20

    This paper reports the identification of a number of by-products, which are produced during the Wacker oxidation of safrole to 3,4-methylenedioxyphenyl-2-propanone (MDP2P) using rho-benzoquinone and palladium chloride when methanol is utilised as the solvent. Also described is the retrieval of these compounds from illicit samples from a clandestine laboratory, which was uncovered in South Australia in September 2003.

  5. Insights into the Biosynthesis of the Benzoquinone Ansamycins Geldanamycin and Herbimycin, Obtained by Gene Sequencing and Disruption†

    OpenAIRE

    Rascher, Andreas; Hu, Zhihao; Buchanan, Greg O.; Reid, Ralph; Hutchinson, C. Richard

    2005-01-01

    Geldanamycin and the closely related herbimycins A, B, and C were the first benzoquinone ansamycins to be extensively studied for their antitumor properties as small-molecule inhibitors of the Hsp90 protein chaperone complex. These compounds are produced by two different Streptomyces hygroscopicus strains and have the same modular polyketide synthase (PKS)-derived carbon skeleton but different substitution patterns at C-11, C-15, and C-17. To set the stage for structural modification by genet...

  6. Metal ion-catalyzed cycloaddition vs hydride transfer reactions of NADH analogues with p-benzoquinones.

    Science.gov (United States)

    Fukuzumi, S; Fujii, Y; Suenobu, T

    2001-10-24

    1-Benzyl-4-tert-butyl-1,4-dihydronicotinamide (t-BuBNAH) reacts efficiently with p-benzoquinone (Q) to yield a [2+3] cycloadduct (1) in the presence of Sc(OTf)(3) (OTf = OSO(2)CF(3)) in deaerated acetonitrile (MeCN) at room temperature, while no reaction occurs in the absence of Sc(3+). The crystal structure of 1 has been determined by the X-ray crystal analysis. When t-BuBNAH is replaced by 1-benzyl-1,4-dihydronicotinamide (BNAH), the Sc(3+)-catalyzed cycloaddition reaction of BNAH with Q also occurs to yield the [2+3] cycloadduct. Sc(3+) forms 1:4 complexes with t-BuBNAH and BNAH in MeCN, whereas there is no interaction between Sc(3+) and Q. The observed second-order rate constant (k(obs)) shows a first-order dependence on [Sc(3+)] at low concentrations and a second-order dependence at higher concentrations. The first-order and the second-order dependence of the rate constant (k(et)) on [Sc(3+)] was also observed for the Sc(3+)-promoted electron transfer from CoTPP (TPP = tetraphenylporphyrin dianion) to Q. Such dependence of k(et) on [Sc(3+)] is ascribed to formation of 1:1 and 1:2 complexes between Q(*)(-) and Sc(3+) at the low and high concentrations of Sc(3+), respectively, which results in acceleration of the rate of electron transfer. The formation constants for the 1:2 complex (K(2)) between the radical anions of a series of p-benzoquinone derivatives (X-Q(*)(-)) and Sc(3+) are determined from the dependence of k(et) on [Sc(3+)]. The K(2) values agree well with those determined from the dependence of k(obs) on [Sc(3+)] for the Sc(3+)-catalyzed addition reaction of t-BuBNAH and BNAH with X-Q. Such an agreement together with the absence of the deuterium kinetic isotope effects indicates that the addition proceeds via the Sc(3+)-promoted electron transfer from t-BuBNAH and BNAH to Q. When Sc(OTf)(3) is replaced by weaker Lewis acids such as Lu(OTf)(3), Y(OTf)(3), and Mg(ClO(4))(2), the hydride transfer reaction from BNAH to Q also occurs besides the

  7. Channelling phenomenon in the gamma irradiated Benzo-quinone and other compounds observed under the scanning electron microscope

    International Nuclear Information System (INIS)

    Scanning Electron Microscope (S.E.M.), has been used to examine the gamma irradiated pure crystals of Benzo-quinone and other compounds in the polycrystaline form. After gamma irradiation, shallow lines (channels) were observed on the crystal's surfaces when the crystal layers arrangements are parallel to the photons beam direction. Holes were also observed when those layers of the crystals are in the nonparallel case. The phenomenon has been studied and analysed in connected with the H-atom bonds disruption, and H-atoms migration through the crystal's layers. (author)

  8. The metabolism of aromatic acids by micro-organisms. A reassessment of the role of o-benzoquinone as a product of protocatechuate metabolism by fungi.

    Science.gov (United States)

    Bilton, R F; Cain, R B

    1968-08-01

    1. The addition of aniline to cultures of several yeasts, Fusarium oxysporum and Neurospora crassa growing with protocatechuate as sole carbon source resulted in the precipitation of dianilino-o-benzoquinone (anil). This product was also formed, however, if the medium was uninoculated. 2. The physical presence of yeast cells (living or dead) increased the anil yields in Debaryomyces subglobosus cultures. 3. No anil was formed if p-hydroxybenzoate was the growth substrate. 4. o-Benzoquinone was a strong inhibitor of protocatechuate 3,4-oxygenase and catechol 1,2-oxygenase in these fungi. 5. It was concluded that o-benzoquinone formation from protocatechuate is independent of living yeast. PMID:5691755

  9. The metabolism of aromatic acids by microorganisms. A reassessment of the role of o-benzoquinone as a product of protocatechuate metabolism by fungi

    Science.gov (United States)

    Bilton, R. F.; Cain, R. B.

    1968-01-01

    1. The addition of aniline to cultures of several yeasts, Fusarium oxysporum and Neurospora crassa growing with protocatechuate as sole carbon source resulted in the precipitation of dianilino-o-benzoquinone (anil). This product was also formed, however, if the medium was uninoculated. 2. The physical presence of yeast cells (living or dead) increased the anil yields in Debaryomyces subglobosus cultures. 3. No anil was formed if p-hydroxybenzoate was the growth substrate. 4. o-Benzoquinone was a strong inhibitor of protocatechuate 3,4-oxygenase and catechol 1,2-oxygenase in these fungi. 5. It was concluded that o-benzoquinone formation from protocatechuate is independent of living yeast. PMID:5691755

  10. Revisiting the stability of endo/exo Diels-Alder adducts between cyclopentadiene and 1,4-benzoquinone

    Energy Technology Data Exchange (ETDEWEB)

    Tormena, Claudio F. [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica. Dept. de Quimica Organica; Lacerda Junior, Valdemar [Universidade Federal do Espirito Santo (UFES), Vitoria, ES (Brazil). Centro de Ciencias Exatas. Dept. de Quimica; Oliveira, Kleber T. de [Universidade Federal do ABC (UFABC), Santo Andre, SP (Brazil). Centro de Ciencias Naturais e Humanas

    2010-07-01

    In this work it is presented a detailed theoretical analysis of the relative stability of endo/exo Diels-Alder adducts formed by the reaction between cyclopentadiene (1) and 1,4-benzoquinone (2). The intrinsic reaction coordinate (IRC) showed the existence of only one transition state for the reaction studied, for both endo 3 and exo 4 adducts. The energies of both adducts were obtained at high level of theory (CBS-Q) confirming that the endo adduct is more stable than exo, which is in the opposite way to the observed in reactions that usually follow Alder's rule. An electronic structure analysis was performed through NBO methodology, indicating that the attractive delocalization interaction predominates over the steric repulsive interaction in the endo adducts. In summary, for the studied cycloaddition reaction the endo adduct is the thermodynamic and kinetic product, which can be also confirmed by experimental data mentioned in this work. (author)

  11. Synthesis of 2-methoxy benzoquinone and 2,6-dimethoxybenzoquinone by selected lactic acid bacteria during sourdough fermentation of wheat germ

    OpenAIRE

    Rizzello, Carlo Giuseppe; Mueller, Thomas; Coda, Rossana; Reipsch, Franziska; Nionelli, Luana; Curiel, José Antonio; Gobbetti, Marco

    2013-01-01

    Background In the last decade, several studies described the promising cytotoxic activity of fermented wheat germ towards cancer cell lines and during in vivo clinical trials. Recent data suggested that the antiproliferative, antimetastatic and immunological effects of this preparation are mainly attributed to quinones. This study aimed at exploiting the potential of sourdough lactic acid bacteria fermentation to release 2-methoxy benzoquinone, and 2,6-dimethoxybenzoquinone, which are natural...

  12. Tetrachloro-p-benzoquinone induces hepatic oxidative damage and inflammatory response, but not apoptosis in mouse: The prevention of curcumin

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Demei; Hu, Lihua; Su, Chuanyang; Xia, Xiaomin; Zhang, Pu; Fu, Juanli; Wang, Wenchao; Xu, Duo; Du, Hong; Hu, Qiuling; Song, Erqun; Song, Yang, E-mail: songyangwenrong@hotmail.com

    2014-10-15

    This study investigated the protective effects of curcumin on tetrachloro-p-benzoquinone (TCBQ)-induced hepatotoxicity in mice. TCBQ-treatment causes significant liver injury (the elevation of serum AST and ALT activities, histopathological changes in liver section including centrilobular necrosis and inflammatory cells), oxidative stress (the elevation of TBAR level and the inhibition of SOD and catalase activities) and inflammation (up-regulation of iNOS, COX-2, IL-1β, IL-6, TNF-α and NF-κB). However, these changes were alleviated upon pretreatment with curcumin. Interestingly, TCBQ has no effect on caspase family genes or B-cell lymphoma 2 (Bcl-2)/Bcl-2 associated X (Bax) protein expressions, which implied that TCBQ-induced hepatotoxicity is independent of apoptosis. Moreover, curcumin was shown to induce phase II detoxifying/antioxidant enzymes HO-1 and NQO1 through the activation of nuclear factor erythroid-derived 2-like 2 (Nrf2). In summary, the protective mechanisms of curcumin against TCBQ-induced hepatoxicity may be related to the attenuation of oxidative stress, along with the inhibition of inflammatory response via the activation of Nrf2 signaling. - Highlights: • TCBQ-intoxication significantly increased AST and ALT activities. • TCBQ-intoxication induced oxidative stress in mice liver. • TCBQ-intoxication induced inflammatory response in mice liver. • TCBQ-intoxication induced hepatotoxicity is independent of apoptosis. • Curcumin relieved TCBQ-induced liver damage remarkably.

  13. Analytical and toxicity characterization of halo-hydroxyl-benzoquinones as stable halobenzoquinone disinfection byproducts in treated water.

    Science.gov (United States)

    Wang, Wei; Qian, Yichao; Li, Jinhua; Moe, Birget; Huang, Rongfu; Zhang, Hongquan; Hrudey, Steve E; Li, Xing-Fang

    2014-05-20

    Exposure to chlorination disinfection byproducts (DBPs) is potentially associated with an increased risk of bladder cancer. Four halobenzoquinones (HBQs) have been detected in treated drinking water and have shown potency in producing reactive oxygen species and inducing damage to cellular DNA and proteins. These HBQs are unstable in drinking water. The fate and behavior of these HBQs in drinking water distribution systems is unclear. Here we report the high-resolution mass spectrometry identification of the transformation products of HBQs as halo-hydroxyl-benzoquinones (OH-HBQs) in water under realistic conditions. To further examine the kinetics of transformation, we developed a solid-phase extraction with ultrahigh-performance liquid chromatography tandem mass spectrometry (SPE-UHPLC-MS/MS) method to determine both the HBQs and OH-HBQs. The method provides reproducible retention times (SD method, we confirmed that decrease of HBQs correlated with increase of OH-HBQs in both the laboratory experiments and several distribution systems, supporting that OH-HBQs were more stable forms of HBQ DBPs. To understand the toxicological relevance of the OH-HBQs, we studied the in vitro toxicity with CHO-K1 cells and determined the IC50 of HBQs and OH-HBQs ranging from 15.9 to 72.9 μM. While HBQs are 2-fold more toxic than OH-HBQs, both HBQs and OH-HBQs are substantially more toxic than the regulated DBPs.

  14. Rapid and sensitive spectrofluorimetric determination of enrofloxacin, levofloxacin and ofloxacin with 2,3,5,6-tetrachloro- p-benzoquinone

    Science.gov (United States)

    Ulu, Sevgi Tatar

    2009-06-01

    A highly sensitive spectrofluorimetric method was developed for the first time, for the analysis of three fluoroquinolones (FQ) antibacterials, namely enrofloxacin (ENR), levofloxacin (LEV) and ofloxacin (OFL) in pharmaceutical preparations through charge transfer (CT) complex formation with 2,3,5,6-tetrachloro- p-benzoquinone (chloranil,CLA). At the optimum reaction conditions, the FQ-CLA complexes showed excitation maxima ranging from 359 to 363 nm and emission maxima ranging from 442 to 488 nm. Rectilinear calibration graphs were obtained in the concentration range of 50-1000, 50-1000 and 25-500 ng mL -1 for ENR, LEV and OFL, respectively. The detection limit was found to be 17 ng mL -1 for ENR, 17 ng mL -1 for LEV, 8 ng mL -1 for OFL, respectively. Excipients used as additive in commercial formulations did not interfere in the analysis. The method was validated according to the ICH guidelines with respect to specificity, linearity, accuracy, precision and robustness. The proposed method was successfully applied to the analysis of pharmaceutical preparations. The results obtained were in good agreement with those obtained using the official method; no significant difference in the accuracy and precision as revealed by the accepted values of t- and F-tests, respectively.

  15. Tert-butyl benzoquinone: mechanism of biofilm eradication and potential for use as a topical antibiofilm agent

    Science.gov (United States)

    Ooi, N.; Eady, E. A.; Cove, J. H.; O'Neill, A. J.

    2016-01-01

    Objectives Tert-butyl benzoquinone (TBBQ) is the oxidation product of tert-butyl hydroquinone (TBHQ), an antimicrobial food additive with >40 years of safe use. TBBQ displays potent activity against Staphylococcus aureus biofilms in vitro. Here, we report on studies to further explore the action of TBBQ on staphylococcal biofilms, and provide a preliminary preclinical assessment of its potential for use as a topical treatment for staphylococcal infections involving a biofilm component. Methods The antibacterial properties of TBBQ were assessed against staphylococci growing in planktonic culture and as biofilms in the Calgary Biofilm Device. Established assays were employed to measure the effects of TBBQ on biofilm structure and bacterial membranes, and to assess resistance potential. A living-skin equivalent was used to evaluate the effects of TBBQ on human skin. Results TBBQ eradicated biofilms of S. aureus and other staphylococcal species at concentrations ≤64 mg/L. In contrast to other redox-active agents exhibiting activity against biofilms, TBBQ did not cause substantial destructuring of the biofilm matrix; instead, the antibiofilm activity of the compound was attributed to its ability to kill slow- and non-growing cells via membrane perturbation. TBBQ acted synergistically with gentamicin, did not damage a living-skin equivalent following topical application and exhibited low resistance potential. Conclusions The ability of TBBQ to eradicate biofilms appears to result from its ability to kill bacteria regardless of growth state. Preliminary evaluation suggests that TBBQ represents a promising candidate for development as a topical antibiofilm agent. PMID:27121399

  16. Tetrachloro-p-benzoquinone induces hepatic oxidative damage and inflammatory response, but not apoptosis in mouse: The prevention of curcumin

    International Nuclear Information System (INIS)

    This study investigated the protective effects of curcumin on tetrachloro-p-benzoquinone (TCBQ)-induced hepatotoxicity in mice. TCBQ-treatment causes significant liver injury (the elevation of serum AST and ALT activities, histopathological changes in liver section including centrilobular necrosis and inflammatory cells), oxidative stress (the elevation of TBAR level and the inhibition of SOD and catalase activities) and inflammation (up-regulation of iNOS, COX-2, IL-1β, IL-6, TNF-α and NF-κB). However, these changes were alleviated upon pretreatment with curcumin. Interestingly, TCBQ has no effect on caspase family genes or B-cell lymphoma 2 (Bcl-2)/Bcl-2 associated X (Bax) protein expressions, which implied that TCBQ-induced hepatotoxicity is independent of apoptosis. Moreover, curcumin was shown to induce phase II detoxifying/antioxidant enzymes HO-1 and NQO1 through the activation of nuclear factor erythroid-derived 2-like 2 (Nrf2). In summary, the protective mechanisms of curcumin against TCBQ-induced hepatoxicity may be related to the attenuation of oxidative stress, along with the inhibition of inflammatory response via the activation of Nrf2 signaling. - Highlights: • TCBQ-intoxication significantly increased AST and ALT activities. • TCBQ-intoxication induced oxidative stress in mice liver. • TCBQ-intoxication induced inflammatory response in mice liver. • TCBQ-intoxication induced hepatotoxicity is independent of apoptosis. • Curcumin relieved TCBQ-induced liver damage remarkably

  17. The peak effect of the photocurrent on the concentration of electron mediator (para-benzoquinone) in thylakoids

    International Nuclear Information System (INIS)

    Highlights: • Photocurrent from the isolated thylakoids has been captured in the presence of an electron mediator. • Several techniques have been used to confirm the nature of the photocurrent. • Peak effect on photocurrent with BQ concentration is found and a simplistic diffusion model is discussed. -- Abstract: This work investigates the photocurrent harvested from the isolated thylakoids. Several tests have been used to verify that the photocurrent measured is indeed from the photosynthesis on the thylakoid membranes. The photocurrent has a linear dependence on light intensity; the photocurrent shares similar frequency dependence as that of absorption spectrum of chlorophyll; the photocurrent decreases or disappears with the application of 3-(3′,4′-dichlorophenyl)-1,1-dimethylurea as an inhibitor. The new finding of this report is the observation of a peak in the photocurrent as a function of the concentration CBQ of electron mediator para-benzoquinone (p-BQ). It is found that the photocurrent measured increases at small CBQ, and a maximum current is obtained at CBQ ≈ 1.8–2 mM and decreases with further increase in CBQ. A simplistic model has been proposed to explain the peak. The effect of bias voltage applied between the electrodes on photocurrent is studied as well

  18. Exposure of hematopoietic stem cells to benzene or 1,4-benzoquinone induces gender-specific gene expression.

    Science.gov (United States)

    Faiola, Brenda; Fuller, Elizabeth S; Wong, Victoria A; Pluta, Linda; Abernethy, Diane J; Rose, Jason; Recio, Leslie

    2004-01-01

    Chronic exposure to benzene results in progressive decline of hematopoietic function and may lead to the onset of various disorders, including aplastic anemia, myelodysplastic syndrome, and leukemia. Damage to macromolecules resulting from benzene metabolites and misrepair of DNA lesions may lead to changes in hematopoietic stem cells (HSCs) that give rise to leukemic clones. We have shown previously that male mice exposed to benzene by inhalation were significantly more susceptible to benzene-induced toxicities than females. Because HSCs are targets for benzene-induced cytotoxicity and genotoxicity, we investigated DNA damage responses in HSC from both genders of 129/SvJ mice after exposure to 1,4-benzoquinone (BQ) in vitro or benzene in vivo. 1,4-BQ is a highly reactive metabolite of benzene that can cause cellular damage by forming protein and DNA adducts and producing reactive oxygen species. HSCs cultured in the presence of 1,4-BQ for 24 hours showed a gender-independent, dose-dependent cytotoxic response. RNA isolated from 1,4-BQ-treated HSCs and HSCs from mice exposed to 100 ppm benzene by inhalation showed altered expression of apoptosis, DNA repair, cell cycle, and growth control genes compared with unexposed HSCs. Rad51, xpc, and mdm-2 transcript levels were increased in male but not female HSCs exposed to 1,4-BQ. Males exposed to benzene exhibited higher mRNA levels for xpc, ku80, ccng, and wig1. These gene expression differences may partially explain the gender disparity in benzene susceptibility. HSC culture systems such as the one used here will be useful for testing the hematotoxicity of various substances, including other benzene metabolites.

  19. Design, Synthesis, Biological Evaluation, and Antioxidant and Cytotoxic Activity of Heteroatom-Substituted 1,4-Naphtho- and Benzoquinones.

    Science.gov (United States)

    Deniz, Nahide Gülşah; Ibis, Cemil; Gokmen, Zeliha; Stasevych, Maryna; Novikov, Volodymyr; Komarovska-Porokhnyavets, Olena; Ozyurek, Mustafa; Guclu, Kubilay; Karakas, Didem; Ulukaya, Engin

    2015-01-01

    In the present paper, we report the synthesis, characterization, and biological evaluation as antifungal, antibacterial, antioxidant, and cytotoxic/anticancer agents of N-, S-, O-substituted-1,4-naphtho- and 2,5-bis(amino-substituted)-1,4-benzoquinone derivatives. In the synthesized compounds, antimicrobial activity at low concentrations against Escherichia coli B-906, Staphylococcus aureus 209-P, and Mycobacterium luteum B-917 bacteria and Candida tenuis VKM Y-70 and Aspergillus niger F-1119 fungi in comparison with controls was identified. 2-(N-Diphenylmethylpiperazin-1-yl)-3-chloro-1,4-naphthoquinone 9a was the most potent, with a minimum inhibitory concentration value of 3.9 µg/mL against test culture M. luteum. The synthesized compounds were screened for their antioxidant capacity using the cupric-reducing antioxidant capacity (CUPRAC) method. 2,2'-[1-(2-Aminoethyl)piperazin-1-yl]-3,3'-dichloro-bis(1,4-naphthoquinone) 10 showed the highest antioxidant capacity, with a 0.455 CUPRAC-trolox equivalent antioxidant capacity (TEAC) coefficient. Other parameters of antioxidant activity (scavenging effects on OH(·), O2(·-), and H2O2) of these compounds were also determined. The cytotoxic activity of the compounds was investigated by employing the sulforhodamine B cell viability assay against A549 (lung), MCF-7 (breast), DU145 (prostate), and HT-29 (colon) cancer cell lines. Compound 10 exhibited the most powerful cytotoxic activity at a concentration of 20 µM against all cell lines. In addition to the strongest antioxidant activity of compound 10, it also had lowest IC50 values (activity.

  20. Electrochemical Assay of Effects of Organophosphate Poisoning on Acetylcholinesterase from Pheretima via2,6-Dimethyl-p-benzoquinone

    Institute of Scientific and Technical Information of China (English)

    WU Wu-ai; LI Jun; GAO Bao-ping; GUO Man-dong

    2012-01-01

    Electroanalytical techniques could be a reliable and promising alternative to classical and sophisticatcd methods because of their simplicity(small and portable),easy use,the ability to deliver fast response with high sensitivity and selectivity.A square wave voltammetric method was developed for the assessment of organophosphorus(OPs) compound impact on acetylcholinesterase(AChE) of Pheretima with 2,6-dimethyl-p-benzoquinone(2,6-DMBQ) as a redox indicator.The substrate of acetylthiocholine is hydrolyzed by AChE and the produced thiocholine reacts with 2,6-DMBQ to give an obvious shift of electrochemical signal.The reduction peak of 2,6-DMBQ is located at around -0.18 V which is far away from the oxidation potential of possible interference components often present in biosample.The decreased rate of reduction current was related with the activity of AChE.The inhibition of parathion-methyl on AChE was assessed.The inhibiton rate of OPs on AChE activity increased quickly during the first 10min inhibition,and after that the value of inhibition rate approached to be constant.AChE lost almost 29.3% of activity after 10 min incubation with 1 μg/mL parathion-methyl and 67.5% of activity with 10 μg/mL parathion-methyl,while the activity that corresponds to 40 μg/mL parathion-methyl was nearly completely inhibited(94.9%).Compared to cyclic voltammetry and amperometry,Square wave voltammetry(SWV) method is a high sensitive electroanalysis with fast scan-rate(only several seconds for one signal value) which is useful to prevent the electrodes from possible fouling or passivation.This method can be employed to assess the inhibition of organophosphate on AChE and investigate OPs impact on environmental animals.

  1. Lineage-related cytotoxicity and clonogenic profile of 1,4-benzoquinone-exposed hematopoietic stem and progenitor cells

    International Nuclear Information System (INIS)

    Hematopoietic stem cells (HSCs) and hematopoietic progenitor cells (HPCs) are sensitive targets for benzene-induced hematotoxicity and leukemogenesis. The impact of benzene exposure on the complex microenvironment of HSCs and HPCs remains elusive. This study aims to investigate the mechanism linking benzene exposure to targeting HSCs and HPCs using phenotypic and clonogenic analyses. Mouse bone marrow (BM) cells were exposed ex vivo to the benzene metabolite, 1,4-benzoquinone (1,4-BQ), for 24 h. Expression of cellular surface antigens for HSC (Sca-1), myeloid (Gr-1, CD11b), and lymphoid (CD45, CD3e) populations were confirmed by flow cytometry. The clonogenicity of cells was studied using the colony-forming unit (CFU) assay for multilineage (CFU-GM and CFU-GEMM) and single-lineage (CFU-E, BFU-E, CFU-G, and CFU-M) progenitors. 1,4-BQ demonstrated concentration-dependent cytotoxicity in mouse BM cells. The percentage of apoptotic cells increased (p < 0.05) following 1,4-BQ exposure. Exposure to 1,4-BQ showed no significant effect on CD3e+ cells but reduced the total counts of Sca-1+, CD11b+, Gr-1+, and CD45+ cells at 7 and 12 μM (p < 0.05). Furthermore, the CFU assay showed reduced (p < 0.05) clonogenicity in 1,4-BQ-treated cells. 1,4-BQ induced CFU-dependent cytotoxicity by significantly inhibiting colony growth for CFU-E, BFU-E, CFU-G, and CFU-M starting at a low concentration of exposure (5 μM); whereas for the CFU-GM and CFU-GEMM, the inhibition of colony growth was remarkable only at 7 and 12 μM of 1,4-BQ, respectively. Taken together, 1,4-BQ caused lineage-related cytotoxicity in mouse HPCs, demonstrating greater toxicity in single-lineage progenitors than in those of multi-lineage. - Highlights: • We examine 1,4-BQ toxicity targeting mouse hematopoietic cell lineages. • 1,4-BQ induces concentration-dependent cytotoxicity in bone marrow (BM) cells. • 1,4-BQ shows lineage-related toxicity on hematopoietic stem and progenitors. • 1,4-BQ toxicity is

  2. Lineage-related cytotoxicity and clonogenic profile of 1,4-benzoquinone-exposed hematopoietic stem and progenitor cells

    Energy Technology Data Exchange (ETDEWEB)

    Chow, Paik Wah [Biomedical Science Programme, School of Diagnostic & Applied Health Sciences, Faculty of Health Sciences, Universiti Kebangsaan Malaysia, Jalan Raja Abdul Muda Aziz, 50300 Kuala Lumpur, Wilayah Persekutuan (Malaysia); Toxicology Laboratory, Faculty of Health Sciences, Universiti Kebangsaan Malaysia, Jalan Raja Muda Abdul Aziz, 50300 Kuala Lumpur (Malaysia); Abdul Hamid, Zariyantey, E-mail: zyantey@ukm.edu.my [Biomedical Science Programme, School of Diagnostic & Applied Health Sciences, Faculty of Health Sciences, Universiti Kebangsaan Malaysia, Jalan Raja Abdul Muda Aziz, 50300 Kuala Lumpur, Wilayah Persekutuan (Malaysia); Toxicology Laboratory, Faculty of Health Sciences, Universiti Kebangsaan Malaysia, Jalan Raja Muda Abdul Aziz, 50300 Kuala Lumpur (Malaysia); Chan, Kok Meng [Environmental Health and Industrial Safety Programme, School of Diagnostic & Applied Health Sciences, Faculty of Health Sciences, Universiti Kebangsaan Malaysia, Jalan Raja Abdul Muda Aziz, 50300 Kuala Lumpur, Wilayah Persekutuan (Malaysia); Toxicology Laboratory, Faculty of Health Sciences, Universiti Kebangsaan Malaysia, Jalan Raja Muda Abdul Aziz, 50300 Kuala Lumpur (Malaysia); Inayat-Hussain, Salmaan Hussain [Environmental Health and Industrial Safety Programme, School of Diagnostic & Applied Health Sciences, Faculty of Health Sciences, Universiti Kebangsaan Malaysia, Jalan Raja Abdul Muda Aziz, 50300 Kuala Lumpur, Wilayah Persekutuan (Malaysia); Rajab, Nor Fadilah [Biomedical Science Programme, School of Diagnostic & Applied Health Sciences, Faculty of Health Sciences, Universiti Kebangsaan Malaysia, Jalan Raja Abdul Muda Aziz, 50300 Kuala Lumpur, Wilayah Persekutuan (Malaysia); Toxicology Laboratory, Faculty of Health Sciences, Universiti Kebangsaan Malaysia, Jalan Raja Muda Abdul Aziz, 50300 Kuala Lumpur (Malaysia)

    2015-04-01

    Hematopoietic stem cells (HSCs) and hematopoietic progenitor cells (HPCs) are sensitive targets for benzene-induced hematotoxicity and leukemogenesis. The impact of benzene exposure on the complex microenvironment of HSCs and HPCs remains elusive. This study aims to investigate the mechanism linking benzene exposure to targeting HSCs and HPCs using phenotypic and clonogenic analyses. Mouse bone marrow (BM) cells were exposed ex vivo to the benzene metabolite, 1,4-benzoquinone (1,4-BQ), for 24 h. Expression of cellular surface antigens for HSC (Sca-1), myeloid (Gr-1, CD11b), and lymphoid (CD45, CD3e) populations were confirmed by flow cytometry. The clonogenicity of cells was studied using the colony-forming unit (CFU) assay for multilineage (CFU-GM and CFU-GEMM) and single-lineage (CFU-E, BFU-E, CFU-G, and CFU-M) progenitors. 1,4-BQ demonstrated concentration-dependent cytotoxicity in mouse BM cells. The percentage of apoptotic cells increased (p < 0.05) following 1,4-BQ exposure. Exposure to 1,4-BQ showed no significant effect on CD3e{sup +} cells but reduced the total counts of Sca-1{sup +}, CD11b{sup +}, Gr-1{sup +}, and CD45{sup +} cells at 7 and 12 μM (p < 0.05). Furthermore, the CFU assay showed reduced (p < 0.05) clonogenicity in 1,4-BQ-treated cells. 1,4-BQ induced CFU-dependent cytotoxicity by significantly inhibiting colony growth for CFU-E, BFU-E, CFU-G, and CFU-M starting at a low concentration of exposure (5 μM); whereas for the CFU-GM and CFU-GEMM, the inhibition of colony growth was remarkable only at 7 and 12 μM of 1,4-BQ, respectively. Taken together, 1,4-BQ caused lineage-related cytotoxicity in mouse HPCs, demonstrating greater toxicity in single-lineage progenitors than in those of multi-lineage. - Highlights: • We examine 1,4-BQ toxicity targeting mouse hematopoietic cell lineages. • 1,4-BQ induces concentration-dependent cytotoxicity in bone marrow (BM) cells. • 1,4-BQ shows lineage-related toxicity on hematopoietic stem and

  3. Redox magnetohydrodynamics enhancement of stripping voltammetry of lead(II), cadmium(II) and zinc(II) ions using 1,4-benzoquinone as an alternative pumping species.

    Science.gov (United States)

    Ensafi, Ali A; Nazari, Z; Fritsch, I

    2012-01-21

    Differential pulse anodic stripping voltammetry (DPASV) coupled with redox-magnetohydrodynamics (MHD) is used to enhance the anodic stripping voltammetry (ASV) response using a mercury thin film-glassy carbon electrode. The sensitivity increased to at least a factor of two (at 1.2 T) and is facilitated by using 20.0 mmol L(-1) 1,4-benzoquinone as an alternative pumping species to enhance ASV by redox-MHD. The MHD force formed by the cross-product of ion flux with magnetic field induces solution convection during the deposition step, enhancing mass transport of the analytes to the electrode surface and increasing their preconcentrated quantity in the mercury thin film. Therefore, larger ASV peaks and improved sensitivities are obtained, compared with analyses performed without a magnet. The influence of pH, 1,4-benzoquinone concentration, accumulation potential, and time are also investigated. Detection limits of 0.05, 0.09 and 2.2 ng mL(-1) Cd(II), Pb(II) and Zn(II) were established with an accumulation time of 65 s. The method is used for the analysis of Cd(II), Pb(II) and Zn(II) in different water samples, certified reference materials, and saliva samples with satisfactory results. PMID:22116833

  4. Pd/Graphene catalytic hydrogenation of benzoquinone to hydroquinone%钯/石墨烯催化苯醌加氢制备氢醌

    Institute of Scientific and Technical Information of China (English)

    杨敬贺; 郁清涛; 毛立群

    2015-01-01

    采用微波辅助加热还原法合成了钯/石墨烯(Pd/G)、钯/活性炭(Pd/AC)、钯/石墨(Pd/Graphite)和钯/二氧化硅(Pd/SiO2),并使用透射电子显微镜观测了钯的形貌及在载体上的分散性。将负载型钯催化剂用于苯醌加氢反应,结果显示,Pd/G催化剂的活性最高,苯醌的转化率达到99%,氢醌的选择性为100%,并且循环7次后催化剂仍保持着较高的转化率和选择性。结构表征表明,石墨烯担载的钯纳米粒子的粒径约为5 nm ,无明显团聚。实验进一步考察了反应溶剂(甲醇、乙醇、丙酮、正丙醇、异丙醇、正丁醇)对 Pd/G催化苯醌加氢反应的影响,结果表明该反应对溶剂较为敏感,其中甲醇和丙酮较适宜作为反应溶剂。当以甲醇作为溶剂时,苯醌的转化率为98%,氢醌选择性为99%;以丙酮为溶剂时,苯醌转化率为98%,氢醌选择性为90%。研究工作表明,作为载体,石墨烯对钯催化剂的催化效果起着稳定和增强作用。%In the present study ,we exploited G as a support for palladium nanoparticles by mi‐crowave assisted reduction of palladium acetate with graphene under hydrogen atmosphere .In the same method ,we also employed graphite ,active carbon and silica as carrier for synthesis palladium graphite (Pd/Graphite) ,palladium active carbon (Pd/AC) and palladium silica (Pd/SiO2 ) .The hydrogenation of benzoquinone reaction has been selected as model reaction for e‐valuating G -based palladium catalysts (Pd/G) ,and the morphology and dispersion of palla‐dium on the carrier were observed by TEM .We utilized the supported palladium catalysts for benzoquinone hydrogenation reaction .The results imply that the Pd/G catalyst shows the high‐est activity .T he conversion of benzoquinone reached 99% and the selectivity to hydroquinone was 100% .In addtion ,the catalytic performance of Pd/G catalyst remained

  5. Charge-transfer complexes of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone with amino molecules in polar solvents

    Science.gov (United States)

    Berto, Silvia; Chiavazza, Enrico; Ribotta, Valentina; Daniele, Pier Giuseppe; Barolo, Claudia; Giacomino, Agnese; Vione, Davide; Malandrino, Mery

    2015-10-01

    The charge-transfer complexes have scientific relevance because this type of molecular interaction is at the basis of the activity of pharmacological compounds and because the absorption bands of the complexes can be used for the quantification of electron donor molecules. This work aims to assess the stability of the charge-transfer complexes between the electron acceptor 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and two drugs, procaine and atenolol, in acetonitrile and ethanol. The stability of DDQ in solution and the time required to obtain the maximum complex formation were evaluated. The stoichiometry and the stability of the complexes were determined, respectively, by Job's plot method and by the elaboration of UV-vis titrations data. The latter task was carried out by using the non-linear global analysis approach to determine the equilibrium constants. This approach to data elaboration allowed us to overcome the disadvantages of the classical linear-regression method, to obtain reliable values of the association constants and to calculate the entire spectra of the complexes. NMR spectra were recorded to identify the portion of the donor molecule that was involved in the interaction. The data support the participation of the aliphatic amino groups in complex formation and exclude the involvement of the aromatic amine present in the procaine molecule.

  6. Synthesis of Dioxa-cage Compounds as a New Probe for the Stereochemistry of the Bisadducts of p-Benzoquinone with 1,3-Cyclodienes

    Institute of Scientific and Technical Information of China (English)

    WU Hsien-Jen; TSAO Ching-Bo; TSAI Ting-Yueh

    2001-01-01

    @@ π-Facial stereoselectivety in Diels-alder reactions and their synthetic applications have attracted considerable attention in recent years. In the Diels-Alder reaction of the cyclopentadiene-quinone cycloadduct 1 with cycloalkadiene, four bisadducts with different stereochemistry could potentially result endo-anti-endo 2, endo-antiexo 3, endo-syn-exo 4, and endo-syn-endo 5. Nevertheless, 2 was the only one formed directly in the cycloaddition of 1 with cyclodienes. The π-facial selectivity in Diels-Alderr reactions of compounds 6 and 7 with cyclodienes was reported and the stereochemistry of the cycloadducts was determined by exhausted chemical correlation, spectral comparsion, and x-ray analyses. We report here the synthesis of dioxa-cge compounds 8-11 as a new probe for the determination of the stereochemistry of the bisadducts of p-benzoquinone with cyclodienes. The synthesis of dioxa-cage compounds 8-11 from the bisadducts 2-5 was achieved by a very short sequence. The stereochemistry of the dioxa-cage 8-11 was unambiguously determined by H-H COSY and NOE experiments.

  7. Synthesis of Dioxa-cage Compounds as a New Probe for the Stereochemistry of the Bisadducts of p-Benzoquinone with 1,3-Cyclodienes

    Institute of Scientific and Technical Information of China (English)

    WU; Hsien-Jen

    2001-01-01

    π-Facial stereoselectivety in Diels-alder reactions and their synthetic applications have attracted considerable attention in recent years. In the Diels-Alder reaction of the cyclopentadiene-quinone cycloadduct 1 with cycloalkadiene, four bisadducts with different stereochemistry could potentially result endo-anti-endo 2, endo-antiexo 3, endo-syn-exo 4, and endo-syn-endo 5. Nevertheless, 2 was the only one formed directly in the cycloaddition of 1 with cyclodienes. The π-facial selectivity in Diels-Alderr reactions of compounds 6 and 7 with cyclodienes was reported and the stereochemistry of the cycloadducts was determined by exhausted chemical correlation, spectral comparsion, and x-ray analyses. We report here the synthesis of dioxa-cge compounds 8-11 as a new probe for the determination of the stereochemistry of the bisadducts of p-benzoquinone with cyclodienes. The synthesis of dioxa-cage compounds 8-11 from the bisadducts 2-5 was achieved by a very short sequence. The stereochemistry of the dioxa-cage 8-11 was unambiguously determined by H-H COSY and NOE experiments.……

  8. The Amelioration of N-Acetyl-p-Benzoquinone Imine Toxicity by Ginsenoside Rg3: The Role of Nrf2-Mediated Detoxification and Mrp1/Mrp3 Transports

    Directory of Open Access Journals (Sweden)

    Sang Il Gum

    2013-01-01

    Full Text Available Previously, we found that Korean red ginseng suppressed acetaminophen (APAP-induced hepatotoxicity via alteration of its metabolic profile involving GSTA2 induction and that ginsenoside Rg3 was a major component of this gene induction. In the present study, therefore, we assessed the protective effect of Rg3 against N-acetyl-p-benzoquinone imine (NAPQI, a toxic metabolic intermediate of APAP. Excess NAPQI resulted in GSH depletion with increases in the ALT and AST activities in H4IIE cells. Rg3 pretreatment reversed GSH depletion by NAPQI. Rg3 resulted in increased mRNA levels of the catalytic and modulatory subunit of glutamate cysteine ligase (GCL, the rate-limiting steps in GSH synthesis and subsequently increased GSH content. Rg3 increased levels of nuclear Nrf2, an essential transcriptional factor of these genes. The knockdown or knockout of the Nrf2 gene abrogated the inductions of mRNA and protein by Rg3. Abolishment of the reversal of GSH depletion by Rg3 against NAPQI was observed in Nrf2-deficient cells. Rg3 induced multidrug resistance-associated protein (Mrp 1 and Mrp3 mRNA levels, but not in Nrf2-deficient cells. Taken together, these results demonstrate that Rg3 is efficacious in protecting hepatocytes against NAPQI insult, due to GSH repletion and coordinated gene regulations of GSH synthesis and Mrp family genes by Nrf2.

  9. The Negative Ion Photoelectron Spectrum of meta -Benzoquinone Radical Anion (MBQ •– ): A Joint Experimental and Computational Study

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Bo; Hrovat, David A.; Deng, S. H. M.; Zhang, Jian; Wang, Xue-Bin; Borden, Weston Thatcher

    2014-03-05

    Negative ion photoelectron (NIPE) spectra of the radical anion of meta-benzoquinone (MBQ, m-OC6H4O) have been obtained at 20 K, using both 355 and 266 nm lasers for electron photodetachment. The spectra show well-resolved peaks and complex spectral patterns. The electron affinity of MBQ is determined from the first resolved peak to be 2.875 ±17 0.010 eV. Single-point, CASPT2/aug-cc-pVTZ//CASPT2/ aug-cc-pVDZ calculations predict accurately the positions of the 0-0 bands in the NIPE spectrum for formation of the four lowest electronic states of neutral MBQ from the 2A2 state of MBQ•-. In addition, the Franck-Condon factors that are computed from the CASPT2/aug-cc-pVDZ optimized geometries,vibrational frequencies, and normal mode vectors, successfully simulate the intensities and frequencies of the vibrational peaks in the NIPE spectrum that are associated with each of these electronic states. The successful simulation of the NIPE spectrum of MBQ•- allows the assignment of 3B2 as the ground state of MBQ, followed by the 1B2 and 1A1 electronic states, respectively 9.0 ± 0.2 and 16.6 ± 0.2 kcal/mol higher in energy than the triplet. These experimental energy differences are in good agreement with the calculated values of 9.7 and 15.7 kcal/mol. The relative energies of these two singlet states in MBQ confirm the previous prediction that their relative energies would be reversed from those in meta-benzoquinodimethane (MBQDM, m-CH2C6H4CH2).

  10. Simultaneous Analysis of Tertiary Butylhydroquinone and 2-tert-Butyl-1,4-benzoquinone in Edible Oils by Normal-Phase High-Performance Liquid Chromatography.

    Science.gov (United States)

    Li, Jun; Bi, Yanlan; Liu, Wei; Sun, Shangde

    2015-09-30

    During the process of antioxidation of tertiary butylhydroquinone (TBHQ) in oil and fat systems, 2-tert-butyl-1,4-benzoquinone (TQ) can be formed. The toxicity of TQ was much more than that of TBHQ. In the work, a normal-phase high-performance liquid chromatography (NP-HPLC) method for the accurate and simultaneous detection of TBHQ and TQ in edible oils was investigated. A C18 column was used to separate TBHQ and TQ, and the gradient elution solutions consisted of n-hexane containing 5% ethyl acetate and n-hexane containing 5% isopropanol. The ultraviolet (UV) detector was set at dual wavelength mode (280 nm for TBHQ and 310 nm for TQ). The column temperature was 30 °C. Before the NP-HPLC analysis, TBHQ and TQ were first extracted by methanol, subjected to vortex treatment, and then filtered through a 0.45 μm membrane filter. Results showed that linear ranges of TBHQ and TQ were both within 0.10-500.00 μg/mL (R(2) > 0.9999). The limit of detection (LOD) and limit of quantification (LOQ) of TBHQ and TQ were below 0.30 and 0.91 μg/mL and below 0.10 and 0.30 μg/mL, respectively. The recoveries of TBHQ and TQ were 98.92-102.34 and 96.28-100.58% for soybean oil and 96.11-99.42 and 98.83-99.24% for lard, respectively. These results showed that NP-HPLC can be successfully used to analyze simultaneously TBHQ and TQ in the oils and fats. PMID:26365419

  11. Study on the electrochemical reduction of tetramethyl-p-benzoquinone%四甲基对苯醌电化学还原研究

    Institute of Scientific and Technical Information of China (English)

    任园园; 金葆康

    2011-01-01

    Cyclic voltammetry, IR spectroelectrochemistry, cyclic voltabsorptometry and derivative cyclic voltabsorptometry techniques were used to investigate the electrochemical reduction of tetramethyl - p - benzoquinone (TMBQ) in CH3CN solution. The experimental results showed that the electrochemical reduction of TMBQ is not simple two-step single electron transfer process. Further study indicated that the reduction process is coupled with following chemical reaction. An irresversible oxidation peak at -0. 32 V was observed. The result suggests that dimerization reaction occurred during the electrochemical reduction process of TMBQ. In situ IR spectroelectrochemistry further confirmed the formation of dimers.%利用循环伏安法、现场红外光谱电化学、循环伏吸法及导数循环伏吸法研究四甲基对苯醌(TMBQ)在乙腈溶液中的电化学氧化还原过程.结果表明:TMBQ的电化学还原并不是简单的两步单电子还原过程.研究发现,还原过程同时伴随后行化学反应.TMBQ的还原产物在-0.32 V处产生不可逆氧化峰,表明在四甲基对苯醌的电化学还原过程中发生了二聚反应.现场红外光谱电化学进一步证实了二聚体的生成.

  12. MiR-133a regarded as a potential biomarker for benzene toxicity through targeting Caspase-9 to inhibit apoptosis induced by benzene metabolite (1,4-Benzoquinone).

    Science.gov (United States)

    Chen, Yujiao; Sun, Pengling; Bai, Wenlin; Gao, Ai

    2016-11-15

    Benzene is an environmental and industrial chemical which is widely utilized in various applications. Our previous study showed that miR-133a expression was down-regulated in chronic benzene poisoning workers, but the mechanism of miR-133a in benzene-induced hematotoxicity remains unclear. In this population-based study, benzene-exposed group recruited workers whose concentration of air benzene was 3.50±1.60mg/m(3), and control workers who were exposed to 0.06±0.01mg/m(3) air benzene. By comparison, Caspase-9 and Caspase-3 was up-regulated while miR-133a expression decreased in benzene-exposed workers. Pearson correlation analysis showed that miR-133a was reversely correlated with pro-apoptotic gene Caspase-9 in population-based study. Moreover, multiple linear regressions indicated that miR-133a was positively associated with blood cells count. To explore the underlying mechanism of miR-133a in benzene-induced hematotoxicity, AO/EB staining and TEM ultrastructural analysis were conducted to verify the activation of apoptosis in Human Leukemic U937 Cells induced by benzene metabolites (1,4-Benzoquinone, 1,4-BQ), while the mechanism of miR-133a in 1,4-BQ-induced apoptosis was performed using lentivirus vectors transfection. The results demonstrated that 1,4-BQ evidently induced mitochondria-mediated apoptosis and increased pro-apoptotic genes (Caspase-9 and Caspase-3) expression in a dose-dependent manner. The mechanistic study showed 1,4-BQ decreased miR-133a expression and miR-133a over-expression attenuated 1, 4-BQ-caused upregulation of Caspase-9, Caspase-3 and apoptosis. In conclusion, our research suggested that benzene induced hematotoxicity by decreasing miR-133a and caspase-dependent apoptosis which might contribute to the underlying mechanism of miR-133a in benzene-induced hematotoxicity.

  13. Spectrophotometric determination of repaglinide in tablets based on charge-transfer complexation reaction with chloranilic acid and dichloro-dicyano benzoquinone

    Directory of Open Access Journals (Sweden)

    Cijo Madathil X.

    2011-01-01

    Full Text Available Two simple, accurate, precise, inexpensive, selective and sensitive spectrophotometric methods are described for the determination of repaglinide (RPG in bulk drug and its tablets. The methods were based on the charge- transfer complex reaction between RPG in acetonitrile with p-chloranilic acid (CAA or 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ in dioxane and subsequent formation of intensely colored radical anions of the reagents which were measured at 520 nm (CAA or 590 nm (DDQ. Several experimental variables affecting the complex formation, stability of the colored species and sensitivity of the reaction were optimized. Under the optimized conditions, Beer’s law was obeyed over the concentration ranges of 20-400 and 5-80 μg ml-1 RPG for CAA and DDQ methods, respectively, and the corresponding correlation coefficients were 0.9995 and 0.9998. The apparent molar absorptivity values were 1.02x103 and 4.60x103 for CAA and DDQ methods respectively, with corresponding Sandell sensitivity values of 0.4438 and 0.0984 μg cm-2. Limits of detection (LOD were calculated to be 7.07 and 2.42 μg ml-1 and the limits of quantification (LOQ were 21.43 and 7.33 μg ml-1 RPG, for CAA method and DDQ method, respectively. Validation results demonstrated that the inter day and intra day accuracy were up to 97.56%. The precision determined did not exceed 2.5% of RSD. The methods were successfully used for the determination of RPG in tablet form and the results were in good agreement with the label claims as shown by the recoveries which were in the range of 99.22- 102.8% with standard deviation values < 2%. The accuracy of the method was confirmed by recovery studies via standardaddition procedure with excellent recovery 98.24-104.0 ± 1.08-3.35.

  14. Spectrophotometric study of interaction of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone with diaza-18-crown-6 and diaza-15-crown-5 in acetonitrile and chloroform solutions

    Science.gov (United States)

    Hasani, Masoumeh; Shamsipur, Mojtaba

    2005-03-01

    Interactions of diaza-18-crown-6 and diaza-15-crown-5, as electron donors, with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), as an electron acceptor, have been investigated spectrophotometrically in acetonitrile and chloroform solutions. The results indicated immediate formation of an electron donor-electron acceptor complex DA: D+A ⇌fastKDA which is followed by two relatively slow consecutive reactions: DA⟶kDA⟶kProduct The pseudo-first-order rate constants for the formation of the ionic intermediate and the final product have been evaluated at various temperatures by computer fitting of the absorbance time data to appropriate equations. The formation constants of the resulting DA complexes have also been determined. The influences of both the azacrown's structure and the solvent properties on the formation of DA complexes and the rates of subsequent reactions are discussed.

  15. EPR Study on the Complex Formed by Charge-Transfer Processbetween Ground-state Acceptor 2,3-Dicyano-5, 6-dichloro-1,4-benzoquinone and Some Donors and on Cation Radical of Pery-lene (or Pyrene)

    Institute of Scientific and Technical Information of China (English)

    SHI Ji-Liang; ZHOU Cheng-Ming; ZHAO Xin; XU Jia-Yi; JIANG Xi-Kui

    2001-01-01

    EPR Study showed that semi-quinone radical anion of 2,3-dicyano-5,6-dichloro-1,4-benzoquinone (DDQ)was formed in a charge transfer process between groung-state DDQ as accep-tor and each one of following ground state donors,i.e.,4-methyl-4'-tridecyl-2,2'-bipyridyl;4-methyl-4'-nonyl-2,2'-bipyridyl)ruthenium(2+)perchlorate and perylene.EPRstdy also showed that there are perylene cation radical and pyrene catinon radical in thefollowing experimentaql conditions:(a)in98%sulfuric acid.(b)10-3mol/L perylene (orpyrene)was dissolved in trifluoroacetic acid-nitrlbenzene (1:1V/V).

  16. The structure and vibrational spectra of the 2,5-dimethylpyrazine (2,5-DMP) 1:1 adduct with 2,5-dichloro-3,6-dihydroxy-p-benzoquinone (CLA)

    International Nuclear Information System (INIS)

    Graphical abstract: The infrared, Raman and inelastic neutron scattering (INS) spectra of 2,5-DMP with CLA, its crystal structure, the DFT method applied to the crystalline state, the hydrogen bonded OH...N infinite chains without any proton transfer. Research highlights: → A novel complex of 2,5-dimethylpyrazine with 2,5-dichloro-3,6-dihydroxy-p-benzoquinone. → The crystal structure at 100 K is presented. → The infrared, Raman and inelastic neutron scattering spectra are shown. → They are compared with calculated by using the DFT methods applied to the crystalline state. → The calculated structure and the frequencies are well consistent, except of the CH3 torsional mode. - Abstract: The complexation of 2,5-dimethylpyrazine (2,5-DMP) with 2,5-dichloro-3,6-dihydroxy-p-benzoquinone (CLA) leads to the formation of the hydrogen bonded OH...N infinite chains without any proton transfer. In the high and medium frequency region of the IR spectra a characteristic Hadzi's trio with maxima at ca. 2400, 1800 and 1150 cm-1 is observed. The infrared, Raman and inelastic neutron scattering (INS) spectra are compared with those calculated by using the DFT methods applied to the crystalline state. The optimization of the structure by using this theoretical approach is also performed. Very good conformity of the experimental and theoretical structures is visible. The reproduction of vibrational spectra is also good except for the low frequency bands related to the CH3 torsional modes. One gets relatively good agreement by using PWC(dnp) approach. Applications of other theoretical models leads to much higher values of CH3 torsional frequency.

  17. Insights into the mechanism of the reaction between tetrachloro-p-benzoquinone and hydrogen peroxide and their implications in the catalytic role of water molecules in producing the hydroxyl radial.

    Science.gov (United States)

    Li, Ping; Wang, Weihua; Sun, Qiao; Li, Zhen; Du, Aijun; Bi, Siwei; Zhao, Yan

    2013-08-26

    Detailed mechanisms for the formation of hydroxyl or alkoxyl radicals in the reactions between tetrachloro-p-benzoquinone (TCBQ) and organic hydroperoxides are crucial for better understanding the potential carcinogenicity of polyhalogenated quinones. Herein, the mechanism of the reaction between TCBQ and H2O2 has been systematically investigated at the B3LYP/6-311++G** level of theory in the presence of different numbers of water molecules. We report that the whole reaction can easily take place with the assistance of explicit water molecules. Namely, an initial intermediate is formed first. After that, a nucleophilic attack of H2O2 onto TCBQ occurs, which results in the formation of a second intermediate that contains an OOH group. Subsequently, this second intermediate decomposes homolytically through cleavage of the O-O bond to produce a hydroxyl radical. Energy analyses suggest that the nucleophilic attack is the rate-determining step in the whole reaction. The participation of explicit water molecules promotes the reaction significantly, which can be used to explain the experimental phenomena. In addition, the effects of F, Br, and CH3 substituents on this reaction have also been studied.

  18. Antinociceptive Effect of Tephrosia sinapou Extract in the Acetic Acid, Phenyl-p-benzoquinone, Formalin, and Complete Freund’s Adjuvant Models of Overt Pain-Like Behavior in Mice

    Directory of Open Access Journals (Sweden)

    Renata M. Martinez

    2016-01-01

    Full Text Available Tephrosia toxicaria, which is currently known as Tephrosia sinapou (Buc’hoz A. Chev. (Fabaceae, is a source of compounds such as flavonoids. T. sinapou has been used in Amazonian countries traditional medicine to alleviate pain and inflammation. The purpose of this study was to evaluate the analgesic effects of T. sinapou ethyl acetate extract in overt pain-like behavior models in mice by using writhing response and flinching/licking tests. We demonstrated in this study that T. sinapou extract inhibited, in a dose (1–100 mg/kg dependent manner, acetic acid- and phenyl-p-benzoquinone- (PBQ- induced writhing response. Furthermore, it was active via intraperitoneal, subcutaneous, and peroral routes of administration. T. sinapou extract also inhibited formalin- and complete Freund’s adjuvant- (CFA- induced flinching/licking at 100 mg/kg dose. In conclusion, these findings demonstrate that T. sinapou ethyl acetate extract reduces inflammatory pain in the acetic acid, PBQ, formalin, and CFA models of overt pain-like behavior. Therefore, the potential of analgesic activity of T. sinapou indicates that it deserves further investigation.

  19. Effects of Homologous Expression of 1,4-Benzoquinone Reductase and Homogentisate 1,2-Dioxygenase Genes on Wood Decay in Hyper-Lignin-Degrading Fungus Phanerochaete sordida YK-624.

    Science.gov (United States)

    Mori, Toshio; Koyama, Genki; Kawagishi, Hirokazu; Hirai, Hirofumi

    2016-10-01

    We investigated the function of 1,4-benzoquinone reductase (BQR)- and homogentisate 1,2-dioxygenase (HGD)-like genes in wood degradation by Phanerochaete sordida YK-624, which exhibits high ligninolytic activity and selectivity. We determined homologous expression in the genomic and cDNA sequences of BQR- and HGD-like genes in P. sordida YK-624 (PsBQR and PsHGD). Both genes shared high homology (≥90 % amino acid sequence similarity) with the corresponding genes in Phanerochaete chrysosporium. These genes were co-transformed with a reporter gene into an uracil auxotrophic mutant of P. sordida YK-624. The PsBQR and PsHGD co-transformants exhibited lower holocellulolytic activity and higher ligninolytic selectivity than the control transformants. In liquid culture with vanillin, both co-transformants significantly accelerated vanillin degradation. Thus, we suggest that the rapid metabolism of low-molecular weight lignin fragments, due to the homologous expression of BQR- and HGD-like genes, affects quinone redox cycling to produce hydroxyl radicals, thereby decreasing holocellulose degradation and increasing ligninolytic selectivity. PMID:27363425

  20. Application of soft- and hard-modelling approaches to resolution of kinetics of electron donor-acceptor complex formation of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone with imipramine in different solutions

    International Nuclear Information System (INIS)

    Kinetics of electron donor-acceptor (EDA) complex formation of imipramine and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) was investigated spectrophotometrically in acetonitrile, 1,2-dichloroethane, and chloroform solutions using soft- and hard-modelling approaches. From the results of exploratory analysis of kinetic data and the spectral changes by soft-modelling approaches, evolving factor analysis (EFA) and orthogonal projection approach (OPA), a consecutive two-steps reaction with two intermediates was proposed for the process in acetonitrile and 1,2-dichloroethane media and one with a single intermediate in chloroform solution. Secondly, by applying, multivariate nonlinear least squares hard-modelling approach on the collected experimental kinetic data matrix, the nonlinear parameters (rate constants) as well as the linear parameters (spectral profiles) were obtained by fitting the collected experimental kinetic data matrix to the proposed model. Small values of standard deviation in the resulting parameters and sum of squares of the residuals (ssq) obtained showed the proper selection of the model. Furthermore, the values of lack of fit and percent of explained variance confirmed the correct identified models. Identification of the model with the aid of soft-modelling approaches followed by application of the hard-modelling approaches decreases significantly the rotational ambiguity associated with the obtained concentration and spectral profiles. Variations in the kinetic constants were in complete agreement with the model proposed and the solvent polarities

  1. The Diels-Alder reaction of 2-trans-cinamoyl-1-4-benzoquinone with buta-1,3 diene and 2,3-dimethylbuta-1,3-diene; Reacciones Diels-Alde de 1,4-benzoquinonas mono- y 2,3-disustituidas con 1,3-dienos

    Energy Technology Data Exchange (ETDEWEB)

    Farina, F.; Valderrama, J.A. [Instituto de Quimica Organica General, CSIC, Madrid (Spain)

    1995-12-01

    The Diels-Alder reaction of 2-trans-cinamoyl-1,4-benzoquinone (12) with buta-1,3-diene (9) and 2,3-dimethylbuta-1,3-diene (10) afforded exclusively the corresponding angular adducts 14 and 15 in high yields. The cycloaddition of 2-acetyl-3-methoxy. 2-acetyl-3-chloro-and 2,3-acetyl-3-butylthio-1,4-benzoquinone 5-7 with buta-1,3-diene (9); 2,3-dimenthylbuta-1,3-diene (10) and 2,3-dichlorobuta-1,3-diene (11) afforded sitespecifically, the 4a,5,8,8a-tetrahydro-1,4-naphthoquinones 21-23 and 1,4-dihydroxy-5,8-dihydronaphthalene (19). Similary, 2-methoxycarbonyl-3-chloro-1,4-benzoquinona (8) reacts with dienes 9 and 10 to afford adducts 20 and 23 generated by attack of the dienes to the C5-C6 double bond of the quinones. The course of these reactions was interpreted on the basis of electronic and/or steric hindrance effects of the OMe,Cl and Sbut groups by decreasing the activation effect of the COMe and CO{sub 2}Me substituents. 14 refs.

  2. Density functional theory study on the formation of reactive benzoquinone imines by hydrogen abstraction

    DEFF Research Database (Denmark)

    Leth, Rasmus; Rydberg, Patrik; Jørgensen, Flemming Steen;

    2015-01-01

    Many drug compounds are oxidized by cytochrome P450 (CYP) enzymes to form reactive metabolites. This study presents density functional theory calculations of the CYP-mediated metabolism of acetaminophen and a series of related compounds that can form reactive metabolites by hydrogen abstraction....... The substitution pattern affects the activation barrier for hydrogen abstraction by up to 30 kJ/mol. A correlation (R(2) = 0.72) between the transition-state energies and the corresponding substrate radical energies has been established. Using this correlation is significantly less time-demanding than using...

  3. Simulation of interindividual differences in inactivation of reactive para-benzoquinone imine metabolites of diclofenac by glutathione S-transferases in human liver cytosol.

    Science.gov (United States)

    den Braver, Michiel W; Zhang, Yongjie; Venkataraman, Harini; Vermeulen, Nico P E; Commandeur, Jan N M

    2016-07-25

    Diclofenac is a widely prescribed NSAID that causes severe idiosyncratic drug induced liver injury (IDILI) in a small part of the patient population. Formation of protein-reactive metabolites is considered to play a role in the development of diclofenac-induced IDILI. Therefore, a high hepatic activity of enzymes involved in bioactivation of diclofenac is expected to increase the risk for liver injury. However, the extent of covalent protein binding may also be determined by activity of protective enzymes, such as glutathione S-transferases (GSTs). This is supported by an association study in which a correlation was found between NSAID-induced IDILI and the combined null genotypes of GSTM1 and GSTT1. In the present study, the activity of 10 different recombinant human GSTs in inactivation of protein-reactive quinoneimine (QI) metabolites of diclofenac was tested. Both at low and high GSH concentrations, high activities of GSTA1-1, A2-2, A3-3, M1-1, M3-3 and P1-1 in the inactivation of these QIs were found. By using the expression levels of GSTs in livers of 22 donors, a 6-fold variation in GST-dependent inactivation of reactive diclofenac metabolites was predicted. Moreover, it was shown in vitro that GSTs can strongly increase the efficiency of GSH to protect against the alkylation of the model thiol N-acetylcysteine by reactive diclofenac metabolites. The results of this study demonstrate that variability of GST expression may significantly contribute to the inter-individual differences in susceptibility to diclofenac-induced liver injury. In addition, expression levels of GSTs in in vitro models for hepatotoxicity may be important factors determining sensitivity to diclofenac cytotoxicity. PMID:27183920

  4. Study of tetrachloro-p-benzoquinone with 1-methylimidazole in dichloromethane under ground State%四氯苯醌与N-甲基咪唑在二氯甲烷中的基态作用研究

    Institute of Scientific and Technical Information of China (English)

    郭小永; 郭洪玲; 严宝珍

    2003-01-01

    研究了四氯苯醌(CA)与N-甲基咪唑(NMIm)在CH2Cl2中的基态作用,结果表明二者反应形成CA与NMIm的摩尔比为1∶1的电荷转移络合物(CTC),并采用UV-Vis、IR、及NMR进行了表征.应用Benesi-Hildebrand方程计算得到该CTC的平衡常数KCT=6.234×10-2L*mol-1,及摩尔消光系数εCT=8.442×103(L*mol-1*cm-1).

  5. Interaction of carboranyl boron-centred radicals with phosphites and addition of carborane-containing and some others phosphoranyl radicals to 3,6-di-tret.butyl-ortho-benzoquinone

    International Nuclear Information System (INIS)

    Reactivity of B-carboranyl radicals in their interaction with phosphites has been studied. It is shown, that preparative photolysis of bis (m-carborane-9-yl) mercury ad bis (p-carborane-2-yl) mercury with trimethylphosphite results in dimethyl esters of m- and p-B-carboranylphosphponic acids. Interaction between carboranyl boron-centred radicals and phosphites proceeds via phosphoranyl radical formation. The difference in reactivity of isomeric B-carboranyl radicals is connected with decrease of attacking radical electronegativity in the series of p- > m- > 0 - carboranes

  6. Sequence Classification: 291311 [

    Lifescience Database Archive (English)

    Full Text Available Non-TMB Non-TMH Non-TMB Non-TMB Non-TMB Non-TMB >gi|49176426|ref|YP_026269.1| 2-octaprenyl-6-methoxy...-1,4-benzoquinone --> 2-octaprenyl-3-methyl-6-methoxy-1,4-benzoquinone || http://www.ncbi.nlm.nih.gov/protein/49176426 ...

  7. Sequence Classification: 296597 [

    Lifescience Database Archive (English)

    Full Text Available Non-TMB Non-TMH Non-TMB Non-TMB Non-TMB Non-TMB >gi|15804425|ref|NP_290465.1| 2-octaprenyl-6-methoxy...-1,4-benzoquinone --> 2-octaprenyl-3-methyl-6-methoxy-1,4-benzoquinone || http://www.ncbi.nlm.nih.gov/protein/15804425 ...

  8. Formation of CTC by 2-chloro-5-methoxyl-p-benzoquinone and tertiary amines in acetonitrile%胺与2-氯-5-甲氧基对苯醌在乙腈中形成电荷转移络合物的研究

    Institute of Scientific and Technical Information of China (English)

    郭洪玲; 郭小永; 严宝珍

    2003-01-01

    用"连续变化法"测出三乙胺、三正丁基胺与2-氯-5-甲氧基对苯醌在乙腈中形成的基态电荷转移络合物(CTC)均以1∶1相结合,并且用Hildebrand-Benesi方程分别计算出CTC的平衡常数KCT、摩尔吸光系数εCT和形成CTC的能量变化ΔGCT.

  9. Quenching of bacteriochlorophyll fluorescence in chlorosomes from Chloroflexus aurantiacus by exogenous quinones

    DEFF Research Database (Denmark)

    Tokita, S; Frigaard, N-U; Hirota, M;

    2000-01-01

    The quenching of bacteriochlorophyll (BChl) c fluorescence in chlorosomes isolated from Chloroflexus aurantiacus was examined by the addition of various benzoquinones, naphthoquinones (NQ), and anthraquinones (AQ). Many quinones showed strong quenching in the micromolar or submicromolar range. Th...

  10. Albumin Adducts of Electrophilic Benzene Metabolites in Benzene-Exposed and Control Workers

    OpenAIRE

    Lin, Yu-Sheng; Vermeulen, Roel; Tsai, Chin H.; Waidyanatha, Suramya; Lan, Qing; Rothman, Nathaniel; Smith, Martyn T.; Zhang, Luoping; Shen, Min; Li, Guilan; Yin, Songnian; Kim, Sungkyoon; Rappaport, Stephen M.

    2006-01-01

    Background Metabolism of benzene produces reactive electrophiles, including benzene oxide (BO), 1,4-benzoquinone (1,4-BQ), and 1,2-benzoquinone (1,2-BQ), that are capable of reacting with blood proteins to produce adducts. Objectives The main purpose of this study was to characterize relationships between levels of albumin adducts of these electrophiles in blood and the corresponding benzene exposures in benzene-exposed and control workers, after adjusting for important covariates. Because se...

  11. Role of Quinones in Electron Transfer of PQQ–Glucose Dehydrogenase Anodes—Mediation or Orientation Effect

    Energy Technology Data Exchange (ETDEWEB)

    Babanova, Sofia; Matanovic, Ivana; Chavez, Madelaine Seow; Atanassov, Plamen

    2015-06-24

    In this study, the influence of two quinones (1,2- and 1,4-benzoquinone) on the operation and mechanism of electron transfer in PQQ-dependent glucose dehydrogenase (PQQ–sGDH) anodes has been determined. Benzoquinones were experimentally explored as mediators present in the electrolyte. The electrochemical performance of the PQQ–sGDH anodes with and without the mediators was examined and for the first time molecular docking simulations were used to gain a fundamental understanding to explain the role of the mediator molecules in the design and operation of the enzymatic electrodes. It was proposed that the higher performance of the PQQ–sGDH anodes in the presence of 1,2- and 1,4-benzoquinones introduced in the solution is due to the shorter distance between these molecules and PQQ in the enzymatic molecule. It was also hypothesized that when 1,4-benzoquinone is adsorbed on a carbon support, it would play the dual role of a mediator and an orienting agent. At the same time, when 1,2-benzoquinone and ubiquinone are adsorbed on the electrode surface, the enzyme would transfer the electrons directly to the support, and these molecules would primarily play the role of an orienting agent.

  12. Electrogenerated chemiluminescence quenching of Ru(bpy)32+ (bpy=2,2′-bipyridine) in the presence of acetaminophen, salicylic acid and their metabolites

    International Nuclear Information System (INIS)

    Quenching of Ru(bpy) 32+ (bpy=2,2′-bipyridine) coreactant electrogenerated chemiluminescence (ECL) has been observed in the presence of acetaminophen, salicylic acid and related complexes. However, no quenching is observed with the acetylsalicylic acid. In most instances, quenching is observed with 100-fold excess of quencher (compared to ECL luminophore) with complete quenching observed between 10,000 and 100,000 fold excess. Fluorescence and UV–vis experiments coupled with bulk electrolysis support the formation of benzoquinone products upon electrochemical oxidation. The mechanism of quenching may involve the interaction of the electrochemically generated benzoquinone species with (i) the ⁎Ru(bpy)32+ excited state or (ii) highly energetic coreactant radicals. - Highlights: ▶ Efficient quenching of the electrogenerated chemiluminescence is observed. ▶ Acetaminophen, salicylic acid and related compounds can be detected. ▶ The mechanism of quenching involves benzoquinones formed upon electrolysis.

  13. "Quinone Millipedes" Reconsidered: Evidence for a Mosaic-Like Taxonomic Distribution of Phenol-Based Secretions across the Julidae.

    Science.gov (United States)

    Bodner, Michaela; Vagalinski, Boyan; Makarov, Slobodan E; Antić, Dragan Ž; Vujisić, Ljubodrag V; Leis, Hans-Jörg; Raspotnig, Günther

    2016-03-01

    The defensive chemistry of juliformian millipedes is characterized mainly by benzoquinones ("quinone millipedes"), whereas the secretions of the putative close outgroup Callipodida are considered to be exclusively phenolic. We conducted a chemical screening of julid secretions for phenolic content. Most species from tribes Cylindroiulini (15 species examined), Brachyiulini (5 species examined), Leptoiulini (15 species examined), Uncigerini (2 species examined), Pachyiulini (3 species examined), and Ommatoiulini (2 species examined) had non-phenolic, in most cases exclusively benzoquinonic secretions. In contrast, tribes Cylindroiulini, Brachyiulini, and Leptoiulini also contained representatives with predominantly phenol-based exudates. In detail, p-cresol was a major compound in the secretions of the cylindroiulines Styrioiulus pelidnus and S. styricus (p-cresol content 93 %) and an undetermined Cylindroiulus species (p-cresol content 51 %), in the brachyiulines Brachyiulus lusitanus (p-cresol content 21 %) and Megaphyllum fagorum (p-cresol content 92 %), as well as in an undescribed Typhloiulus species (p-cresol content 32 %, Leptoiulini). In all species, p-cresol was accompanied by small amounts of phenol. The secretion of M. fagorum was exclusively phenolic, whereas phenols were accompanied by benzoquinones in all other species. This is the first incidence of clearly phenol-dominated secretions in the Julidae. We hypothesize a shared biosynthetic route to phenols and benzoquinones, with benzoquinones being produced from phenolic precursors. The patchy taxonomic distribution of phenols documented herein supports multiple independent regression events in a common pathway of benzoquinone synthesis rather than multiple independent incidences of phenol biosynthesis. PMID:26971956

  14. Regioselective Wacker Oxidation of Internal Alkenes: Rapid Access to Functionalized Ketones Facilitated by Cross-Metathesis

    KAUST Repository

    Morandi, Bill

    2013-07-26

    Wacka wacka: The title reaction makes use of a wide range of directing groups (DG) to enable the highly regioselective oxidation of alkenes, and occurs predictably at the distal position. Both E and Z alkenes afford valuable functionalized ketones and cross-metathesis was shown to facilitate the preparation of the starting materials. BQ=benzoquinone.

  15. ONO-pincer ruthenium complex-bound norvaline for efficient catalytic oxidation of methoxybenzenes with hydrogen peroxide.

    Science.gov (United States)

    Yoshida, Ryota; Isozaki, Katsuhiro; Yokoi, Tomoya; Yasuda, Nobuhiro; Sadakane, Koichiro; Iwamoto, Takahiro; Takaya, Hikaru; Nakamura, Masaharu

    2016-08-21

    The enhanced catalytic activity of ruthenium complex-bound norvaline Boc-l-[Ru]Nva-OMe 1, in which the ONO-pincer ruthenium complex Ru(pydc)(terpy) 2 is tethered to the α-side chain of norvaline, has been demonstrated for the oxidation of methoxybenzenes to p-benzoquinones with a wide scope of substrates and unique chemoselectivity. PMID:27314504

  16. Sequence Classification: 295614 [

    Lifescience Database Archive (English)

    Full Text Available Non-TMB TMH Non-TMB Non-TMB Non-TMB Non-TMB >gi|15803442|ref|NP_289475.1| 2-octaprenyl-6-methoxy...phenol--> 2-octaprenyl-6-methoxy-1, 4-benzoquinone || http://www.ncbi.nlm.nih.gov/protein/15803442 ...

  17. Sequence Classification: 290421 [

    Lifescience Database Archive (English)

    Full Text Available Non-TMB TMH Non-TMB Non-TMB Non-TMB Non-TMB >gi|16130809|ref|NP_417383.1| 2-octaprenyl-6-methoxy...phenol--> 2-octaprenyl-6-methoxy-1, 4-benzoquinone || http://www.ncbi.nlm.nih.gov/protein/16130809 ...

  18. First total synthesis of yanuthones: novel farnesylated epoxycyclohexenoid marine natural products

    OpenAIRE

    Mehta, Goverdhan; Pan, Subhas Chandra

    2005-01-01

    The total synthesis of the recently isolated marine natural products of mixed biosynthetic origin, yanuthones A, 13 C and 22-deacylyanuthone A,has been accomplished following a short regio- and stereocontrolled approach involving the key intermediacy of 2-farnesyl-p-benzoquinone.

  19. Redox cycling of potential antitumor aziridinylquinones

    NARCIS (Netherlands)

    Lusthof, Klaas J.; Mol, de Nicolaas J.; Richter, Wilma; Janssen, Lambert H.M.; Butler, John; Hoey, Brigid M.; Verboom, Willem; Reinhoudt, David N.

    1992-01-01

    The formation of reactive oxygen intermediates (ROI) during redox cycling of newly synthetized potential antitumor 2,5-bis (1-aziridinyl)-1,4-benzoquinone (BABQ) derivatives has been studied by assaying the production of ROI (superoxide, hydroxyl radical, and hydrogen peroxide) by xanthine oxidase i

  20. Males of Hylamorpha elegans burmeister (Coleoptera: Scarabaeidae) are attracted to odors released from conspecific females.

    Science.gov (United States)

    Quiroz, Andrés; Palma, Ruben; Etcheverría, Paulina; Navarro, Vicente; Rebolledo, Ramón

    2007-04-01

    The behavioral responses of Hylamorpha elegans L. (Coleoptera: Scarabaeidae, Rutelinae) to the semiochemicals released from conspecific individual adults were studied, with particular attention paid to female attraction of males. Odors released from virgin females significantly attracted male conspecifics in both the field and laboratory olfactometer and wind tunnel bioassays. However, females did not attract other females, and males attracted no one. The response of male H. elegans to (1) compounds (1,4-hydroquinone and 1,4-benzoquinone) released only by unmated females; (2) the essential oil of the secondary host (Nothofagus obliqua); and (3) the blend of 1,4-hydroquinone and 1,4-benzoquinone with N. obliqua essential oil was studied. The blend of 1,4-benzoquinone mixed with essential oil at the trial concentration was attractive with males. The same response was found with 1,4-hydroquinone alone. The essential oil did not have the expected attractant effect on conspecific males. These results suggest that, when combined with essential oil, 1,4-benzoquinone may function in the sexual behavior of males and females. These findings are discussed in terms of the ecological role of this putative sexual pheromone and its potential use in a strategy of control of this pest.

  1. Chromosphores in cellulosics, XI: isoloation and identification of residual chromophores from bacterial cellulose

    Science.gov (United States)

    In the present work, bacterial cellulose (BC) was analyzed for its chromophore content with the chromophore release and identification (CRI) method. In aged BC, seven chromophores were unambiguously identified, despite their very low (ppb) presence. The compounds contain 2-hydroxy-[1,4]benzoquinone,...

  2. Inhibitory effect of benzene metabolites on nuclear DNA synthesis in bone marrow cells

    International Nuclear Information System (INIS)

    Effects of endogenously produced and exogenously added benzene metabolites on the nuclear DNA synthetic activity were investigated using a culture system of mouse bone marrow cells. Effects of the metabolites were evaluated by a 30-min incorporation of [3H]thymidine into DNA following a 30-min interaction with the cells in McCoy's 5a medium with 10% fetal calf serum. Phenol and muconic acid did not inhibit nuclear DNA synthesis. However, catechol, 1,2,4-benzenetriol, hydroquinone, and p-benzoquinone were able to inhibit 52, 64, 79, and 98% of the nuclear DNA synthetic activity, respectively, at 24 μM. In a cell-free DNA synthetic system, catechol and hydroquinone did not inhibit the incorporation of [3H]thymidine triphosphate into DNA up to 24 μM but 1,2,4-benzenetriol and p-benzoquinone did. The effect of the latter two benzene metabolites was completely blocked in the presence of 1,4-dithiothreitol (1 mM) in the cell-free assay system. Furthermore, when DNA polymerase α, which requires a sulfhydryl (SH) group as an active site, was replaced by DNA polymerase 1, which does not require an SH group for its catalytic activity, p-benzoquinone and 1,2,4-benzenetriol were unable to inhibit DNA synthesis. Thus, the data imply the p-benzoquinone and 1,2,4-benzenetriol inhibited DNA polymerase α, consequently resulting in inhibition of DNA synthesis in both cellular and cell-free DNA synthetic systems. The present study identifies catechol, hydroquinone, p-benzoquinone, and 1,2,4-benzenetriol as toxic benzene metabolites in bone marrow cells and also suggests that their inhibitory action on DNA synthesis is mediated by mechanism(s) other than that involving DNA damage as a primary cause

  3. Synthesis of 1,3,4-Thiadiazole, 1,3,4-Thiadiazine, 1,3,6-Thiadiazepane and Quinoxaline Derivatives from Symmetrical Dithiobiureas and Thioureidoethylthiourea Derivatives

    Directory of Open Access Journals (Sweden)

    A. Abou-Zied

    2005-08-01

    Full Text Available Reactions of N,N`-disubstituted hydrazinecarbothioamides 8a-c and substituted thioureidoethylthioureas 9a-c with 2,3,5,6-tetrachloro-1,4-benzoquinone (chloranil, 10a and 2,3,5,6-tetrabromo-1,4-benzoquinone (bromanil, 10b to form N,N`-disubstituted [1,3,4]thiadiazole-2,5-diamines 11a-c, 6,7-dichloro-3-substituted amino-1H-benzo[1,3,4]- thiadiazine-5,8-diones 12a-c, 2,3,7,8-tetrahalothianthrene-1,4,6,9-tetraones 13a,b, 5,6,8- trihalo-7-oxo-3,7-dihydro-2H-quinoxaline-1-carbothioic acid substituted amides 14a-c, 15a-c and 7-substituted imino-[1,3,6]thiadiazepane-3-thiones 16a-c are reported. Rationales for the observed conversions are presented.

  4. Synthesis of 1,3,4-Thiadiazole, 1,3,4-Thiadiazine, 1,3,6-Thiadiazepane and Quinoxaline Derivatives from Symmetrical Dithiobiureas and Thioureidoethylthiourea Derivatives

    OpenAIRE

    Abou-Zied, A.; K. El-Shaieb; A. Mourad; Hassan, A

    2005-01-01

    Reactions of N,N`-disubstituted hydrazinecarbothioamides 8a-c and substituted thioureidoethylthioureas 9a-c with 2,3,5,6-tetrachloro-1,4-benzoquinone (chloranil, 10a) and 2,3,5,6-tetrabromo-1,4-benzoquinone (bromanil, 10b) to form N,N`-disubstituted [1,3,4]thiadiazole-2,5-diamines 11a-c, 6,7-dichloro-3-substituted amino-1H-benzo[1,3,4]- thiadiazine-5,8-diones 12a-c, 2,3,7,8-tetrahalothianthrene-1,4,6,9-tetraones 13a,b, 5,6,8- trihalo-7-oxo-3,7-dihydro-2H-quinoxaline-1-carbothioic acid substit...

  5. Millipedes as food for humans

    DEFF Research Database (Denmark)

    Enghoff, Henrik; Manno, Nicola; Tchibozo, Sévérin;

    2014-01-01

    The first record of millipedes (Diplopoda) being regularly used for food by humans (the Bobo people of Burkina Faso) is given, including information on how the millipedes are prepared. The species in question are Tymbodesmus falcatus (Karsch, 1881) and Sphenodesmus sheribongensis (Schiøtz, 1966......) (Gomphodesmidae) and an unidentified species of Spirostreptidae. New information on the nutritional value of millipedes is provided; unsaturated fatty acids, calcium, and iron contents are particularly high. The millipedes’ defensive secretions, hydrogen cyanide and benzoquinones, present a severe challenge...... for the spread of millipedes as an everyday food source. On the other hand, the possibility that benzoquinones may act as insect-repellents, as known from studies on nonhuman primates, and that sublethal cyanide ingestionmay enhance human innate resistance tomalaria, suggests promising ethnomedical perspectives...

  6. Synthesis and reactivity of aliphatic sulfur pentafluorides from substituted (pentafluorosulfanyl)benzenes.

    Science.gov (United States)

    Vida, Norbert; Václavík, Jiří; Beier, Petr

    2016-01-01

    Oxidation of 3- and 4-pentafluorosulfanyl-substituted anisoles and phenols with hydrogen peroxide and sulfuric acid provided a mixture of SF5-substituted muconolactone, maleic, and succinic acids. A plausible mechanism for the formation of the aliphatic SF5 compounds was presented and their chemical reactivity was investigated. SF5-substituted para-benzoquinone was synthesized; its oxidation led to an improved yield of 2-(pentafluorosulfanyl)maleic acid. The reaction of SF5-substituted maleic anhydride and para-benzoquinone with cyclopentadiene afforded the Diels-Alder adducts. Decomposition of 3-(pentafluorosulfanyl)muconolactone in acidic, neutral and basic aqueous media was investigated and the decarboxylation of 2-(pentafluorosulfanyl)maleic acid provided 3-(pentafluorosulfanyl)acrylic acid. PMID:26877813

  7. Transient Effects of Salt Shock on the Photosynthetic Machinery in Synechocystis sp. PCC 6803

    Institute of Scientific and Technical Information of China (English)

    毛海滨; 阮翔; 李国富; 公衍道; 张秀芳; 赵南明

    2002-01-01

    The transient effects of NaCl on chlorophyll (Chl) fluorescence in Synechocystis sp. PCC 6803 cells were examined. In dark-adapted cells, salt shock induced a transition from state 2 to state 1, and the artificial quinones, phenyl-1,4-benzoquinone (PBQ) and 2,5-dibromo-3-methyl-6-isopropyl-1,4-benzoquinone (DBMIB), quenched the Chl fluorescence markedly after addition of 0.8 mol/L NaCl. In light-adapted cells, the addition of NaCl caused a significant increase in the stationary fluorescence yield, which resulted in a decrease in the quantum yield of photosystem II (PSII). The results indicate that salt shock can induce a change in the affinity between the photosystems and the phycobilisomes (PBS) and can perturb the orientation of the Chl molecules in PSII.

  8. Cytotoxic Terpene Quinones from Marine Sponges

    OpenAIRE

    Marina Gordaliza

    2010-01-01

    The 1,4-benzoquinone moiety is a common structural feature in a large number of compounds that have received considerable attention owing to their broad spectrum of biological activities. The cytotoxic and antiproliferative properties of many natural sesquiterpene quinones and hydroquinones from sponges of the order Dictyoceratida, such as avarol, avarone, illimaquinone, nakijiquinone and bolinaquinone, offer promising opportunities for the development of new antitumor agents. The present rev...

  9. Enantioselective total synthesis of (−)-epoxyquinols A and B. Novel, convenient access to chiral epoxyquinone building blocks through enzymatic desymmetrization

    OpenAIRE

    Mehta, Goverdhan; Islam, Kabirul

    2004-01-01

    Following our recent total synthesis of the biologically potent natural products epoxyquinols A and B in racemic form, we have now accomplished the total synthesis of the (−)-epoxyquinols A and B, anti-podes of the angiogenesis inhibiting natural products, through a protocol that involves enzymatic desymmetrization of a versatile epoxyquinone derivative, readily available from the Diels–Alder adduct of cyclopentadiene and p-benzoquinone.

  10. Trypanocidal activity of a new pterocarpan and other secondary metabolites of plants from Northeastern Brazil flora.

    Science.gov (United States)

    Vieira, Nashira Campos; Espíndola, Laila Salmen; Santana, Jaime Martins; Veras, Maria Leopoldina; Pessoa, Otília Deusdênia Loiola; Pinheiro, Sávio Moita; de Araújo, Renata Mendonça; Lima, Mary Anne Sousa; Silveira, Edilberto Rocha

    2008-02-15

    Two hundred fifteen compounds isolated from plants of Northeastern Brazil flora have been assayed against epimastigote forms of Trypanosoma cruzi, using the tetrazolium salt MTT as an alternative method. Eight compounds belonging to four different species: Harpalyce brasiliana (Fabaceae), Acnistus arborescens and Physalis angulata (Solanaceae), and Cordia globosa (Boraginaceae) showed significant activity. Among them, a novel and a known pterocarpan, a chalcone, four withasteroids, and a meroterpene benzoquinone were the represented chemical classes.

  11. Pyranose Dehydrogenase from Agaricus campestris and Agaricus xanthoderma: Characterization and Applications in Carbohydrate Conversions

    OpenAIRE

    Clemens K Peterbauer; Dietmar Haltrich; Petra Staudigl; Iris Krondorfer

    2013-01-01

    Pyranose dehydrogenase (PDH) is a flavin-dependent sugar oxidoreductase that is limited to a rather small group of litter-degrading basidiomycetes. The enzyme is unable to utilize oxygen as an electron acceptor, using substituted benzoquinones and (organo) metal ions instead. PDH displays a broad substrate specificity and intriguing variations in regioselectivity, depending on substrate, enzyme source and reaction conditions. In contrast to the related enzyme pyranose 2-oxidase (POx), PDHs fr...

  12. Optimization of SPE/GC/HPLC Analytical Procedure for Determination of Phenol, Quinones, and Carboxylic Acids in Water Samples

    OpenAIRE

    Katarzyna Bielicka-Daszkiewicz; Monika Hadzicka; Adam Voelkel

    2012-01-01

    Chromatographic techniques are among the most useful analytical methods. Gas and liquid chromatography were used in the analysis of some organic compounds: phenol, hydroquinone, benzoquinone, and maleic and fumaric acids. The analytical way for the determination of these compounds in water samples was investigated. Solid-phase extraction (SPE) technique was used on the sample preparation step, different divinylbenzene-based sorbents were applied. Calibration curves of given compounds were lin...

  13. Quinones from Heliotropium ovalifolium.

    Science.gov (United States)

    Guntern, A; Ioset, J R; Queiroz, E F; Foggin, C M; Hostettmann, K

    2001-10-01

    Two new benzoquinones, heliotropinones A and B, have been isolated from the aerial parts of Heliotropium ovalifolium. Their structures were elucidated by spectrometric methods including high resolution electrospray ionization (ESI-HR), EI mass spectrometry, 1H, 13C and 2D NMR experiments. The two quinones demonstrated antifungal activities against Cladosporium cucumerinum and Candida albicans as well as antibacterial activity against Bacillus subtilis. PMID:11576613

  14. A novel fixative for immunofluorescence staining of CD133-positive glioblastoma stem cells

    OpenAIRE

    Sherman, Jonathan H.; Redpath, Gerard T.; Redick, Jan A.; Purow, Benjamin W.; Laws, Edward R.; Jane, John A.; Shaffrey, Mark E.; Hussaini, Isa M.

    2011-01-01

    Isolation of glioblastoma stem cells requires incubation of tumor cells in a neural stem cell media. Neurospheres containing these glioblastoma stem cells are formed after approximately a five-day period. These cells can then be analyzed for the presence of stem cell markers. Immunofluorescence staining for these markers can serve as a valuable tool for analyzing the intact neurosphere directly in stem cell media. Here we present the use of a novel fixative (1,4-benzoquinone) for immunofloure...

  15. Synthesis and reactivity of aliphatic sulfur pentafluorides from substituted (pentafluorosulfanyl)benzenes

    OpenAIRE

    Vida, Norbert; Václavík, Jiří; Beier, Petr

    2016-01-01

    Oxidation of 3- and 4-pentafluorosulfanyl-substituted anisoles and phenols with hydrogen peroxide and sulfuric acid provided a mixture of SF5-substituted muconolactone, maleic, and succinic acids. A plausible mechanism for the formation of the aliphatic SF5 compounds was presented and their chemical reactivity was investigated. SF5-substituted para-benzoquinone was synthesized; its oxidation led to an improved yield of 2-(pentafluorosulfanyl)maleic acid. The reaction of SF5-substituted maleic...

  16. Adsorption and dehydrogenation of tetrahydroxybenzene on Cu(111)

    DEFF Research Database (Denmark)

    Bebensee, Fabian; Svane, K.; Bombis, Christian;

    2013-01-01

    Adsorption of tetrahydroxybenzene (THB) on Cu(111) and Au(111) surfaces is studied using a combination of STM, XPS, and DFT. THB is deposited intact, but on Cu(111) it undergoes gradual dehydrogenation of the hydroxyl groups as a function of substrate temperature, yielding a pure dihydroxy......-benzoquinone phase at 370 K. Subtle changes to the adsorption structure upon dehydrogenation are explained from differences in molecule–surface bonding....

  17. Electrochemical reactions and ionization processes

    OpenAIRE

    Girault, Hubert; Liu, Baohong; Qiao, Liang; Bi, Hongyan; Prudent, Michel; Lion, Niels; Abonnenc, Mélanie

    2010-01-01

    Electrochemical or photo-electrochemical reactions in both electrospray ionization and laser desorption ionization are discussed stressing the role of the electrode reaction in influencing the ionization process. In particular, upon application of a high voltage during electrospray ionization, the emitter includes a working electrode, where redox reactions are observed, such as electro-generation of benzoquinone and metal ions. In contrast, the target plate in laser-induced desorption ionizat...

  18. Crystal structure determination of thymoquinone by high-resolution X-ray powder diffraction

    OpenAIRE

    Pagola, S.; Benavente, A; Raschi, A.; Romano, E; Molina, M. A. A.; Stephens, P.W.

    2004-01-01

    The crystal structure of 2-isopropyl-5-methyl-1,4-benzoquinone (thymoquinone) and its thermal behavior—as necessary physical and chemical properties—were determined in order to enhance the current understanding of thymoquinone chemical action by using high resolution x-ray powder diffraction, Fourier transform infrared spectroscopy (FTIR), and 3 thermo-analytical techniques thermogravimetric analysis (TGA), differential thermal analysis (DTA), and differential scanning calorimetry (DSC). The ...

  19. Efficient and Highly Aldehyde Selective Wacker Oxidation

    KAUST Repository

    Teo, Peili

    2012-07-06

    A method for efficient and aldehyde-selective Wacker oxidation of aryl-substituted olefins using PdCl 2(MeCN) 2, 1,4-benzoquinone, and t-BuOH in air is described. Up to a 96% yield of aldehyde can be obtained, and up to 99% selectivity can be achieved with styrene-related substrates. © 2012 American Chemical Society.

  20. “Quinone Millipedes” Reconsidered: Evidence for a Mosaic-Like Taxonomic Distribution of Phenol-Based Secretions across the Julidae

    OpenAIRE

    Bodner, Michaela; Vagalinski, Boyan; Makarov, Slobodan E.; Antić, Dragan Ž.; Ljubodrag V. Vujisić; Leis, Hans-Jörg; Raspotnig, Günther

    2016-01-01

    The defensive chemistry of juliformian millipedes is characterized mainly by benzoquinones (”quinone millipedes”), whereas the secretions of the putative close outgroup Callipodida are considered to be exclusively phenolic. We conducted a chemical screening of julid secretions for phenolic content. Most species from tribes Cylindroiulini (15 species examined), Brachyiulini (5 species examined), Leptoiulini (15 species examined), Uncigerini (2 species examined), Pachyiulini (3 species examined...

  1. Resistive molecular memories: influence of molecular parameters on the electrical bistability.

    Science.gov (United States)

    Di Motta, Simone; Di Donato, Eugenio; Negri, Fabrizia; Orlandi, Giorgio; Fazzi, Daniele; Castiglioni, Chiara

    2009-05-13

    The electrical bistability behavior of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) along with two additional benzoquinone derivatives (TCQ and TCN) and pentacene (PNT) is investigated by computing intra- and intermolecular charge transfer parameters and by comparing the efficiency of bulk charge transport and charge injection at the electrode/organic interface in the presence of neutral and charged molecular species. The bulk charge transport is modeled assuming a charge hopping regime and by computing hopping rates and mobilities. Molecular dynamics simulations are carried out to estimate the effect of thermal disorder on charge transfer integrals. The efficiency of the interface transport is estimated by comparing the electron affinities of benzoquinone derivatives and the ionization potential of pentacene with the work function of commonly employed electrodes. It is shown that the observed memory effect can be rationalized in terms of an interplay of the two transport mechanisms by showing that the OFF state is dominated by interface limited phenomena and the ON state may be determined also by bulk transport limited phenomena. While the contribution of collective effects cannot be ruled out for the macroscopic memory phenomenon, we show that, at a molecular level, sizable intramolecular reorganization energies are fundamental for the efficiency of the device, provided their magnitude does not hamper the charge transport across the device. It is suggested that control over molecular parameters might be exploited to design more efficient resistive molecular memories. PMID:19374415

  2. Oxidative 4-dechlorination of polychlorinated phenols is catalyzed by extracellular fungal lignin peroxidases

    International Nuclear Information System (INIS)

    The extracellular lignin peroxidases (ligninases) of Phanerochaete chrysosporium catalyzed H2O2-dependent spectral changes in several environmentally significant polychlorinated phenols: 2,4-dichloro-, 2,4,5-trichloro-, 2,4,6-trichloro-, and pentachlorophenol. Gas chromatography/mass spectrometry of reduced and acetylated reaction products showed that, in each case, lignin peroxidase catalyzed a 4-dechlorination of the starting phenol to yield a p-benzoquinone. The oxidation of 2,4-dichlorophenol also yielded a dechlorinated coupling dimer, tentatively identified as 2-chloro-6-(2,4-dichlorophenoxy)-p-benzoquinone. Experiments on the stoichiometry of 2,4,6-trichlorophenol oxidation showed that this substrate was quantitatively dechlorinated to give the quinone and inorganic chloride. H218O-labeling experiments on 2,4,6-trichlorophenol oxidation demonstrated that water was the source of the new 4-oxo substituent in 2,6-di-chloro-p-benzoquinone. The results indicate a mechanism whereby lignin peroxidase oxidizes a 4-chlorinated phenol to an electrophilic intermediate, perhaps the 4-chlorocyclohexadienone cation. Nucleophilic attack by water and elimination of HCl then ensue at the 4-position, which produces the quinone. Lignin peroxidases have previously been implicated in the degradation by Phanerochaete of several nonphenolic aromatic pollutants. It appears likely from their results that these peroxidases could also catalyze the initial dechlorination of certain polychlorinated phenols in vivo

  3. Near-IR squaraine dye-loaded gated periodic mesoporous organosilica for photo-oxidation of phenol in a continuous-flow device.

    Science.gov (United States)

    Borah, Parijat; Sreejith, Sivaramapanicker; Anees, Palapuravan; Menon, Nishanth Venugopal; Kang, Yuejun; Ajayaghosh, Ayyappanpillai; Zhao, Yanli

    2015-09-01

    Periodic mesoporous organosilica (PMO) has been widely used for the fabrication of a variety of catalytically active materials. We report the preparation of novel photo-responsive PMO with azobenzene-gated pores. Upon activation, the azobenzene gate undergoes trans-cis isomerization, which allows an unsymmetrical near-infrared squaraine dye (Sq) to enter into the pores. The gate closure by cis-trans isomerization of the azobenzene unit leads to the safe loading of the monomeric dye inside the pores. The dye-loaded and azobenzene-gated PMO (Sq-azo@PMO) exhibits excellent generation of reactive oxygen species upon excitation at 664 nm, which can be effectively used for the oxidation of phenol into benzoquinone in aqueous solution. Furthermore, Sq-azo@PMO as the catalyst was placed inside a custom-built, continuous-flow device to carry out the photo-oxidation of phenol to benzoquinone in the presence of 664-nm light. By using the device, about 23% production of benzoquinone with 100% selectivity was achieved. The current research presents a prototype of transforming heterogeneous catalysts toward practical use. PMID:26601266

  4. Pulse electroanalysis at gold-gold micro-trench electrodes: chemical signal filtering.

    Science.gov (United States)

    Dale, Sara E C; Marken, Frank

    2013-01-01

    Bipotentiostatic control of micro- and nano-trench sensor systems provides new opportunities for enhancing signals (employing feedback currents) and for improved selectivity (by "chemical filtering"). In this study both phenomena are exploited with a gold-gold micro-trench electrode with ca. 70 microm width and ca. 800 microm trench depth. In "generator-collector mode", feedback current enhancement is demonstrated for the hydroquinone/ benzoquinone redox system. Next, a "modulator-sensor mode" experiment is developed in which one electrode potential is stepped into the negative potential region (employing the normal pulse voltammetry method) to induce an oscillating pH change locally in the micro-trench. The resulting shift in the hydroquinone/benzoquinone reversible potential causes a Faradaic sensor signal (employing chronoamperometry). This method provides a "chemical filter" by selecting pH-sensitive redox processes only, and by showing enhanced sensitivity in the region of low buffer capacity. The results for the chemically reversible hydroquinone/benzoquinone system are contrasted to the detection of the chemically irreversible ammonia oxidation.

  5. Intermolecular electron transfer from intramolecular excitation and coherent acoustic phonon generation in a hydrogen-bonded charge-transfer solid.

    Science.gov (United States)

    Rury, Aaron S; Sorenson, Shayne; Dawlaty, Jahan M

    2016-03-14

    Organic materials that produce coherent lattice phonon excitations in response to external stimuli may provide next generation solutions in a wide range of applications. However, for these materials to lead to functional devices in technology, a full understanding of the possible driving forces of coherent lattice phonon generation must be attained. To facilitate the achievement of this goal, we have undertaken an optical spectroscopic study of an organic charge-transfer material formed from the ubiquitous reduction-oxidation pair hydroquinone and p-benzoquinone. Upon pumping this material, known as quinhydrone, on its intermolecular charge transfer resonance as well as an intramolecular resonance of p-benzoquinone, we find sub-cm(-1) oscillations whose dispersion with probe energy resembles that of a coherent acoustic phonon that we argue is coherently excited following changes in the electron density of quinhydrone. Using the dynamical information from these ultrafast pump-probe measurements, we find that the fastest process we can resolve does not change whether we pump quinhydrone at either energy. Electron-phonon coupling from both ultrafast coherent vibrational and steady-state resonance Raman spectroscopies allows us to determine that intramolecular electronic excitation of p-benzoquinone also drives the electron transfer process in quinhydrone. These results demonstrate the wide range of electronic excitations of the parent of molecules found in many functional organic materials that can drive coherent lattice phonon excitations useful for applications in electronics, photonics, and information technology. PMID:26979698

  6. Quinone-formaldehyde polymer as an active material in Li-ion batteries

    Science.gov (United States)

    Pirnat, Klemen; Mali, Gregor; Gaberscek, Miran; Dominko, Robert

    2016-05-01

    A benzoquinone polymer is synthesized by the polymerisation of hydrobenzoquinone and formaldehyde, followed by oxidation process using a hydrogen peroxide to convert hydroquinone to quinone. As prepared materials are characterized with FTIR, 1H-13C CPMAS NMR, pyrolysis coupled with gas chromatography (GC) and mass spectrometer (MS), TGA-MS analysis, EDX, elemental analysis, XRD, SEM and TEM microscopies and BET nitrogen adsorption. The benzoquinone polymer shows an excellent electrochemical performance when used as a positive electrode material in Li-ion secondary batteries. Using an electrolyte consisting 1 M bis(trifluoromethane)-sulfonimide lithium salt dissolved in 1,3-dioxolane and dimethoxyethane in a vol. ratio 1:1 (1 M LiTFSI/DOL + DME = 1:1) a stable capacity close to 150 mAh/g can be obtained. Compared to other electroactive materials based on benzoquinones it has a supreme capacity stability and is prepared by a simple synthesis using easily accessible starting materials. Further improvements in the capacity value (up to the theoretical value of 406 mAh/g) can be foreseen by achieving a higher degree of oxidation and by modification of polymerization process to enhance the electronic and ionic conductivity.

  7. Electrogenerated chemiluminescence quenching of Ru(bpy){sub 3} {sup 2+} (bpy=2,2 Prime -bipyridine) in the presence of acetaminophen, salicylic acid and their metabolites

    Energy Technology Data Exchange (ETDEWEB)

    Haslag, Catherine S. [Department of Chemistry, Missouri State University, Springfield, Missouri 65897 (United States); Richter, Mark M., E-mail: MarkRichter@missouristate.edu [Department of Chemistry, Missouri State University, Springfield, Missouri 65897 (United States)

    2012-03-15

    Quenching of Ru(bpy) {sub 3}{sup 2+} (bpy=2,2 Prime -bipyridine) coreactant electrogenerated chemiluminescence (ECL) has been observed in the presence of acetaminophen, salicylic acid and related complexes. However, no quenching is observed with the acetylsalicylic acid. In most instances, quenching is observed with 100-fold excess of quencher (compared to ECL luminophore) with complete quenching observed between 10,000 and 100,000 fold excess. Fluorescence and UV-vis experiments coupled with bulk electrolysis support the formation of benzoquinone products upon electrochemical oxidation. The mechanism of quenching may involve the interaction of the electrochemically generated benzoquinone species with (i) the {sup Low-Asterisk }Ru(bpy){sub 3}{sup 2+} excited state or (ii) highly energetic coreactant radicals. - Highlights: Black-Right-Pointing-Triangle Efficient quenching of the electrogenerated chemiluminescence is observed. Black-Right-Pointing-Triangle Acetaminophen, salicylic acid and related compounds can be detected. Black-Right-Pointing-Triangle The mechanism of quenching involves benzoquinones formed upon electrolysis.

  8. Nitrogen-rich higher-molecular soil organic compounds patterned by lignin degradation products: Considerations on the nature of soil organic nitrogen

    Science.gov (United States)

    Liebner, Falk; Bertoli, Luca; Pour, Georg; Klinger, Karl; Ragab, Tamer; Rosenau, Thomas

    2016-04-01

    The pathways leading to accumulation of covalently bonded nitrogen in higher-molecular soil organic matter (SOM) are still a controversial issue in soil science and geochemistry. Similarly, structural elucidation of the variety of the types of nitrogenous moieties present in SOM is still in its infancy even though recent NMR studies suggest amide-type nitrogen to form the majority of organically bonded nitrogen which is, however, frequently not in accordance with the results of wet-chemical analyses. Following the modified polyphenol theory of Flaig and Kononova but fully aware of the imperfection of a semi-abiotic simulation approach, this work communicates the results of a study that investigated some potential nitrogen accumulation pathways occurring in the re-condensation branch of the theory following the reactions between well-known low-molecular lignin and carbohydrate degradation products with nitrogenous nucleophiles occurring in soils under aerobic conditions. Different low-molecular degradation products of lignin, cellulose, and hemicellulose, such as hydroquinone, methoxyhydroquinone, p-benzoquinone, 2,5-dihydroxy-[1,4]benzoquinone, glucose, xylose, and the respective polysaccharides, i.e. cellulose, xylan as well as various types of lignin were subjected to a joint treatment with oxygen and low-molecular N-nucleophiles, such as ammonia, amines, and amino acids in aqueous conditions, partly using respective 15N labeled compounds for further 15N CPMAS NMR studies. Product mixtures derived from mono- and polysaccharides have been comprehensively fractionated and analyzed by GC/MS after derivatization. Some of ammoxidized polyphenols and quinones have been analyzed by X-ray photoelectron spectroscopy. Some products, such as those obtained from ammoxidation of methoxy hydroquinone using 15N labeled ammonia were fractionated following the IHSS protocol. Individual humin (H), humic acid (HA), and fulvic acid (FA) fractions were subjected to elemental analyses

  9. Analytical Study for the Charge-Transfer Complexes of Rosuvastatin Calcium with π-Acceptors

    Directory of Open Access Journals (Sweden)

    Nourah Z. Alzoman

    2013-07-01

    Full Text Available Studies were carried out to investigate the charge-transfer (CT reaction of ROS-Ca, as a n-electron donor with various p-acceptors: tetracyanoethylene, p-chloranilic acid, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, 2,3,5,6-tetrabromo-1,4-benzoquinone, 1,3,5-trinitrobenzene, 2,3,5,6-tetrachloro-1,4-benzoquinone, 7,7,8,8-tetracyano-quinodimethane, and 2,4,7-trinitro-9-fluorenone. Different colored CT complexes were obtained. The reaction mechanism and site of interaction were determined by ultraviolet-visible spectrophotometric techniques and computational molecular modeling. The formation of the colored complexes was utilized in the development of simple, rapid and accurate spectrophotometric methods for the determination of ROS-Ca. Under the optimum reaction conditions, linear relationships with good correlation coefficients (0.9984–0.9995 were found between the absorbances and the concentrations of ROS-Ca in the range of 2–200 mg mL−1. The limits of detection ranged from 0.41 to 12.24 mg mL−1. No interference could be observed from the additives commonly present in the tablets or from the drugs that are co-formulated with ROS-Ca in its combined formulations. The methods were successfully applied to the analysis of tablets with good accuracy and precision; the recovery percentages ranged from 99.54–100.46 ± 1.58–1.82%. The results were compared favorably with the reported method. The proposed methods are practical and valuable for routine application in quality control laboratories for determination of ROS-Ca in its bulk form and tablets.

  10. Analytical study for the charge-transfer complexes of losartan potassium

    Energy Technology Data Exchange (ETDEWEB)

    Darwish, Ibrahim A. [Department of Pharmaceutical Analytical Chemistry, Faculty of Pharmacy, Assiut University, Assiut 71526 (Egypt)]. E-mail: iadarwish@yahoo.com

    2005-09-06

    Studies were carried out, for the first time, to investigate the charge-transfer reactions of losartan potassium (LOS-K) as n-electron donor with the {sigma}-acceptor iodine and various {pi}-acceptors: 7,7,8,8-tetracyanoquinodimethane, 1,3,5-trinitrobenzene, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, p-chloranilic acid, tetracyanoethylene, 2,3,5,6-tetrabromo-1,4-benzoquinone, 2,3,5,6-tetrachloro-1,4-benzoquinone, and 2,4,7-trinitro-9-fluorenone. Different colored charge-transfer complexes and radical anions were obtained. Different variables affecting the reactions were studied and optimized. The formed complexes and the site of interaction were examined by UV-vis, IR, and {sup 1}H NMR techniques, and computational molecular modeling. The formation of the colored complexes were utilized in the development of simple, rapid and accurate spectrophotometric methods for the analysis of LOS-K in pure form as well as in its pharmaceutical tablets. Under the optimum reaction conditions, linear relationships with good correlation coefficients (0.9985-0.9998) were found between the absorbances and the concentrations of LOS-K in the range of 2-200 {mu}g ml{sup -1}. The limits of assays detection ranged from 0.61 to 19.65 {mu}g ml{sup -1}. No interference could be observed from the co-formulated hydrochlorothiazide (HCTZ), as well as from the additives commonly present in the tablets. The methods were successfully applied to the analysis of tablets from different manufacturers that contain LOS-K, alone or combined with HCTZ, with good accuracy and precision; the recovery percentages ranged from 98.96 {+-} 1.62% to 101.58 {+-} 1.29%. The results were compared favourably with the reported method.

  11. Biosynthesis of firefly luciferin in adult lantern: decarboxylation of L-cysteine is a key step for benzothiazole ring formation in firefly luciferin synthesis.

    Directory of Open Access Journals (Sweden)

    Yuichi Oba

    Full Text Available BACKGROUND: Bioluminescence in fireflies and click beetles is produced by a luciferase-luciferin reaction. The luminescence property and protein structure of firefly luciferase have been investigated, and its cDNA has been used for various assay systems. The chemical structure of firefly luciferin was identified as the D-form in 1963 and studies on the biosynthesis of firefly luciferin began early in the 1970's. Incorporation experiments using (14C-labeled compounds were performed, and cysteine and benzoquinone/hydroquinone were proposed to be biosynthetic component for firefly luciferin. However, there have been no clear conclusions regarding the biosynthetic components of firefly luciferin over 30 years. METHODOLOGY/PRINCIPAL FINDINGS: Incorporation studies were performed by injecting stable isotope-labeled compounds, including L-[U-(13C3]-cysteine, L-[1-(13C]-cysteine, L-[3-(13C]-cysteine, 1,4-[D6]-hydroquinone, and p-[2,3,5,6-D]-benzoquinone, into the adult lantern of the living Japanese firefly Luciola lateralis. After extracting firefly luciferin from the lantern, the incorporation of stable isotope-labeled compounds into firefly luciferin was identified by LC/ESI-TOF-MS. The positions of the stable isotope atoms in firefly luciferin were determined by the mass fragmentation of firefly luciferin. CONCLUSIONS: We demonstrated for the first time that D- and L-firefly luciferins are biosynthesized in the lantern of the adult firefly from two L-cysteine molecules with p-benzoquinone/1,4-hydroquinone, accompanied by the decarboxylation of L-cysteine.

  12. Comparison of various organic compounds destruction on rare earths doped Ti/Sb-SnO{sub 2} electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Cui, Yu-Hong [School of Environmental Science and Engineering, Huazhong University of Science and Technology, No. 1037 Luoyu Road, Hongshan District, Wuhan 430074 (China); State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, No. 73 Huanghe Road, Nangang District, Harbin 150090 (China); Feng, Yu-Jie, E-mail: yujief@hit.edu.cn [State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, No. 73 Huanghe Road, Nangang District, Harbin 150090 (China); Liu, Junfeng; Ren, Nanqi [State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, No. 73 Huanghe Road, Nangang District, Harbin 150090 (China)

    2012-11-15

    Highlights: Black-Right-Pointing-Pointer Different REs doping has distinct effect on the Ti/Sb-SnO{sub 2} electrode performance. Black-Right-Pointing-Pointer Gd or Eu improves the performance of Ti/Sb-SnO{sub 2} on aromatic ring cleavage. Black-Right-Pointing-Pointer Catechol is more refractory to be degraded than benzoquinone and hydroquinone. Black-Right-Pointing-Pointer The molecular structure of organic compound influences its degradation rate. - Abstract: Ti/Sb-SnO{sub 2} and three kinds of rare earths (REs), namely Ce, Gd, and Eu doped Ti/Sb-SnO{sub 2} electrodes were prepared and tested for their capacity on electrocatalytic degradation of three kinds of basal aromatic compounds (benzoquinone, hydroquinone and catechol) and six kinds of aliphatic acids (maleic acid, fumaric acid, succinic acid, malonic acid, oxalic acid and acetic acid). The elimination of selected organics as well as their TOC removal with different doped Ti/Sb-SnO{sub 2} electrodes was described by first-order kinetics. Compared with Ti/Sb-SnO{sub 2}, the Gd and Eu doped electrodes show better performance on the degradation of most of the selected organics, while Ce doped electrode shows either closely or lower efficiency on the degradation of these selected organics. Besides electrode material, the molecular structure of organic compound has obvious effect on its degradation in the electrocatalytic process. Catechol is more resistant to the electrophilic attack by hydroxyl radicals than benzoquinone and hydroquinone. The compound with more complicate molecular structure or longer carbon chain is more difficult to be mineralized. The aliphatic acid with higher oxygen content or more double bonds is more readily to be oxidized in the electrocatalytic process.

  13. FT-IR study of the ring-retaining products from the reaction of OH radicals with phenol, o-, m-, and p-cresol

    International Nuclear Information System (INIS)

    The ring-retaining products of the OH-initiated degradation of phenol and o-, m-, and p-cresol in the presence of NOx have been investigated and their formation yields determined. The experiments were carried out in a large volume reactor at (298±2)K and 1000 mbar total pressure of synthetic air using FT-IR spectroscopy for the analysis of reactants and products. The products observed and their respective molar yields were: from phenol: 1,2-dihydroxybenzene (80.4±12.1)%, 1,4-benzoquinone (3.7±1.2)% and 2-nitrophenol (5.8±1.0)%; from o-cresol: 3-methyl-1,2-dihydroxybenzene (73.4±14.6)%, methyl-1,4-benzoquinone (6.8±1.0)% and 6-methyl-2-nitrophenol (6.8±1.5)%; from m-cresol: 3-methyl-1,2-dihydroxybenzene (68.6±13.4)%, 4-methyl-1,2-dihydroxybenzene (9.7±2.7)%, methyl-1,4-benzoquinone (11.3±2.5)%, 5-methyl-2-nitrophenol (4.4±1.5)% and 3-methyl-2-nitrophenol (4.3±1.6)% and from p-cresol: 4-methyl-1,2-dihydroxybenzene (64.1±11.3)% and 4-methyl-2-nitrophenol (7.6±2.2)%. Reaction pathways leading to the observed products are proposed and potential ramifications for the atmospheric reaction mechanisms of aromatic hydrocarbons are considered. (Author)

  14. FT-IR study of the ring-retaining products from the reaction of OH radicals with phenol, o-, m-, and p-cresol

    Science.gov (United States)

    Olariu, Romeo Iulian; Klotz, Björn; Barnes, Ian; Becker, Karl Heinz; Mocanu, Raluca

    The ring-retaining products of the OH-initiated degradation of phenol and o-, m-, and p-cresol in the presence of NO x have been investigated and their formation yields determined. The experiments were carried out in a large volume reactor at (298±2) K and 1000 mbar total pressure of synthetic air using FT-IR spectroscopy for the analysis of reactants and products. The products observed and their respective molar yields were: from phenol: 1,2-dihydroxybenzene (80.4±12.1)%, 1,4-benzoquinone (3.7±1.2)% and 2-nitrophenol (5.8±1.0)%; from o-cresol: 3-methyl-1,2-dihydroxybenzene (73.4±14.6)%, methyl-1,4-benzoquinone (6.8±1.0)% and 6-methyl-2-nitrophenol (6.8±1.5)%; from m-cresol: 3-methyl-1,2-dihydroxybenzene (68.6±13.4)%, 4-methyl-1,2-dihydroxybenzene (9.7±2.7)%, methyl-1,4-benzoquinone (11.3±2.5)%, 5-methyl-2-nitrophenol (4.4±1.5)% and 3-methyl-2-nitrophenol (4.3±1.6)% and from p-cresol: 4-methyl-1,2-dihydroxybenzene (64.1±11.3)% and 4-methyl-2-nitrophenol (7.6±2.2)%. Reaction pathways leading to the observed products are proposed and potential ramifications for the atmospheric reaction mechanisms of aromatic hydrocarbons are considered.

  15. Pd-catalyzed decarboxylative Heck vinylation of 2-nitrobenzoates in the presence of CuF2

    Directory of Open Access Journals (Sweden)

    Lukas J. Gooßen

    2010-05-01

    Full Text Available A new protocol for the decarboxylative Heck vinylation of benzoic acids is disclosed. In the presence of a catalyst system generated in situ from Pd(OAc2 (2 mol %, CuF2 (2 equiv, and benzoquinone (0.5 equiv in NMP, a wide range of olefins were coupled with various 2-nitrobenzoates at 130 °C with the release of carbon dioxide to afford the corresponding vinyl arenes in good yields.

  16. Cytotoxic Terpene Quinones from Marine Sponges

    Directory of Open Access Journals (Sweden)

    Marina Gordaliza

    2010-11-01

    Full Text Available The 1,4-benzoquinone moiety is a common structural feature in a large number of compounds that have received considerable attention owing to their broad spectrum of biological activities. The cytotoxic and antiproliferative properties of many natural sesquiterpene quinones and hydroquinones from sponges of the order Dictyoceratida, such as avarol, avarone, illimaquinone, nakijiquinone and bolinaquinone, offer promising opportunities for the development of new antitumor agents. The present review summarizes the structure and cytotoxicity of natural terpenequinones/hydroquinones and their bioactive analogues and derivatives.

  17. Fate of 15N-labelled urea as affected by organic amendments and oils applied to rice

    International Nuclear Information System (INIS)

    The present study was undertaken to explore the possibility of using 2 organic compounds (p-benzoquinone and catechol), 2 oils (neem oil (Azadirachta indica A. Juss) and linseed oil (Linum usitatissimum Linn.) oil) and 3 polyphenolic plant residues, viz. catechu (Acacia catechu (L.f.) Willd.), babul acacia (Acacia nilotica (Linn.) Willd. ex Del. sub.indica (Benth.) Brenan, syn. A. arabica (Lamk.) Willd.) and yellow myrobalan (Terminalia chebula Retz.) when applied with 15N-tagged urea to observe their effectiveness in decreasing N losses. (author). 8 refs

  18. Geldanamycin inhibits proliferation and motility of Her2/neu-overexpressing SKBr3 breast cancer cells

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Objective Benzoquinone ansamycin antibiotic, geldanamycin (GA), is a new anticancer agent that could inhibit Hsp90 by occupying its NH2-terminal ATP-binding site. This study was to investigate the antitumor efficacy of GA on Her2/neu tyrosine kinase overexpressing human breast cancer cell line SKBr3. Methods The degradation of Her2/neu tyrosine kinase was analyzed by Western blotting, the proliferation index was determined by MTT assay, cell cycle distribution was detected by flow cytometry, Cyclin D1 mRNA ...

  19. Mechanism of activation of mouse liver microsomal glutations S—transferase by paracetamol treatment

    Institute of Scientific and Technical Information of China (English)

    ZhenY; LouYJ

    2002-01-01

    Microsomal glutathion S-transferase(mGST) is one of the important detoxifcation enzymes in vivo,its modifying activation by drugs has been paid more attention to in pertinent field recently.This study was to explore the influence of paracetamol(Par) on mGST and its possible mechanism in vivo,and to further reveal the biological significance.Par is metabolized to N-acetyl-p-benzoquinone imine(NAPQI) by CYP2E1 and mGST is activated by sulfhydryl modification.

  20. Isolation and structures of some selenium and tellurium derivatives of 1, 4, 5, 8, 9, 12-hexabromododecahydrotriphenylene as co-crystals of triphenylene

    Indian Academy of Sciences (India)

    Poonam Rajesh Prasad; Harkesh B Singh; Ray J Butcher

    2014-09-01

    The synthesis and characterization of low-valent organoselenium and tellurium derivatives of hexabromododecahydrotriphenylene has been attempted. The reaction of hexabromododecahydrotriphenylene with in situ generated disodium dichalcogenides (Na2E2; E = Se, Te) afforded insoluble chalcododecahydrotriphenylene derivatives, 20, 21 respectively. Attempted aromatization of 20 and 21 using DDQ (2, 3-dichloro-5, 6-dicyano-1,4-benzoquinone) as an oxidizing agent afforded the co-crystals. The hexaselenophenyl derivative, 22 and the hexaselenocyanate derivative 23 were synthesized by the reaction of in situ generated sodium arylselenolate/potassium selenocyanate with hexabromododecahydrotriphenylene, respectively. The compounds were characterized by common spectroscopic tools and a few by single crystal x-ray crystallographic studies.

  1. Foamable compositions and formations treatment

    Energy Technology Data Exchange (ETDEWEB)

    Clampitt, R.L.

    1981-11-17

    Thermally stable foamable gelled compositions are disclosed suitable for postprimary oil recovery e.g., steam- or gas-foamed systems comprising water, a surfactant, a polymeric viscosifier, an aldehyde component, and at least one phenolic component such as resorcinol, catechol, and the like, as well as selected oxidized phenolic materials such as 1,4-benzoquinone of natural or synthetic origin and natural and modified tannins. The gel compositions can additionally contain gel stabilizers such as sulfomethylated quebracho (Smq) and chemical buffering agents such as sodium bicarbonate.

  2. An approach to seco-prezizaane sesquiterpenoids: enantioselective total synthesis of (+)-1S-minwanenone.

    Science.gov (United States)

    Mehta, Goverdhan; Shinde, Harish M

    2012-09-21

    A strategy of general applicability toward seco-prezizaane sesquiterpenes, from a chiral, tricyclic synthon, readily available via an enzymatic resolution step from the Diels-Alder adduct of cyclopentadiene and p-benzoquinone, has been devised. Our approach enables harnessing of the stereochemical proclivities of the norbornyl system to install the desired stereochemistry at the key stereogenic centers. Recourse to an interesting stratagem to realign a stereochemical divergence into stereoreconvergence forms the cornerstone of our successful approach. The first total synthesis of (+)-1S-minwanenone, a prototypical member of seco-prezizaane subclass, has been accomplished. PMID:22897237

  3. In vitro depolymerization of lignin by manganese peroxidase of Phanerochaete chrysosporium

    International Nuclear Information System (INIS)

    Homogeneous manganese peroxidase catalyzed the in vitro partial depolymerization of four different 14C-labeled synthetic lignin preparations. Gel permeation profiles demonstrated significant depolymerization of 14C-sidechain-labeled syringyl lignin, a 14C-sidechain-labeled syringyl-guaiacyl copolymer (angiosperm lignin), and depolymerization of 14C-sidechain- and 14C-ring-labeled guaiacyl lignins (gymnosperm lignin). 3,5-Dimethoxy-1,4-benzo-quinone, 3,5-dimethoxy-1,4-hydroquinone, and syringylaldehyde were identified as degradation products of the syringyl and syringyl-guaiacyl lignins. These results suggest that manganese peroxidase plays a significant role in the depolymerization of lignin by Phanerochaete chrysosporium

  4. Role of Hydroquinone-Thiol Conjugates in Benzene-Mediated Toxicity

    OpenAIRE

    Lau, Serrine S.; Kuhlman, Christopher; Bratton, Shawn B.; Monks, Terrence J.

    2009-01-01

    Hydroquinone (HQ) is a metabolite of benzene, and in combination with phenol (PHE), reproduces benzene myelotoxicity. HQ readily oxidizes to 1,4-benzoquinone (1,4-BQ) followed by the reductive addition of glutathione (GSH). Subsequent cycles of oxidation and GSH addition give rise to a variety of mono-, and multi-GSH substituted conjugates. Following administration of PHE/HQ (1.1 mmol/kg/0.9 mmol/kg, ip) to male Sprague-Dawley (SD) rats, 2-(glutathion-S-yl)HQ [GS-HQ], 2,5-bis-(glutathion-S-yl...

  5. Cytochromes P450 in benzene metabolism and involvement of their metabolites and reactive oxygen species in toxicity.

    OpenAIRE

    I. Gut; Nedelcheva, V; Soucek, P; Stopka, P.; Tichavská, B

    1996-01-01

    Cytochrome P450 (CYP) 2E1 was the most efficient CYP enzyme that oxidized benzene to soluble and covalently bound metabolites in rat and human liver microsomes. The covalent binding was due mostly to the formation of benzoquinone (BQ), the oxidation product of hydroquinone (HQ), and was inversely related to the formation of soluble metabolites. In rats, inhalation of benzene (4 mg/liter of air) caused a rapid destruction of CYP2B1 previously induced by phenobarbital. The ability of benzene me...

  6. Excited complexes in oxidation-reduction photoreactions of pigments. I. Spectral detection of triplet state exciplex in the chlorophyll oxidation reaction.

    Science.gov (United States)

    Andreeva, N E; Chibisov, A K

    1976-01-01

    Photooxidation of chlorophyll "a" with p-benzoquinone in toluene and dioxane is studied by the method of flash photolysis. It is shown that in nonpolar medium the triplet exiplex is the product of this reaction. The experiments on competitive quenching of chlorophyll triplet state with naphthacene prove the diffusion mechanism of exiplex formation. The spectrum of triplet-triplet absorption of the exiplex is presented and the rate constant of intercombination degradation equalling 1.103 sec(-1) is measured. Possible structure of the exiplex is discussed. PMID:1252529

  7. Synthesis of mesomeric betaine compounds with imidazolium-enolate structure

    Directory of Open Access Journals (Sweden)

    Nina Gonsior

    2012-03-01

    Full Text Available The synthesis of a heterocyclic mesomeric betaine by quaternization reaction of 1-butylimidazole and tetrabromo-1,4-benzoquinone is presented. The structure was verified by means of X-ray single-crystal analysis, NMR and IR spectroscopy. Inclusion complexes of the heterocyclic mesomeric betaine with randomly methylated (1.8 β-cyclodextrin were investigated by UV–vis spectroscopy. Furthermore, the reaction conditions were applied to poly(vinylimidazole and 1,4-bis(1H-imidazol-1-ylbutane to obtain functionalized polymer networks and condensate polymers, respectively.

  8. Oxidation of some disubstituted anisole derivatives with ceric perchlorate in perchloric acid solution

    International Nuclear Information System (INIS)

    The influence of concentration of particular reagents on the kinetics of Ce(IV) reduction by 2,6-dimethyl and 3,5-dimethyl-anisole as well as 2-methoxy-5-methyl- and 4-methoxy-2-methyl-aniline in perchloric acid solution was investigated, establishing the stoichiometry of these processes. Some intermediate products - macromolecular, derivatives of p-benzoquinone and 4,4'-diphenoquinone - were separated and identified. The effects of substituents and the conditions of performed oxidation processes on the kind and yields of the resultant products were considered. (author). 22 refs, 1 fig., 1 tab

  9. Spectroelectrochemical studies of nuclease-active zinc(II) coordination compounds from the ligands Hpyramol and Hpyrimol

    Energy Technology Data Exchange (ETDEWEB)

    Ozalp-Yaman, Seniz, E-mail: seniz@atilim.edu.t [Atilim University, Engineering Faculty, Chemistry Group, 06836 Ankara (Turkey); Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, 2300 RA Leiden (Netherlands); Hoog, Paul de; Maheswari, Palanisamy Uma; Casellas, Helene [Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, 2300 RA Leiden (Netherlands); Golobic, Amalija; Kozlevcar, Bojan [University of Ljubljana, Faculty of Chemistry and Chemical Technology, Askerceva 5, P.O. Box 537, 1001 Ljubljana (Slovenia); Gamez, Patrick; Reedijk, Jan [Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, 2300 RA Leiden (Netherlands)

    2010-12-01

    The electrochemical oxidation of four zinc(II) coordination compounds from the ligands 4-methyl-2-(2-pyridylmethyl)aminophenol (Hpyramol) and 4-methyl-2-(2-pyridylmethylene)aminophenol (Hpyrimol) with chloride or acetate as counter-ions has been studied by in situ spectroelectrochemistry in dimethylformamide (DMF). Low-temperature EPR studies of electrolyte solutions of all zinc compounds indicate the presence of a phenoxyl radical with a g-value in the range 2.070-2.099, which is illustrative for an electron delocalization over the metal centre. The final product of this oxidative process is shown to be a benzoquinone methide derivative.

  10. Electrochemical Synthesis of 5-Purin-6'-ylthiocatechols in Aqueous Medium

    Institute of Scientific and Technical Information of China (English)

    LIU Fu-Jian; ZENG Cheng-Chu; PING Da-Wei; CAI Yuan-Li; ZHONG Ru-Gang

    2008-01-01

    The electrochemical synthesis of 5-purin-6'-ylthiocatechols was carried out by anodic oxidation of catechol derivatives la--ld in the presence of 6-mercaptopurine (2) in aqueous solution.Results of cyclic voltammetry and controlled-potential electrolysis indicated that the starting catechols were first oxidized to the corresponding o-benzoquinone,which underwent further Michael addition with 6-mercaptopurine to produce titled products 3a--3d following an EC (E=electrochemical and C=chemical step) mechanism.Such work further demonstrates the versatility of the anodic oxidation of catechols and their in-situ transformation for the synthesis of derivatized catechols.

  11. Preparation of Cross-linking Copolymerization of Chitosan and AMPS in Ionic Liquid%离子液体中壳聚糖/AMPS共聚交联微球的制备

    Institute of Scientific and Technical Information of China (English)

    张聪璐; 胡筱敏; 侯晓虹; 陶颖婷

    2013-01-01

    Cross-linking copolymerization of 2-acrylamide-2-methylpro panesulfonic acid (AMPS) and chitosan in ionic liquid was studied using ceric ammonium nitrate (CAN) as an initiator, p-benzoquinone as resistance polymerization retarder, and glycine hydrochloride ionic liquid water solution as reaction medium. The obtained product was characterized by SEM, FTIR and TGA. The results showed that, the reaction rate and grafting ratio were improved greatly by [Gly]Cl as reaction medium. The obtained product was regular spherical , the particle diameter was about 2 μm. And the product had smooth surface, some resistance to acid and alkali.

  12. Myrsinoic A acid and its derivative: in vitro inhibitors of photosynthesis; Acido myrsinoico A e derivado: inibidores da fotossintese in vitro

    Energy Technology Data Exchange (ETDEWEB)

    Burger, Marcela Carmen de M.; Oliveira, Gracielle S. de; Menezes, Antonio Carlos S. [Universidade Estadual de Goias, Anapolis, GO (Brazil). Unidade Universitaria de Ciencias Exatas e Tecnologicas; Vieira, Paulo Cezar; Silva, Maria Fatima das G.F. da [Universidade Federal de Sao Carlos (UFSCar), SP (Brazil). Dept. de Quimica; Veiga, Thiago A.M., E-mail: tveiga@unifesp.br [Universidade Federal de Sao Paulo (UNIFESP), SP (Brazil). Inst. de Ciencias Ambientais, Quimicas e Farmaceuticas. Dept. de Ciencias Exatas e da Terra

    2012-07-01

    Myrsinoic A acid, isolated from Myrsine cuneifolia and its hydrogenated derivative had their effect on photosynthesis tested. The compounds inhibited the electron flow (basal, phosphorylating and uncoupled) from water to methyl viologen; therefore, they act as Hill reaction inhibitors in spinach thylakoids. They inhibited partial reactions of PSII electron flow from water to 2,5-dichloro-1,4-benzoquinone, from water to sodium silicomolybdate, and partially electron flow from diphenylcarbazide to 2,6-dichloroindophenol. Their inhibition sites were at the donor and acceptor sides of PSII, between P{sub 680} and Q{sub A}. Chlorophyll {alpha} fluorescence measurements confirmed the behavior of the compounds (pool of quinones). (author)

  13. Mediator-assisted photocurrent extraction from the thylakoids

    International Nuclear Information System (INIS)

    Photocurrent extracted from the thylakoids has been studied as a function of electron mediator concentration. Phenazine methosulfate is used to facilitate the charge transfer from the thylakoid's charge transport chain to the outside medium. The photocurrent has been shown to originate from the photosynthesis on the thylakoid membranes. Comparing with a previous study using para-Benzoquinone as the mediator, a similar peak effect in the photocurrent as a function of concentration is observed, but the magnitude of the current is nearly a thousand times greater. A semi-quantitative analysis is presented to explain the data found in those systems

  14. An NAD(P)H:quinone oxidoreductase 1 (NQO1) enzyme responsive nanocarrier based on mesoporous silica nanoparticles for tumor targeted drug delivery in vitro and in vivo

    Science.gov (United States)

    Gayam, Srivardhan Reddy; Venkatesan, Parthiban; Sung, Yi-Ming; Sung, Shuo-Yuan; Hu, Shang-Hsiu; Hsu, Hsin-Yun; Wu, Shu-Pao

    2016-06-01

    The synthesis and characterization of an NAD(P)H:quinone oxidoreductase 1 (NQO1) enzyme responsive nanocarrier based on mesoporous silica nanoparticles (MSNPs) for on-command delivery applications has been described in this paper. Gatekeeping of MSNPs is achieved by the integration of mechanically interlocked rotaxane nanovalves on the surface of MSNPs. The rotaxane nanovalve system is composed of a linear stalk anchoring on the surface of MSNPs, an α-cyclodextrin ring that encircles it and locks the payload ``cargo'' molecules in the mesopores, and a benzoquinone stopper incorporated at the end of the stalk. The gate opening and controlled release of the cargo are triggered by cleavage of the benzoquinone stopper using an endogenous NQO1 enzyme. In addition to having efficient drug loading and controlled release mechanisms, this smart biocompatible carrier system showed obvious uptake and consequent release of the drug in tumor cells, could selectively induce the tumor cell death and enhance the capability of inhibition of tumor growth in vivo. The controlled drug delivery system demonstrated its use as a potential theranostic material.The synthesis and characterization of an NAD(P)H:quinone oxidoreductase 1 (NQO1) enzyme responsive nanocarrier based on mesoporous silica nanoparticles (MSNPs) for on-command delivery applications has been described in this paper. Gatekeeping of MSNPs is achieved by the integration of mechanically interlocked rotaxane nanovalves on the surface of MSNPs. The rotaxane nanovalve system is composed of a linear stalk anchoring on the surface of MSNPs, an α-cyclodextrin ring that encircles it and locks the payload ``cargo'' molecules in the mesopores, and a benzoquinone stopper incorporated at the end of the stalk. The gate opening and controlled release of the cargo are triggered by cleavage of the benzoquinone stopper using an endogenous NQO1 enzyme. In addition to having efficient drug loading and controlled release mechanisms, this

  15. Terahertz time-domain spectroscopic investigation on quinones

    Institute of Scientific and Technical Information of China (English)

    GE Min; ZHAO HongWei; WANG WenFeng; YU XiaoHan; LI WenXin

    2008-01-01

    Well resolved far-infrared spectra of 1,4-benzoquinone, 1,4-naphthoquinone, and 9, 10-anthraquinonme in polycrystalline form have been measured with terahertz time domain spectroscopy at room tem-perature. The characterizations of power absorption and index of refraction in the frequency range 0.3 -2.0 THz are presented. Theoretical calculation is applied to assist the analysis and assignment of individual THz absorption spectra of the p-quinones with semiempirical AM1, Hartree-Fock (HF), and density functional theory (DFT) method. Observed THz responses are assigned to the translational and torsional vibrations of p-quinone dimer held together by weak hydrogen bonds.

  16. Terahertz time-domain spectroscopic investigation on quinones

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Well resolved far-infrared spectra of 1,4-benzoquinone, 1,4-naphthoquinone, and 9, 10-anthraquinonme in polycrystalline form have been measured with terahertz time domain spectroscopy at room tem- perature. The characterizations of power absorption and index of refraction in the frequency range 0.3 -2.0 THz are presented. Theoretical calculation is applied to assist the analysis and assignment of individual THz absorption spectra of the p-quinones with semiempirical AM1, Hartree-Fock (HF), and density functional theory (DFT) method. Observed THz responses are assigned to the translational and torsional vibrations of p-quinone dimer held together by weak hydrogen bonds.

  17. High throughput microwell spectrophotometric assay for olmesartan medoxomil in tablets based on its charge-transfer reaction with DDQ

    OpenAIRE

    Darwish Ibrahim A; Wani Tanveer A; Khalil Nasr Y.; Abdel-Rahman Hamdy M.

    2014-01-01

    The study describes the development and validation of a new microwell-based spectrophotometric assay for determination of olmesartan medoxomil (OLM) in tablets. The formation of a colored charge-transfer (CT) complex between OLM as an n-electron donor and 2,3-dichloro- -5,6-dicyano-1,4-benzoquinone (DDQ) as a p-electron acceptor was investigated, and employed as the basis for the development of the new assay. The proposed assay was conducted in 96-microwell plates. The absorbance of the color...

  18. Development of a novel 96-microwell assay with high throughput for determination of olmesartan medoxomil in its tablets

    OpenAIRE

    Darwish Ibrahim A; Wani Tanveer A; Khalil Nasr Y.; Al-Shaikh Abdul-Aziz; Al-Morshadi Najm

    2012-01-01

    Abstract A novel 96-microwell-based spectrophotometric assay has been developed and validated for determination of olmesartan medoxomil (OLM) in tablets. The formation of a colored charge-transfer (CT) complex between OLM as a n-electron donor and 2, 5-dichloro-3, 6-dihydroxy-1, 4-benzoquinone (p-chloranilic acid, pCA) as a π-electron acceptor was investigated, for the first time, and employed as a basis in the development of the proposed assay. The proposed assay was carried out in 96-microw...

  19. 2-Bromo-1,6,6-trimethyl-6,7,8,9-tetrahydrophenanthro[1,2-b]furan-10,11-dione

    Directory of Open Access Journals (Sweden)

    Cui-Ping Fan

    2013-06-01

    Full Text Available In the title compound, C19H17BrO3, the ring skeleton is located on a crystallographic mirror plane; two C atoms of the cyclohexene ring are disordered over the two locations to satisfy the preferred ring conformation. In the crystal, C—H...O hydrogen bonds link the molecules into chains along the a axis. π–π stacking interactions between benzoquinone rings, with a centroid–centroid distance of 3.7225 (4 Å, are also observed, which connect the chains into a two-dimensional networkparallel to the ab plane.

  20. Synthesis and characterization of fluorinated polyaminoquinones and fluorinated polyimides

    Science.gov (United States)

    Vaccaro, Eleonora

    Phenolic and quinonoid compounds are widely studied in biological sciences because of their ability to chelate heavy metals like iron and copper and recently have found new applications in synthetic macromolecules. Amino- p-benzoquinone polymers, poly[(2,5-hexamethylenediamino)-1,4-benzoquinone] and poly {[2,5-(2,2'-bistrifluoromethyl)-4,4' -biphenylenediamino]1,4-benzoquinone}, were synthesized and evaluated as adhesion promoters for steel/epoxy joints. An improvement in the torsional shear strength of these joints was observed when these polymers were used as adhesion promoters. The durability of the adhesive bond was also improved after boiling water treatment, relative to untreated and silane treated joints. The improvement in adhesion could be attributed to the formation of a chelate between the polyaminoquinone (PAQ) and the iron surface and a chemical reaction between the PAQ and the epoxy resin. A low molecular weight model compound, bis[2,5-(4-methylanilido)]-1,4-benzoquinone was also used to study coupling between the epoxy adhesive and the steel surface. Electron spin resonance (ESR), atomic absorption spectroscopy and infrared spectroscopy were used to document the epoxy-coupling agent reaction and the chelate formation. Polyimides have acquired importance in the last twenty years as the most promising macromolecules for high technology applications in new materials. Their good thermo-oxidative stability is well known, as well as their high glass transition temperature. Polyimides are versatile polymers, which can be utilized for a wide range of applications: i.e., as matrices for high performance advanced composite materials, as thin films in electronic applications, as structural adhesives and sealants and as membranes for gas separation. A novel anhydride, 1,1,1-trifluoromethyl-1-pentafluorophenylethylidene-2,2-diphthalic anhydride, 8FDA, was synthesized. Five diamines were used in the synthesis of polyimides, namely p-phenylene diamine, 3

  1. Utilization of Charge Transfer and Kinetic Methods for the Determination of Doripenem

    Directory of Open Access Journals (Sweden)

    Nora H. Al-Shaalan

    2012-01-01

    Full Text Available Problem statement: This study presents rapid, uncomplicated and sensitive spectrophotometric techniques for the analysis of doripenem in both its pure and pharmaceutical forms. Approach: The main principle of the approaches and procedures that have been developed is the reaction of doripenem as an n-electron donor to ninhydrin and π-acceptors, such as tetracyanoethylene, 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrachloro-1,4-benzoquinone, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and chloranilic acid. The wavelengths 580, 264, 320, 357, 375 and 465 nm was used for measuring the resulting complexes for ninhydrin, chlorine, chloranilic acid, DDQ, TCNQ and TCNE respectively. Results: The suggested procedures for the determination of doripenem were successfully put into practice with good recovery; the percent recovery ranged from 99.31-100.55. Benes-Hildebrand plots were also used to study the association constants and the free energy changes. Conclusion: The results of the CT method agree with those of the kinetic method and there is no significant difference between them.

  2. Fermented wheat germ extract - nutritional supplement or anticancer drug?

    Directory of Open Access Journals (Sweden)

    Voigt Wieland

    2011-09-01

    Full Text Available Abstract Background Fermented wheat germ extract (FWGE is a multisubstance composition and, besides others, contains 2-methoxy benzoquinone and 2, 6-dimethoxy benzoquinone which are likely to exert some of its biological effects. FWGE interferes with anaerobic glycolysis, pentose cycle and ribonucleotide reductase. It has significant antiproliferative effects and kills tumor cells by the induction of apoptosis via the caspase-poly [ADP-ribose] polymerase-pathway. FWGE interacts synergistically with a variety of different anticancer drugs and exerted antimetastatic properties in mouse models. In addition, FWGE modulates immune response by downregulation of MHC-I complex and the induction of TNF-α and various interleukins. Data in the F-344 rat model provide evidence for a colon cancer preventing effect of FWGE. Clinical data from a randomized phase II trial in melanoma patients indicate a significant benefit for patients treated with dacarbazine in combination with FWGE in terms of progression free survival (PFS and overall survival (OS. Similarly, data from studies in colorectal cancer suggested a benefit of FWGE treatment. Besides extension of OS and PFS, FWGE improved the quality of life in several studies. Conclusion In conclusion, available data so far, justify the use of FWGE as a non-prescription medical nutriment for cancer patients. Further randomized, controlled and large scale clinical studies are mandatory, to further clarify the value of FWGE as a drug component of future chemotherapy regimens.

  3. Modulation of mast cell and basophil functions by benzene metabolites.

    Science.gov (United States)

    Triggiani, Massimo; Loffredo, Stefania; Granata, Francescopaolo; Staiano, Rosaria I; Marone, Gianni

    2011-11-01

    Benzene is a carcinogenic compound used in industrial manufacturing and a common environmental pollutant mostly derived from vehicle emissions and cigarette smoke. Benzene exposure is associated with a variety of clinical conditions ranging from hematologic diseases to chronic lung disorders. Beside its direct toxicity, benzene exerts multiple effects after being converted to reactive metabolites such as hydroquinone and benzoquinone. Mast cells and basophils are primary effector cells involved in the development of respiratory allergies such as rhinitis and bronchial asthma and they play an important role in innate immunity. Benzene and its metabolites can influence mast cell and basophil responses either directly or by interfering with other cells, such as T cells, macrophages and monocytes, which are functionally connected to mast cells and basophils. Hydroquinone and benzoquinone inhibit the release of preformed mediators, leukotriene synthesis and cytokine production in human basophils stimulated by IgE- and non IgE-mediated agonists. Furthermore, these metabolites reduce IgE-mediated degranulation of mast cells and the development of allergic lung inflammation in rats. Both in vitro and in vivo studies indicate that benzene metabolites alter biochemical and functional activities of other immunocompetent cells and may impair immune responses in the lung. These inhibitory effects of benzene metabolites are primarily mediated by interference with early transduction signals such as PI3 kinase. Together, currently available studies indicate that benzene metabolites interfere by multiple mechanisms with the role of basophils and mast cells in innate immunity and in chronic inflammation in the lung. PMID:22103854

  4. Plasmid-encoded degradation of p-nitrophenol and 4-nitrocatechol by Arthrobacter protophormiae.

    Science.gov (United States)

    Chauhan, A; Chakraborti, A K; Jain, R K

    2000-04-21

    Arthrobacter protophormiae strain RKJ100 is capable of utilizing p-nitrophenol (PNP) as well as 4-nitrocatechol (NC) as the sole source of carbon, nitrogen and energy. The degradation of PNP and NC by this microorganism takes place through an oxidative route, as stoichiometry of nitrite molecules was observed when the strain was grown on PNP or NC as sole carbon and energy sources. The degradative pathways of PNP and NC were elucidated on the basis of enzyme assays and chemical characterization of the intermediates by TLC, GC, (1)H NMR, GC-MS, UV spectroscopy, and HPLC analyses. Our studies clearly indicate that the degradation of PNP proceeds with the formation of p-benzoquinone (BQ) and hydroquinone (HQ) and is further degraded via the beta-ketoadipate pathway. Degradation of NC involved initial oxidation to generate 1,2,4-benzenetriol (BT) and 2-hydroxy-1,4-benzoquinone; the latter intermediate is then reductively dehydroxylated, forming BQ and HQ, and is further cleaved via beta-ketoadipate to TCA intermediates. It is likely, therefore, that the same set of genes encode the further metabolism of HQ in PNP and NC degradation. A plasmid of approximately 65 kb was found to be responsible for harboring genes for PNP and NC degradation in this strain. This was based on the fact that PNP(-) NC(-) derivatives were devoid of the plasmid and had simultaneously lost their capability to grow at the expense of these nitroaromatic compounds.

  5. Chemical degradation and toxicity reduction of 4-chlorophenol in different matrices by gamma-ray treatment

    Science.gov (United States)

    Kang, Sung-Wook; Shim, Seung-Bo; Park, Young-Kwon; Jung, Jinho

    2011-03-01

    Gamma-ray treatment of 4-chlorophenol (4-CP) in different matrices was studied in terms of both chemical degradation and toxicity reduction. Degradation of 4-CP in a complex effluent matrix was less efficient than that in ultrapure water. This is most likely due to the consumption of reactive radicals by matrix components, such as dissolved organic matter in effluents. The matrix effect caused much more profound changes in toxicity. Gamma-ray treatment of 4-CP in ultrapure water abruptly increased acute toxicity toward Daphnia magna while slightly decreased toxicity of 4-CP in effluent. In the presence of ZrO 2 catalyst, degradation of 4-CP as well as toxicity reduction was substantially improved mostly by adsorption of 4-CP onto the nanoparticles. It was found that benzoquinone, hydroquinone and 4-chlorocatechol were generated for ultrapure water sample while only 4-chlorocatechol was formed for effluent samples by gamma-ray treatment. As determined in this work, EC 50 values of benzoquinone (0.46 μM), hydroquinone (0.61 μM) and chlorocatechol (8.87 μM) were much lower than those of 4-CP (31.50 μM), explaining different toxicity changes of 4-CP in different matrices by gamma-ray treatment. The observed toxicity of gamma-ray treated 4-CP was well correlated with the one calculated from individual toxicity based on EC 50 value.

  6. Photoproduction of hydrogen peroxide in aqueous solution from model compounds for chromophoric dissolved organic matter (CDOM)

    International Nuclear Information System (INIS)

    Highlights: • CDOM produces hydrogen peroxide in sunlit surface waters. • Quinone moieties have been proposed as the photo-active chromophore in CDOM. • Hydrogen peroxide is produced in irradiated aqueous quinone solutions. • Concentrations and production rates are comparable to humic and fulvic acids. • Optical properties post-irradiation were similar to CDOM. - Abstract: To explore whether quinone moieties are important in chromophoric dissolved organic matter (CDOM) photochemistry in natural waters, hydrogen peroxide (H2O2) production and associated optical property changes were measured in aqueous solutions irradiated with a Xenon lamp for CDOM model compounds (dihydroquinone, benzoquinone, anthraquinone, napthoquinone, ubiquinone, humic acid HA, fulvic acid FA). All compounds produced H2O2 with concentrations ranging from 15 to 500 μM. Production rates were higher for HA vs. FA (1.32 vs. 0.176 mM h−1); values ranged from 6.99 to 0.137 mM h−1 for quinones. Apparent quantum yields (Θapp; measure of photochemical production efficiency) were higher for HA vs. FA (0.113 vs. 0.016) and ranged from 0.0018 to 0.083 for quinones. Dihydroquinone, the reduced form of benzoquinone, had a higher production rate and efficiency than its oxidized form. Post-irradiation, quinone compounds had absorption spectra similar to HA and FA and 3D-excitation–emission matrix fluorescence spectra (EEMs) with fluorescent peaks in regions associated with CDOM

  7. Mechanistic study of ozonation of p-nitrophenol in aqueous solution

    Institute of Scientific and Technical Information of China (English)

    SHI Hui-xiang; XU Xian-wen; XU Xin-hua; WANG Da-hui; WANG Qi-da

    2005-01-01

    Ozonlysis in the treatment of p-nitrophenol solution was studied in this paper. The results indicated that the decomposition of pnitrophenol was accelerated as the gas flow rate or pH value increased. When gaseous ozone concentration was 20.11 mg/L and pH was 3, after 24 min reaction, the removal rate of p-nitrophenol reached 73.04%, 86. 11%, 91.71 % and 95 % at the gas flow rate of 32, 40, 48and 56 ml/min respectively. And when pH was 3, 4, 5, 6, the decomposition rate was 66.38%, 82.09%, 90.46%, 97.50% after a 20min reaction respectively. It was mainly O3 molecule that took part in the decomposition when pH was 3. The main intermediates during the decomposition include catechol, o-benzoquinone, hydroquinone, p-benzoquinone, phenol, fumaric acid, maleic acid, oxalic acid and formic acid. The decomposition mechanism of p-nitrophenol was also discussed.

  8. Halogen vs hydrogen bonding in thiazoline-2-thione stabilization with σ- and π-electron acceptors adducts: Theoretical and experimental study

    Science.gov (United States)

    El-Sheshtawy, Hamdy S.; Salman, Hassan M. A.; El-Kemary, Maged

    2015-02-01

    Molecular charge-transfer complexes (CT) between thiazoline-2-thione (THZ) and different σ- (I2) and π-acceptors (Tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), and 2,3,5,6-tetrachloro-1,4-benzoquinone (CHL)) were investigated. UV-Vis absorption spectroscopy and theoretical calculations using both MP2/aug-cc-pVDZ-PP and B3LYP/6-311++G(d,p) level of theory were corroborated to study the nature of the stabilizing forces for THZ-I2, THZ-DDQ, THZ-TCNE, and THZ-CHL. Halogen bonding (XB) was the stabilizing attractive force in THZ-I2 and THZ-CHL whereas; hydrogen bonding (HB) was dominated in both THZ-TCNE, and THZ-DDQ complexes. Formation constant (K), extinction coefficient (ɛ), thermodynamic parameters such as enthalpy change (ΔH), entropy (ΔS), and Gibbs free energy (ΔG) were measured in different solvents.

  9. Effect of cationic plastoquinone SkQ1 on electron transfer reactions in chloroplasts and mitochondria from pea seedlings.

    Science.gov (United States)

    Samuilov, V D; Kiselevsky, D B

    2015-04-01

    Plastoquinone bound with decyltriphenylphosphonium cation (SkQ1) penetrating through the membrane in nanomolar concentrations inhibited H2O2 generation in cells of epidermis of pea seedling leaves that was detected by the fluorescence of 2',7'-dichlorofluorescein. Photosynthetic electron transfer in chloroplasts isolated from pea leaves is suppressed by SkQ1 at micromolar concentrations: the electron transfer in chloroplasts under the action of photosystem II or I (with silicomolybdate or methyl viologen as electron acceptors, respectively) is more sensitive to SkQ1 than under the action of photosystem II + I (with ferricyanide or p-benzoquinone as electron acceptors). SkQ1 reduced by borohydride is oxidized by ferricyanide, p-benzoquinone, and, to a lesser extent, by silicomolybdate, but not by methyl viologen. SkQ1 is not effective as an electron acceptor supporting O2 evolution from water in illuminated chloroplasts. The data on suppression of photosynthetic O2 evolution or consumption show that SkQ1, similarly to phenazine methosulfate, causes conversion of the chloroplast redox-chain from non-cyclic electron transfer mode to the cyclic mode without O2 evolution. Oxidation of NADH or succinate in mitochondria isolated from pea roots is stimulated by SkQ1.

  10. Characterization of pyranose dehydrogenase from Agaricus meleagris and its application in the C-2 specific conversion of D-galactose.

    Science.gov (United States)

    Sygmund, Christoph; Kittl, Roman; Volc, Jindrich; Halada, Petr; Kubátová, Elena; Haltrich, Dietmar; Peterbauer, Clemens K

    2008-02-01

    Pyranose dehydrogenase (PDH) of the mushroom Agaricus meleagris was purified from mycelial culture media to substantial homogeneity using ion-exchange and hydrophobic interaction chromatography. The native enzyme is a monomeric polypeptide with a molecular mass of 66,547Da as determined by matrix-assisted laser desorption/ionisation mass spectrometry containing approximately 7% carbohydrate and covalently bound flavin adenine dinucleotide. The enzyme exhibited a broad sugar substrate tolerance, oxidizing different aldopyranoses to the corresponding C-2 or C-2,3 (di)dehydro sugars. Preferred electron donors with the highest k(cat)/K(m) values were major sugar constituents of cellulose and hemicellulose, namely d-glucose, D-galactose, l-arabinose, D-xylose and cellobiose. This indicates a possible physiological role of the enzyme in lignocellulose breakdown. PDH showed no detectable activity with oxygen, and its reactivity towards electron acceptors was limited to various substituted benzoquinones and complexed metal ions, with the ferricenium ion and the benzoquinone imine 2,6-dichloroindophenole displaying the highest k(cat)/K(m). The enzyme catalyzed in up to 95% yields the regiospecific conversion of D-galactose to 2-dehydro-D-galactose, an intermediate in a possible biotechnologically interesting process for redox isomerization of D-galactose to the prebiotic sugar D-tagatose. PMID:18083263

  11. Electrocatalytic oxidation of phenol from wastewater using Ti/SnO2-Sb2O4 electrode: chemical reaction pathway study.

    Science.gov (United States)

    Loloi, Mahshid; Rezaee, Abbas; Aliofkhazraei, Mahmood; Rouhaghdam, Alireza Sabour

    2016-10-01

    In this study, a titanium plate was impregnated with SnO2 and Sb (Ti/SnO2-Sb2O4) for the electrocatalytic removal of phenol from wastewater, and the chemical degradation pathway was presented. The effects of various parameters such as pH, current density, supporting electrolyte, and initial phenol concentration were studied. At optimum conditions, it was found that phenol was quickly oxidized into benzoquinone because of the formation of various strong radicals during electrolysis by the Ti/SnO2-Sb2O4 anode from 100 to acid such as oxalic acid and formic acid. HPLC analysis showed only trace amounts of benzoquinone remaining in the solution. The efficiency of TOC removal at the Ti/SnO2-Sb2O4 anode surface showed a degradation rate of 49 % over 2 h. Results showed that the molecular oxygen potential at the electrode was 1.7 V. The phenol removal mechanism at the surface of the Ti/SnO2-Sb2O4 anode was influenced by the pH. Under acidic conditions, the mechanism of electron transfer occurred directly, whereas under alkaline conditions, the mechanism can be indirect. This research shows that the proposed electrolyte can significantly influence the efficiency of phenol removal. It can be concluded that the treatment using an appropriate Ti/SnO2-Sb2O4 electrode surface can result in the rapid oxidation of organic pollutants. PMID:27406226

  12. Potential mechanism for pentachlorophenol-induced carcinogenicity: a novel mechanism for metal-independent production of hydroxyl radicals.

    Science.gov (United States)

    Zhu, Ben-Zhan; Shan, Guo-Qiang

    2009-06-01

    The hydroxyl radical ((*)OH) has been considered to be one of the most reactive oxygen species produced in biological systems. It has been shown that (*)OH can cause DNA, protein, and lipid oxidation. One of the most widely accepted mechanisms for (*)OH production is through the transition metal-catalyzed Fenton reaction. Pentachlorophenol (PCP) was one of the most widely used biocides, primarily for wood preservation. PCP is now ubiquitously present in our environment and even found in people who are not occupationally exposed to it. PCP has been listed as a priority pollutant by the U.S. Environmental Protection Agency (EPA) and classified as a group 2B environmental carcinogen by the International Association for Research on Cancer (IARC). The genotoxicity of PCP has been attributed to its two major quinoid metabolites: tetrachlorohydroquinone and tetrachloro-1,4-benzoquinone (TCBQ). Although the redox cycling of PCP quinoid metabolites to generate reactive oxygen species is believed to play an important role, the exact molecular mechanism underlying PCP genotoxicity is not clear. Using the salicylate hydroxylation assay and electron spin resonance (ESR) secondary spin-trapping methods, we found that (*)OH can be produced by TCBQ and H(2)O(2) independent of transition metal ions. Further studies showed that TCBQ, but not its corresponding semiquinone radical, the tetrachlorosemiquinone radical (TCSQ(*)), is essential for (*)OH production. The major reaction product between TCBQ and H(2)O(2) was identified to be trichloro-hydroxy-1,4-benzoquinone (TrCBQ-OH), and H(2)O(2) was found to be the source and origin of the oxygen atom inserted into this reaction product. On the basis of these data, we propose that (*)OH production by TCBQ and H(2)O(2) is not through a semiquinone-dependent organic Fenton reaction but rather through the following novel mechanism: a nucleophilic attack of H(2)O(2) to TCBQ, leading to the formation of an unstable trichloro-hydroperoxyl-1

  13. The effect of free radical inhibitor on the sensitized radiation crosslinking and thermal processing stabilization of polyurethane shape memory polymers

    International Nuclear Information System (INIS)

    The effects of free radical inhibitor on the electron beam crosslinking and thermal processing stabilization of novel radiation crosslinkable polyurethane shape memory polymers (SMPs) blended with acrylic radiation sensitizers have been determined. The SMPs in this study possess novel processing capabilities—that is, the ability to be melt processed into complex geometries as thermoplastics and crosslinked in a secondary step using electron beam irradiation. To increase susceptibility to radiation crosslinking, the radiation sensitizer pentaerythritol triacrylate (PETA) was solution blended with thermoplastic polyurethane SMPs made from 2-butene-1,4-diol and trimethylhexamethylene diisocyanate (TMHDI). Because the thermoplastic melt processing methods such as injection molding are often carried out at elevated temperatures, sensitizer thermal instability is a major processing concern. Free radical inhibitor can be added to provide thermal stabilization; however, inhibitor can also undesirably inhibit radiation crosslinking. In this study, we quantified both the thermal stabilization and radiation crosslinking inhibition effects of the inhibitor 1,4-benzoquinone (BQ) on polyurethane SMPs blended with PETA. Sol/gel analysis of irradiated samples showed that the inhibitor had little to no inverse effects on gel fraction at concentrations of 0–10,000 ppm, and dynamic mechanical analysis showed only a slight negative correlation between BQ composition and rubbery modulus. The 1,4-benzoquinone was also highly effective in thermally stabilizing the acrylic sensitizers. The polymer blends could be heated to 150 °C for up to 5 h or to 125 °C for up to 24 h if stabilized with 10,000 ppm BQ and could also be heated to 125 °C for up to 5 h if stabilized with 1000 ppm BQ without sensitizer reaction occurring. We believe this study provides significant insight into methods for manipulation of the competing mechanisms of radiation crosslinking and thermal stabilization of

  14. Heterogeneous Reactions of Surface-Adsorbed Catechol: A Comparison of Tropospheric Aerosol Surrogates

    Science.gov (United States)

    Hinrichs, R. Z.; Woodill, L. A.

    2009-12-01

    Surface-adsorbed organics can alter the chemistry of tropospheric solid-air interfaces, such as aerosol and ground level surfaces, thereby impacting photochemical cycles and altering aerosol properties. The nature of the surface can also influence the chemistry of the surface-adsorbed organic. We employed diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to monitor the adsorption of gaseous catechol on several tropospheric aerosol surrogates and to investigate the subsequent reactivity of adsorbed-catechol with nitrogen dioxide and, in separate preliminary experiments, ozone. Graphite, kaolinite, and sodium halide (NaF, NaCl, NaBr) powders served as carbonaceous, mineral and sea salt aerosol surrogates, respectively. Broad OH stretching bands for adsorbed catechol shifted to lower wavenumber with peak frequencies following the trend NaBr > NaCl > NaF ≈ kaolinite, consistent with the increasing basicity of the halide anions and basic Brønsted sites on kaolinite. The dark heterogeneous reaction of NO2 with NaCl-adsorbed catechol at relative humidity (RH) 4-nitrocatechol and oxidation forming 1,2-benzoquinone and the ring cleavage product muconic acid, with product yields of 88%, 8%, and 4%, respectively. 4-Nitrocatechol was the dominant product for catechol adsorbed on NaF and kaolinite, while NaBr-adsorbed catechol produced less 4-nitrocatechol and more 1,2-benzoquinone and muconic acid. For all three sodium halides, the reactions of NO2 with adsorbed catechol were orders of magnitude faster than between NO2 and each NaX substrate. 4-Nitrocatechol rates and product yields were consistent with the relative ability of each substrate to enhance the deprotonated nature of adsorbed-catechol. Increasing the relative humidity caused the rate of each product channel to decrease and also altered the product branching ratios. Most notably, 1,2-benzoquinone formation decreased significantly even at 13% RH. The dramatic reactivity of surface

  15. Inactivation of Coprinus cinereus peroxidase by 4-chloroaniline during turnover: comparison with horseradish peroxidase and bovine lactoperoxidase.

    Science.gov (United States)

    Chang, H C; Holland, R D; Bumpus, J A; Churchwell, M I; Doerge, D R

    1999-12-15

    The peroxidase from Coprinus cinereus (CPX) catalyzed oxidative oligomerization of 4-chloroaniline (4-CA) forming several products: N-(4-chlorophenyl)-benzoquinone monoamine (dimer D), 4,4'-dichloroazobenzene (dimer E); 2-(4-chloroanilino)-N-(4-chlorophenyl)-benzoquinone (trimer F); 2-amino-5-chlorobenzoquinone-di-4-chloroanil (trimer G); 2-(4-chloroanilino)-5-hydroxybenzoquinone-di-4-chloroanil (tetramer H) and 2-amino-5-(-4-chlroanilino)-benzoquinone-di-4-chloroanil (tetramer 1). In the presence of 4-CA and H2O2, CPX was irreversibly inactivated within 10 min. Inactivation of CPX in the presence of H2O2 was a time-dependent, first-order process when the concentration of 4-CA was varied between 0 and 2.5 mM. The apparent dissociation constant (Ki) for CPX and 4-CA was 0.71 mM. The pseudo-first order rate constant for inactivation (k(inact)), was 1.15 x 10(-2) s(-1). Covalent incorporation of 20 mole 14C-4-CA per mole of inactivated CPX was observed. The partition ratio was about 2200 when either 4-CA or H2O2 was used as the limiting substrate. These results show that 4-CA is a metabolically activated inactivator (i.e. a suicide substrate). Unmodified heme and hydroxymethyl heme were isolated from native, 4-CA-inactivated and H2O2-incubated CPX. Inactivation resulted in significant losses in both heme contents. Analysis of tryptic peptides from 4-CA-inactivated CPX by MALDI-TOF/ MS and UV-VIS spectrophotometry suggested that trimer G and tetramer H were the major 4-CA derivatives that were covalently bound, including to a peptide (MGDAGF-SPDEVVDLLAAHSLASQEGLNSAIFR) containing the heme binding site. These studies show that heme destruction and covalent modification of the polypeptide chain are both important for the inactivation of CPX. These results were compared with similar studies on 4-CA-inactivated horseradish peroxidase (HRP) and bovine lactoperoxidase (LPO) during the oxidation of 4-CA.

  16. Energy-level tailoring in a series of redox-rich quinonoid-bridged diruthenium complexes containing tris2-pyridylmethyl)amine as a co-ligand.

    Science.gov (United States)

    Weisser, Fritz; Huebner, Ralph; Schweinfurth, David; Sarkar, Biprajit

    2011-05-01

    Reactions of [{Ru(tmpa)}2(μ-Cl)2][ClO4]2, (2[ClO4]2, tmpa=tris(2-pyridylmethyl)amine) with 2,5-dihydroxy-1,4-benzoquinone (L1), 2,5-di-[2,6-(dimethyl)-anilino]-1,4-benzoquinone (L2), or 2,5-di-[2,4,6-(trimethyl)-anilino)]-1,4-benzoquinone (L3) in the presence of a base led to the formation of the dinuclear complexes [{Ru(tmpa)}2(μ-L1-2H)][ClO4]2 (3[ClO4]2), [{Ru(tmpa)}2(μ-L2-2H)][ClO4]2 (4[ClO4]2), and [{Ru(tmpa)}2(μ-L3-2H)][ClO4]2 (5[ClO4]2). Structural characterization of 5[ClO4]2 showed the localization of the double bonds within the quinonoid ring and a twisting of the mesityl substituents with respect to the quinonoid plane. Cyclic voltammetry of the complexes show two reversible oxidation and quinonoid-based reduction processes. Results obtained from UV/Vis/NIR and EPR spectroelectrochemistry are invoked to discuss ruthenium- versus quinonoid-ligand-centered redox activity. The complex 3[ClO4]2 is compared to the reported complex [{Ru(bpy)}2(μ-L1-2 H)]2+ (12+, bpy=2,2′-bipyridine). The effects of substituting the bidentate and better π-accepting bpy co-ligands with tetradentate tmpa ligands [pure σ-donating (amine) as well as σ-donating and π-accepting (pyridines)] on the redox and electronic properties of the complexes are discussed. Comparisons are also made between complexes containing the dianionic forms of the all-oxygen-donating L1 ligand with the L2 and L3 ligands containing an [O,N,O,N] donor set. The one-electron oxidized forms of the complexes show absorption in the NIR region. The position as well as the intensity of this band can be tuned by the substituents on the quinonoid bridge. In addition, this band can be switched on and off by using tunable redox potentials, making such systems attractive candidates for NIR electrochromism. PMID:21688408

  17. Antibacterial activities and structure-activity relationships of a panel of 48 compounds from Kenyan plants against multidrug resistant phenotypes.

    Science.gov (United States)

    Omosa, Leonidah K; Midiwo, Jacob O; Mbaveng, Armelle T; Tankeo, Simplice B; Seukep, Jackson A; Voukeng, Igor K; Dzotam, Joachim K; Isemeki, John; Derese, Solomon; Omolle, Ruth A; Efferth, Thomas; Kuete, Victor

    2016-01-01

    In the current study forty eight compounds belonging to anthraquinones, naphthoquinones, benzoquinones, flavonoids (chalcones and polymethoxylated flavones) and diterpenoids (clerodanes and kauranes) were explored for their antimicrobial potential against a panel of sensitive and multi-drug resistant Gram-negative and Gram-positive bacteria. The minimal inhibitory concentration (MIC) determinations on the tested bacteria were conducted using modified rapid INT colorimetric assay. To evaluate the role of efflux pumps in the susceptibility of Gram-negative bacteria to the most active compounds, they were tested in the presence of phenylalanine arginine β-naphthylamide (PAβN) (at 30 µg/mL) against selected multidrug resistance (MDR) bacteria. The anthraquinone, emodin, naphthaquinone, plumbagin and the benzoquinone, rapanone were active against methicillin resistant Staphylococcus aureus (MRSA) strains of bacteria with MIC values ranging from 2 to 128 μg/mL. The structure activity relationships of benzoquinones against the MDR Gram-negative phenotype showed antibacterial activities increasing with increase in side chain length. In the chalcone series the presence of a hydroxyl group at C3' together with a methoxy group and a second hydroxyl group in meta orientation in ring B of the chalcone skeleton appeared to be necessary for minimal activities against MRSA. In most cases, the optimal potential of the active compounds were not attained as they were extruded by bacterial efflux pumps. However, the presence of the PAβN significantly increased the antibacterial activities of emodin against Gram-negative MDR E. coli AG102, 100ATet; K. pneumoniae KP55 and KP63 by >4-64 g/mL. The antibacterial activities were substantially enhanced and were higher than those of the standard drug, chloramphenicol. These data clearly demonstrate that the active compounds, having the necessary pharmacophores for antibacterial activities, including some quinones and chalcones are

  18. Anodic oxygen-transfer electrocatalysis at iron-doped lead dioxide electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Feng, Jianren

    1994-10-01

    The research illustrated in this thesis was performed under the guidance of Professor Dennis C. Johnson beginning in March 1987. Chapter 2 concentrates on the development and electrocatalytic properties of iron-doped {beta}-PbO{sub 2} films on noble-metal substrates. Chapter 3 focuses attention on the preparation and characterization of iron-doped {beta}-PbO{sub 2} films on titanium substrates (Fe-PbO{sub 2}/Ti). Chapter 4 discusses anodic evolution of ozone at Fe-PbO{sub 2}/Ti electrodes. Chapter 5 describes electrochemical incineration of p-benzoquinone (BQ) at Fe-PbO{sub 2}/Ti electrodes. In addition, the Appendix includes another published paper which is a detailed study of {alpha}-PbO{sub 2} films deposited on various types of stainless steel substrates.

  19. Microwave assisted wet oxidation of p-nitrophenol

    Institute of Scientific and Technical Information of China (English)

    BO; Longli; CHEN; Shuo; QUAN; Xie; LIU; Xitao; ZHAO; Huimin

    2005-01-01

    Aqueous solution of p-nitrophenol (PNP) was treated continuously by microwave assisted wet oxidation while flowing through a granular activated carbon (GAC) fixed bed. PNP was pre-adsorbed onto GAC prior to being put into the reactor so as to prevent PNP adsorption on GAC during microwave irradiation. PNP solutions with different initial concentration (218.6 mg/L and 1200 mg/L) were treated under conditions of microwave power 500 W, liquid flow 6.4 mL/min and air flow 40 mL/min or 60 mL/min. The results indicated that the removal of PNP was higher than 90% and more than 65% PNP was mineralized. Phenol, nitrobenzene, hydroquinone and benzoquinone occurred as course products during the operation process, which were degraded further. The biodegradability of the outflow was improved greatly by microwave assisted wet oxidation.

  20. Study and Elimination of the Interference of Aluminium on the Voltammetric Determination of Uranium with Chloranilic Acid. Application to the Determination of Uranium in Waters and Geological Samples

    International Nuclear Information System (INIS)

    The interference of aluminium during the voltammetric determination of uranium with 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone (chloranilic acid) has been investigated. The presence of aluminium originates a voltammetric signal due to its chloranilic acid complex at the same potential range as the uranium analytical signal appears. The interference of aluminium can be overcome by addition of an appropriate amount of sodium fluoride as complexing reagent. The determination of uranium by adsorptive stripping voltammetry (AdSV) can be carried out at concentration levels as low as 1 μg/L in the presence of 100 μg/L aluminium after the addition of 100μL of 0.1 mol/L NaF. The method can be applied to the determination of uranium in aluminium-containing waters and geological samples containing high aluminium levels. (Author) 19 refs

  1. Programmed Transport and Release of Cells by Self-Propelled Micromotors.

    Science.gov (United States)

    Yoshizumi, Yoshitaka; Okubo, Kyohei; Yokokawa, Masatoshi; Suzuki, Hiroaki

    2016-09-20

    Autonomous transport and release of bacterial cells by self-propelled micromotors were achieved. The motors consisted of zinc and platinum hemispheres formed on polystyrene beads and moved as a result of simultaneous redox reactions occurring on both metal ends. The highly negative redox potential of zinc enabled the selection of a wide variety of organic redox compounds as fuels, such as methanol and p-benzoquinone. The movement of motors was observed in solutions of fuels. To realize autonomous capture, transport, and release of cargo, a self-assembled monolayer (SAM) was formed on the platinum part of the motor. This SAM could be desorbed by coupling the reaction with the dissolution of zinc, which could also be controlled by adjusting the concentration of Zn(2+) ions. Escherichia coli (E. coli) cells were captured by the motor (due to hydrophobic interactions), transported, and released following SAM desorption at the mixed potential. PMID:27571037

  2. Effects of gamma irradiation on food contact polyethylene, polypropylene and polystyrene: additives and other chemicals

    International Nuclear Information System (INIS)

    The effects of gamma irradiation on additives, oligomers, and other chemicals in food contact polyethylene, polypropylene and polystyrene were investigated. Polyethylene and polypropylene products contained several antioxidants, lubricants and plasticizers. After gamma irradiation, the contents of all the antioxidants significantly decreased. Irgafos 168 disappeared the fastest. Lubricants and plasticizers decreased to some extent or not at all. 2,4-Di-tert-butylphenol was detected not only after irradiation but also before irradiation, and 1,3-di-tert-butylbenzene and 2,6-di-tert-butyl-1,4-benzoquinone were detected only after irradiation. They were presumed to be degradation products of the irradiation, though the former should be also a degradation product of the manufacturing process. On the other hand, the polystyrene products contained styrene dimers and trimers and their contents did not change after the gamma irradiation. (author)

  3. Study on US/O3 mechanism in p-chlorophenol decomposition

    Institute of Scientific and Technical Information of China (English)

    XU Xian-wen; XU Xin-hua; SHI Hui-xiang; WANG Da-hui

    2005-01-01

    Study on the effects of sonolysis, ozonolysis and US/O3 system on the decomposition ofp-chlorophenol in aqueous solutions indicated that in the cases of US/O3 system, individual ozonolysis and sonolysis, the decomposition rate of p-chlorophenol reached 78.78%, 56.20%, 2.79% after a 16-min reaction while its CODcr (chemical oxygen demand) removal rate was 97.02%, 62.17%, 3.67% after a 120-min reaction. The decomposition reaction ofp-chlorophenol follows pseudo-first-order kinetics. The enhancement factors ofp-chlorophenol and its CODer under US/O3 system reached 63% and 237% respectively. The main intermediates during the decomposition include catechol, hydroquinone, p-benzoquinone, phenol, fumaric acid, maleic acid,oxalic acid and formic acid. The decomposition mechanism of p-chlorophenol was also discussed.

  4. Tetra- and octa-[4-(2-hydroxyethyl)phenoxy bearing novel metal-free and zinc(II) phthalocyanines: Synthesis, characterization and investigation of photophysicochemical properties

    International Nuclear Information System (INIS)

    In this study, four novel phthalonitriles (1–4) and their corresponding metal-free (5–8) and zinc(II) phthalocyanine derivatives (9–12) bearing 4-(hydroxyethyl)phenoxy groups were synthesized. These novel compounds were characterized by IR, elemental analyses, 1H-NMR, UV–vis, and MALDI-TOF spectral data. Furthermore, photophysical (fluorescence quantum yields and lifetimes) and photochemical properties (singlet oxygen generation and photodegradation quantum yields) of these phthalocyanines were investigated in dimethylsulfoxide. The studied zinc(II) phthalocyanines generated highly singlet oxygen which is very important for the photodynamic therapy (PDT) of cancer. The fluorescence quenching behaviour of the newly synthesized phthalocyanine compounds were also investigated using 1,4-benzoquinone. - Highlights: • Octa and tetra 4-(hydroxyethyl)phenoxy substituted metal-free and zinc(II) phthalocyanines. • Study of photophysicochemical properties of eight new phthalocyanines. • Highly singlet oxygen generation for novel zinc(II) phthalocyanine photosensitizers

  5. Excited state electron transfer in systems with a well-defined geometry. [cyclophane

    Energy Technology Data Exchange (ETDEWEB)

    Kaufmann, K.J.

    1980-12-01

    The effect of temperature, dielectric strength and ligand on the structure of the mesopyropheophorbide cyclophanes will be studied. ESR, NMR, emission and absorption spectroscopy, as well as circular dichroism will be used. The changes in structure will be correlated with changes in the photochemical activity. Electron acceptors such as benzoquinone will be utilized to stabilize the charge separation. Charge separation in porphyrin quinone dimers will also be studied. It was found that electron transfer in the cyclophane system is relatively slow. This is presumably due to an orientation requirement for fast electron transfer. Solvent dielectric also is important in producing a charge separation. Decreasing the temperature effects the yield of charge transfer, but not the kinetics.

  6. Use of Ionic Liquids in Recycle of Palladium Catalysts for Synthesis of Polyketone

    Institute of Scientific and Technical Information of China (English)

    TIAN Jing; GUO Jintang; ZHANG Xuemei; ZHANG Xin; XU Yongshen

    2008-01-01

    Room temperature ionic liquids as solvents for palladium-catalyzed copolymerization of carbon monoxide and styrene were prepared by reaction of aqueous lead tetrafluoroborate with correspond-ing chloride or bromide salts. The recyclability of palladium composite catalyst in various ionic liquids was investigated.[Pd(bipy)2][BF4]2 showed a lower catalytic activity than [Pd(bipy)2][PF6]2 in similar conditions, although the catalytic activity of each composite catalyst in ionic liquids still existed after 4 successive recycles. It was shown the catalytic activity of palladium composite catalyst was higher than that of the catalyst formed in situ from palladium acetate, 2,2'-bipyridyl, and HA (A=PF6-, BF4-) in ionic liquids. The effects of volume of ionic liquids, reaction time, and the dosage of benzoquinone on the copolymerization were also studied.

  7. Inhibitory effects of sudanese medicinal plant extracts on hepatitis C virus (HCV) protease.

    Science.gov (United States)

    Hussein, G; Miyashiro, H; Nakamura, N; Hattori, M; Kakiuchi, N; Shimotohno, K

    2000-11-01

    One hundred fifty-two methanol and water extracts of different parts of 71 plants commonly used in Sudanese traditional medicine were screened for their inhibitory effects on hepatitis C virus (HCV) protease (PR) using in vitro assay methods. Thirty-four extracts showed significant inhibitory activity (>/=60% inhibition at 100 microg/mL). Of these, eight extracts, methanol extracts of Acacia nilotica, Boswellia carterii, Embelia schimperi, Quercus infectoria, Trachyspermum ammi and water extracts of Piper cubeba, Q. infectoria and Syzygium aromaticum, were the most active (>/=90% inhibition at 100 microg/mL). From the E. schimperi extract, two benzoquinones, embelin (I) and 5-O-methylembelin (II), were isolated and found as potent HCV-PR inhibitors with IC(50) values of 21 and 46 microM, respectively. Inhibitory activities of derivatives of I against HCV-PR as well as their effects on other serine proteases were also investigated. PMID:11054840

  8. Evaluation of herbicidal potential of depsides from Cladosporium uredinicola, an endophytic fungus found in Guava fruit

    Energy Technology Data Exchange (ETDEWEB)

    Medeiros, Livia S. de; Sampaio, Olivia M.; Silva, Maria Fatima das G.F. da; Rodrigues Filho, Edson [Departamento de Quimica, Universidade Federal de Sao Carlos, SP (Brazil); Veiga, Thiago Andre M., E-mail: tveiga@unifesp.br [Instituto de Ciencias Ambientais, Quimicas e Farmaceuticas, Universidade Federal de Sao Paulo, Diadema, SP (Brazil)

    2012-08-15

    Two natural products produced by Cladosporium uredinicola, an endophytic fungus isolated from guava fruit, were evaluated for their effects on photosynthesis. Both of them inhibited electron flow (basal, phosphorylating, and uncoupled) from water to methylviologen (MV), acting as Hill reaction inhibitors in freshly lysed spinach thylakoids. These polyketides, belonging to depsides class, inhibited partial reactions of photosystem II (PS II) electron flow from water to 2,5-dichloro-1,4-benzoquinone (DCBQ), from water to sodium silicomolybdate (SiMo Na{sup +}), and partially inhibited electron flow from 1,5-diphenylcarbazide (DPC) to 2,6-dichloroindophenol (DCPIP). These results established that the depsides sites of inhibition are located on the donor and acceptor sides of PS II, between P680 and QA . Chlorophyll a fluorescence measurements corroborated this mechanism of action. None of the tested compounds inhibited photosystem I (PS I) electron transport. (author)

  9. Nitrogen Forms in Synthetic Humic Acids Using Nitrogen—15 Nuclear Magnetic Resonance Technique

    Institute of Scientific and Technical Information of China (English)

    ZHUOSU-NENG; WENQI-XIAO

    1993-01-01

    15N-labelled phenolic polymers were synthesized by reactions of p-benzoquinone and 1,4-diphenol with 15N-labelled glycine and were studied by using 15N CP-MAS NMR technique in combination with chemical approaches.Results showed that the proportion of polymer nitrogen as N-phenyl amino acid N was not as great as expected,only accounting for 5%-15%;and most of N in polymers occurred in the forms of amide,pyrrole-and indole-like nitrogen,aliphatic amines and isonitrile.It seems that great differences existed between synthetic humic acids and soil humic acids in the type and distribution of nitrogen forms.

  10. Theoretical elucidation of structure-activity relationship of flavonoid antioxidants

    Institute of Scientific and Technical Information of China (English)

    张红雨

    1999-01-01

    AM1 method was employed to calculate flavonoid antioxidants, and the results obtained are as follows. Firstly, flavonoid hydroxyls at ortho position were more active than the hydroxyls at meta position in scavenging oxygen-free radicals, which resulted from the facts that (ⅰ) the former were stabilized by forming intramolecular hydrogen bond and (ⅱ) ortho benzoquinone formed in the former structures through resonance, which resulted in large percentage of distribution of spin density on ortho oxygen and low internal energy. Secondly, electron-attracting effect of ring C of chromone-flavonoids showed some passive effects on hydroxyls of ring A, making the OH less active. As ring C had little effect on ring B and hydroxyls of ring B in most flavonoids were at ortho position, the rule summarized from experiments showing that hydroxyls of ring B were more active in scavenging oxygen-free radicals was elucidated.

  11. Evaluation of herbicidal potential of depsides from Cladosporium uredinicola, an endophytic fungus found in Guava fruit

    International Nuclear Information System (INIS)

    Two natural products produced by Cladosporium uredinicola, an endophytic fungus isolated from guava fruit, were evaluated for their effects on photosynthesis. Both of them inhibited electron flow (basal, phosphorylating, and uncoupled) from water to methylviologen (MV), acting as Hill reaction inhibitors in freshly lysed spinach thylakoids. These polyketides, belonging to depsides class, inhibited partial reactions of photosystem II (PS II) electron flow from water to 2,5-dichloro-1,4-benzoquinone (DCBQ), from water to sodium silicomolybdate (SiMo Na+), and partially inhibited electron flow from 1,5-diphenylcarbazide (DPC) to 2,6-dichloroindophenol (DCPIP). These results established that the depsides sites of inhibition are located on the donor and acceptor sides of PS II, between P680 and QA . Chlorophyll a fluorescence measurements corroborated this mechanism of action. None of the tested compounds inhibited photosystem I (PS I) electron transport. (author)

  12. Mineralization of aqueous pentachlorophenolate by anodic contact glow discharge electrolysis

    Institute of Scientific and Technical Information of China (English)

    Haiming Yang; Meguru Tezuka

    2011-01-01

    Exhaustive mineralization of pentachlorophenolate ion (PCP) in phosphate buffer was carried out using anodic contact glow discharge electrolysis (CGDE), in which plasma was sustained between the electrolyte and anode. During CGDE, PCP degraded smoothly. The amount of total organic carbon decreased significantly, indicating the eventual conversion of the carbon atoms of benzene nucleus to inorganic carbons. Furthermore, chlorine atoms in PCP were liberated as chloride ions. As a primary intermediate product, 2,3,5,6-tetrachloro-1,4-benzoquinone was detected, and oxalate and formate as byproducts were also found. It was revealed that disappearance of PCP obeyed first-order kinetics. The reaction rate was generally unaffected by both O2 and inert gases in the cell, although it decreased by raising initial pH of solution. In addition, a plausible reaction pathway involving hydroxyl radical was proposed.

  13. Santal monohydrate, an isoflavone isolated from Wyethia mollis

    Directory of Open Access Journals (Sweden)

    Kyle S. Knight

    2014-03-01

    Full Text Available The title compound [systematic name: 3-(3,4-dihydroxyphenyl-5-hydroxy-7-methoxy-4H-chromen-4-one monohydrate], C16H12O6·H2O, is a monohydrate of a natural product santal isolated from Wyethia mollis. In the santal molecule, the dihedral angle between the benzoquinone and dihydroxyphenyl fragments is 53.9 (1° and an intramolecular O—H...O hydrogen bond occurs. In the crystal, O—H...O hydrogen bonds link the components into corrugated layers parallel to the ac plane. The short distance of 3.474 (5 Å between the centroids of the benzene rings in neighbouring santal molecules reveals then existence of π–π interactions within the layers.

  14. Aqueous 4-nitrophenol decomposition and hydrogen peroxide formation induced by contact glow discharge electrolysis.

    Science.gov (United States)

    Liu, Yongjun; Wang, Degao; Sun, Bing; Zhu, Xiaomei

    2010-09-15

    Liquid-phase decomposition of 4-nitrophenol (4-NP) and formation of hydrogen peroxide (H(2)O(2)) induced by contact glow discharge electrolysis (CGDE) were investigated. Experimental results showed that the decays of 4-NP and total organic carbon (TOC) obeyed the first-order and pseudo-first-order reaction kinetics, respectively. The major intermediate products were 4-nitrocatechol, hydroquinone, benzoquinone, hydroxyhydroquinone, organic acids and nitrite ion. The final products were carbon dioxide and nitrate ion. The initial formation rate of H(2)O(2) decreased linearly with increasing initial concentration of 4-NP. Addition of iron ions, especially ferric ion, to the solution significantly enhanced the 4-NP removal due to the additional hydroxyl radical formation through Fenton's reaction. A reaction pathway is proposed based on the degradation kinetics and the distribution of intermediate products.

  15. Electrochemical and morphological characterization of gold nanoparticles deposited on boron-doped diamond electrode

    Energy Technology Data Exchange (ETDEWEB)

    Limat, Meriadec; El Roustom, Bahaa [Ecole Polytechnique Federale de Lausanne (EPFL), Institute of Chemical Sciences and Engineering, CH-1015 Lausanne (Switzerland); Jotterand, Henri [Ecole Polytechnique Federale de Lausanne (EPFL), Institute of Physics of the Complex Matter, CH-1015 Lausanne (Switzerland); Foti, Gyoergy [Ecole Polytechnique Federale de Lausanne (EPFL), Institute of Chemical Sciences and Engineering, CH-1015 Lausanne (Switzerland)], E-mail: gyorgy.foti@epfl.ch; Comninellis, Christos [Ecole Polytechnique Federale de Lausanne (EPFL), Institute of Chemical Sciences and Engineering, CH-1015 Lausanne (Switzerland)

    2009-03-30

    A novel two-step method was employed to synthesize gold nanoparticles dispersed on boron-doped diamond (BDD) electrode. It consisted of sputter deposition at ambient temperature of maximum 15 equivalent monolayers of gold, followed by a heat treatment in air at 600 deg. C. Gold nanoparticles with an average diameter between 7 and 30 nm could be prepared by this method on polycrystalline BDD film electrode. The obtained Au/BDD composite electrode appeared stable under conditions of electrochemical characterization performed using ferri-/ferrocyanide and benzoquinone/hydroquinone redox couples in acidic medium. The electrochemical behavior of Au/BDD was compared to that of bulk Au and BDD electrodes. Finally, the Au/BDD composite electrode was regarded as an array of Au microelectrodes dispersed on BDD substrate.

  16. The protective effect of thymoquinone, an anti-oxidant and anti--inflammatory agent, against renal injury: A review

    Directory of Open Access Journals (Sweden)

    Ragheb Ahmed

    2009-01-01

    Full Text Available Thymoquinone (TQ, 2-Isopropyl-5-methyl-1, 4-benzoquinone, is one of the most active ingredients of Nigella Sativa seeds. TQ has a variety of beneficial properties including anti-oxidative and anti-inflammatory activities. Studies have provided original observations on the role of oxidative stress and inflammation in the development of renal diseases such as glomerulo-nephritis and drug-induced nephrotoxicity. The renoprotective effects of TQ have been demons-trated in animal models. Also, TQ has been used successfully in treating allergic diseases in humans. The aim of this review is to highlight the importance of reactive oxygen species in renal pathophysiology and the intriguing possibility for a role of TQ in the prevention of and/or protection from renal injury in humans.

  17. A complementary switching mechanism for organic memory devices to regulate the conductance of binary states

    Science.gov (United States)

    Vyas, Giriraj; Dagar, Parveen; Sahu, Satyajit

    2016-06-01

    We have fabricated an organic non-volatile memory device wherein the ON/OFF current ratio has been controlled by varying the concentration of a small organic molecule, 2,3-Dichloro-5,6-dicyano-p-benzoquinone (DDQ), in an insulating matrix of a polymer Poly(4-vinylphenol) (PVP). A maximum ON-OFF ratio of 106 is obtained when the concentration of DDQ is half or 10 wt. % of PVP. In this process, the switching direction for the devices has also been altered, indicating the disparity in conduction mechanism. Conduction due to metal filament formation through the active material and the voltage dependent conformational change of the organic molecule seem to be the motivation behind the gradual change in the switching direction.

  18. Photophysical, Photochemical, and BQ Quenching Properties of Zinc Phthalocyanines with Fused or Interrupted Extended Conjugation

    Directory of Open Access Journals (Sweden)

    Gülşah Gümrükçü

    2014-01-01

    Full Text Available The effects of substituents and solvents on the photophysical and photochemical parameters of zinc(II phthalocyanines containing four Schiff’s base substituents attached directly and through phenyleneoxy-bridges on peripheral positions are reported. The group effects on peripheral position and the continual and intermittent conjugation of the phthalocyanine molecules on the photophysical and photochemical properties are also investigated. General trends are described for photodegradation, singlet oxygen, and fluorescence quantum yields of these compounds in dimethylsulfoxide (DMSO, dimethylformamide (DMF, and tetrahydrofurane (THF. Among the different substituents, phthalocyanines with cinnamaldimine moieties (1c and 2c have the highest singlet oxygen quantum yields (ΦΔ and those with nitro groups (1a and 2a have the highest fluorescence quantum yields in all the solvents used. The fluorescence of the substituted zinc(II phthalocyanine complexes is effectively quenched by 1,4-benzoquinone (BQ in these solvents.

  19. Size distribution and chemical composition of secondary organic aerosol formed from Cl-initiated oxidation of toluene

    Institute of Scientific and Technical Information of China (English)

    Mingqiang Huang; Weijun Zhang; Xuejun Gu; Changjin Hu; Weixiong Zhao; Zhenya Wang; Li Fang

    2012-01-01

    Secondary organic aerosol (SOA) formed from Cl-initiated oxidation of toluene was investigated in a home-made smog chamber.The size distribution and chemical composition of SOA particles were measured using aerodynamic particle sizer spectrometer and the aerosol laser time-of-flight mass spectrometer (ALTOFMS),respectively.According to a large number of single aerosol diameter and mass spectra,the size distribution and chemical composition of SOA were obtained statistically.Experimental results showed that SOA particles created by Cl-initiated oxidation of toluene is predominantly in the form of fine particles,which have diameters less than 2.5 μm (i.e.,PM2.5),and glyoxal,benzaldehyde,benzyl alcohol,benzoquinone,benzoic acid,benzyl hydroperoxide and benzyl methyl nitrate are the major products components in the SOA.The possible reaction mechanisms leading to these products are also proposed.

  20. Measuring protection of aromatic wine thiols from oxidation by competitive reactions vs wine preservatives with ortho-quinones.

    Science.gov (United States)

    Nikolantonaki, Maria; Magiatis, Prokopios; Waterhouse, Andrew L

    2014-11-15

    Quinones are central intermediates in wine oxidation that can degrade the quality of wine by reactions with varietal thiols, such as 3-sulfanylhexanol, decreasing desirable aroma. Protection by wine preservatives (sulphur dioxide, glutathione, ascorbic acid and model tannin, phloroglucinol) was assessed by competitive sacrificial reactions with 4-methyl-1,2-benzoquinone, quantifying products and ratios by HPLC-UV-MS. Regioselectivity was assessed by product isolation and identification by NMR spectroscopy. Nucleophilic addition reactions compete with two electron reduction of quinones by sulphur dioxide or ascorbic acid, and both routes serve as effective quenching pathways, but minor secondary products from coupled redox reactions between the products and reactants are also observed. The wine preservatives were all highly reactive and thus all very protective against 3-sulfanylhexanol loss to the quinone, but showed only additive antioxidant effects. Confirmation of these reaction rates and pathways in wine is needed to assess the actual protective action of each tested preservative. PMID:24912696

  1. A silica-immobilized pt2+catalyst for the selective, aerobic oxidation of methane via an electron-transfer chain

    Institute of Scientific and Technical Information of China (English)

    Zengjian An; Xiulian Pan; Xiumei Liu; Xiuwen Han; Xinhe Bao

    2008-01-01

    The combination of Pt2+, benzoquinone and NaNO2 forms an electron-transfer chain, which leads to the oxidation of methane by O2 in CF3COOH aqueous solution. The overall turnover number per hour (TOF) of methane at 120 ℃ is 0.5 h-1, however, only about one fourth (23%) of methane is converted to the desired product of methanol in the formation of CF3COOCH3. The over-oxidation of methane to CO2, over the catalyst with the Pt2+ species immobilized via 2,2'-bipyridyl as a ligand on the silica substrate, is depressed distinctly. Under the same conditions, the conversion to methanol dominates, and no CO2 is observed, on account of the over-oxidation of methane, as confirmed by the isotope experiment.

  2. Multiferroic materials based on organic transition-metal molecular nanowires.

    Science.gov (United States)

    Wu, Menghao; Burton, J D; Tsymbal, Evgeny Y; Zeng, Xiao Cheng; Jena, Puru

    2012-09-01

    We report on the density functional theory aided design of a variety of organic ferroelectric and multiferroic materials by functionalizing crystallized transition-metal molecular sandwich nanowires with chemical groups such as -F, -Cl, -CN, -NO(2), ═O, and -OH. Such functionalized polar wires exhibit molecular reorientation in response to an electric field. Ferroelectric polarizations as large as 23.0 μC/cm(2) are predicted in crystals based on fully hydroxylized sandwich nanowires. Furthermore, we find that organic nanowires formed by sandwiching transition-metal atoms in croconic and rhodizonic acids, dihydroxybenzoquinone, dichloro-dihydroxy-p-benzoquinone, or benzene decorated by -COOH groups exhibit ordered magnetic moments, leading to a multiferroic organometallic crystal. When crystallized through hydrogen bonds, the microscopic molecular reorientation translates into a switchable polarization through proton transfer. A giant interface magnetoelectric response that is orders of magnitude greater than previously reported for conventional oxide heterostructure interfaces is predicted. PMID:22881120

  3. Preparation and phytotoxicity of sorgoleone analogues

    Directory of Open Access Journals (Sweden)

    Luiz Cláudio de Almeida Barbosa

    2001-12-01

    Full Text Available 3,5-Dimethoxybenzylic alcohol was converted into the 2-acetoxy-5-methoxy-3-(pent-1-yl-1,4-benzoquinone (12, in seven steps, with an overall yield of 14.6%. The natural quinone sorgoleone (1 was isolated from Sorghum bicolor and converted into the corresponding quinone (13 having a saturated side chain. The selective effects of these compounds (1, 12 and 13, at the dose of 5.6 mug of a.i./ g of substrate, on the growth of Cucumis sativus, Lactuca sativa, Desmodium tortuosum, Hyptis suaveolens and Euphorbia heterophylla were evaluated. All three compounds caused some inhibition on the root growth of the test plants (0.0-69.19% with the aerial parts less affected. The results showed that the triene unit of the sorgoleone side chain is not essential for the phytotoxicity and also the synthetic quinone was as active as the natural product.

  4. Quinones and non-quinones from the defensive secretion of Unciger transsilvanicus (Verhoeff, 1899 (Diplopoda, Julida, Julidae, from Serbia

    Directory of Open Access Journals (Sweden)

    Sekulić Tatjana Lj.

    2014-01-01

    Full Text Available A complex mixture of compounds was identified from the secretion of specimens of Unciger transsilvanicus. Phenol and p-cresol were detected for the first time in the family Julidae, and for the second time in the order Julida. Thirteen quinones were identified, with a great relative abundance of toloquinone and 2-methoxy-3-methyl-1,4-benzoquinone. Hydroquinone was detected for the first time in the order Julida. Besides these compounds, isopentyl hexacosatetraenoate and isopentyl esters of saturated and unsaturated fatty acids with chain lengths from C14 to C20were identified. The most abundant non-quinone compound was isopentyl eicosenoate. The relative abundance of quinone and non-quinone in the defensive fluid of U. transsilvanicus was 77% and 23%, respectively. The phylogenetic importance of the registered compounds is briefly discussed. [Projekat Ministarstva nauke Republike Srbije, br. 173038 i br. 172053

  5. Studies on the Chemical Constituents of Hedyotis (Hedyotis)Ⅷ. Isolation and Identification of Chemical Constituents in Goldhair Hedyotis (Hedyotis chrysotricha)%耳草属植物的化学研究Ⅷ.黄毛耳草化学成分的分离和鉴定

    Institute of Scientific and Technical Information of China (English)

    彭江南; 冯孝章; 梁晓天

    1999-01-01

    从中药黄毛耳草Hedyotis chrysotricha中分离并鉴定出10个化合物,经鉴定为:咖啡酸(caffeic acid,Ⅰ),东莨菪内酯(scopoletin,Ⅱ),2,6-二甲氧基对苯醌(2,6-dimethoxy-1,4-benzoquinone,Ⅲ),七叶内酯(aesculetin,Ⅳ),异落叶松树脂醇(isolarisiresinol, Ⅴ),β-谷甾醇(β-sitosterol, Ⅵ),胡萝卜苷(daucosterol,Ⅶ),异鼠李素-3-芸香糖苷(nicotiflorin,Ⅷ),水仙苷(narcissin,Ⅸ)和芦丁(rutin,Ⅹ).除Ⅱ和Ⅵ外均为首次从该植物中分得.

  6. Biologically active cannabinoids from high-potency Cannabis sativa.

    Science.gov (United States)

    Radwan, Mohamed M; Elsohly, Mahmoud A; Slade, Desmond; Ahmed, Safwat A; Khan, Ikhlas A; Ross, Samir A

    2009-05-22

    Nine new cannabinoids (1-9) were isolated from a high-potency variety of Cannabis sativa. Their structures were identified as (+/-)-4-acetoxycannabichromene (1), (+/-)-3''-hydroxy-Delta((4'',5''))-cannabichromene (2), (-)-7-hydroxycannabichromane (3), (-)-7R-cannabicoumarononic acid A (4), 5-acetyl-4-hydroxycannabigerol (5), 4-acetoxy-2-geranyl-5-hydroxy-3-n-pentylphenol (6), 8-hydroxycannabinol (7), 8-hydroxycannabinolic acid A (8), and 2-geranyl-5-hydroxy-3-n-pentyl-1,4-benzoquinone (9) through 1D and 2D NMR spectroscopy, GC-MS, and HRESIMS. The known sterol beta-sitosterol-3-O-beta-d-glucopyranosyl-6'-acetate was isolated for the first time from cannabis. Compounds 6 and 7 displayed significant antibacterial and antifungal activities, respectively, while 5 displayed strong antileishmanial activity. PMID:19344127

  7. Spectroscopic studies of charge transfer complexes between colchicine and some π acceptors

    Science.gov (United States)

    Arslan, Mustafa; Duymus, Hulya

    2007-07-01

    Charge transfer complexes between colchicine as donor and π acceptors such as tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano- p-benzoquinone (DDQ), p-chloranil ( p-CHL) have been studied spectrophotometrically in dichloromethane at 21 °C. The stoichiometry of the complexes was found to be 1:1 ratio by the Job method between donor and acceptors with the maximum absorption band at a wavelength of 535, 585 and 515 nm. The equilibrium constant and thermodynamic parameters of the complexes were determined by Benesi-Hildebrand and van't Hoff equations. Colchicine in pure form and in dosage form was applied in this study. The formation constants for the complexes were shown to be dependent on the structure of the electron acceptors used.

  8. Tetra- and octa-[4-(2-hydroxyethyl)phenoxy bearing novel metal-free and zinc(II) phthalocyanines: Synthesis, characterization and investigation of photophysicochemical properties

    Energy Technology Data Exchange (ETDEWEB)

    Köksoy, Baybars [Marmara University, Department of Chemistry, 34722 Kadıköy, Istanbul (Turkey); Durmuş, Mahmut [Gebze Technical University, Department of Chemistry, 41400 Gebze, Kocaeli (Turkey); Bulut, Mustafa, E-mail: mbulut@marmara.edu.tr [Marmara University, Department of Chemistry, 34722 Kadıköy, Istanbul (Turkey)

    2015-05-15

    In this study, four novel phthalonitriles (1–4) and their corresponding metal-free (5–8) and zinc(II) phthalocyanine derivatives (9–12) bearing 4-(hydroxyethyl)phenoxy groups were synthesized. These novel compounds were characterized by IR, elemental analyses, {sup 1}H-NMR, UV–vis, and MALDI-TOF spectral data. Furthermore, photophysical (fluorescence quantum yields and lifetimes) and photochemical properties (singlet oxygen generation and photodegradation quantum yields) of these phthalocyanines were investigated in dimethylsulfoxide. The studied zinc(II) phthalocyanines generated highly singlet oxygen which is very important for the photodynamic therapy (PDT) of cancer. The fluorescence quenching behaviour of the newly synthesized phthalocyanine compounds were also investigated using 1,4-benzoquinone. - Highlights: • Octa and tetra 4-(hydroxyethyl)phenoxy substituted metal-free and zinc(II) phthalocyanines. • Study of photophysicochemical properties of eight new phthalocyanines. • Highly singlet oxygen generation for novel zinc(II) phthalocyanine photosensitizers.

  9. Exposure to benzene metabolites causes oxidative damage in Saccharomyces cerevisiae.

    Science.gov (United States)

    Raj, Abhishek; Nachiappan, Vasanthi

    2016-06-01

    Hydroquinone (HQ) and benzoquinone (BQ) are known benzene metabolites that form reactive intermediates such as reactive oxygen species (ROS). This study attempts to understand the effect of benzene metabolites (HQ and BQ) on the antioxidant status, cell morphology, ROS levels and lipid alterations in the yeast Saccharomyces cerevisiae. There was a reduction in the growth pattern of wild-type cells exposed to HQ/BQ. Exposure of yeast cells to benzene metabolites increased the activity of the anti-oxidant enzymes catalase, superoxide dismutase and glutathione peroxidase but lead to a decrease in ascorbic acid and reduced glutathione. Increased triglyceride level and decreased phospholipid levels were observed with exposure to HQ and BQ. These results suggest that the enzymatic antioxidants were increased and are involved in the protection against macromolecular damage during oxidative stress; presumptively, these enzymes are essential for scavenging the pro-oxidant effects of benzene metabolites. PMID:27016252

  10. Functionalized Nanostructures: Redox-Active Porphyrin Anchors for Supramolecular DNA Assemblies

    KAUST Repository

    Börjesson, Karl

    2010-09-28

    We have synthesized and studied a supramolecular system comprising a 39-mer DNA with porphyrin-modified thymidine nucleosides anchored to the surface of large unilamellar vesicles (liposomes). Liposome porphyrin binding characteristics, such as orientation, strength, homogeneity, and binding site size, was determined, suggesting that the porphyrin is well suited as a photophysical and redox-active lipid anchor, in comparison to the inert cholesterol anchor commonly used today. Furthermore, the binding characteristics and hybridization capabilities were studied as a function of anchor size and number of anchoring points, properties that are of importance for our future plans to use the addressability of these redox-active nodes in larger DNA-based nanoconstructs. Electron transfer from photoexcited porphyrin to a lipophilic benzoquinone residing in the lipid membrane was characterized by steady-state and time-resolved fluorescence and verified by femtosecond transient absorption. © 2010 American Chemical Society.

  11. A solid fuel which has good flamability, stability and combustability

    Energy Technology Data Exchange (ETDEWEB)

    Iketani, Yu.; Masunetaka, K.; Nisino, A.; Takeuti, Ya.

    1983-09-27

    A solid fuel is patented which contains a carbon material, an oxidizing agent which has a breakdown point above the flash point of the carbon bearing material, a sublimating organic product and a binder. Coal, heat treated coal, coke and so on may be used for the carbon bearing material. The oxidizing agent consists of Ca (NO3)2, Ba (NO3)2, Sr(NO3)2, KCLO4, KCLO3 and bichromates and is used in a volume of 5 to 35 percent. The sublimating product may contain at least one of the following substances: camphor, metaldehyde, hexamethylendiamine, hexamethylentetraline and n-benzoquinone and is added in a volume of greater than or equal to 4 percent. The binder may be one of the following substances: tar, natural cellulose (Ts), rubber, cement, colloidal SG, colloidal ammonium and phosphates.

  12. Accurate Ionization Potentials and Electron Affinities of Acceptor Molecules IV: Electron-Propagator Methods.

    Science.gov (United States)

    Dolgounitcheva, O; Díaz-Tinoco, Manuel; Zakrzewski, V G; Richard, Ryan M; Marom, Noa; Sherrill, C David; Ortiz, J V

    2016-02-01

    Comparison of ab initio electron-propagator predictions of vertical ionization potentials and electron affinities of organic, acceptor molecules with benchmark calculations based on the basis set-extrapolated, coupled cluster single, double, and perturbative triple substitution method has enabled identification of self-energy approximations with mean, unsigned errors between 0.1 and 0.2 eV. Among the self-energy approximations that neglect off-diagonal elements in the canonical, Hartree-Fock orbital basis, the P3 method for electron affinities, and the P3+ method for ionization potentials provide the best combination of accuracy and computational efficiency. For approximations that consider the full self-energy matrix, the NR2 methods offer the best performance. The P3+ and NR2 methods successfully identify the correct symmetry label of the lowest cationic state in two cases, naphthalenedione and benzoquinone, where some other methods fail. PMID:26730459

  13. Gold-catalyzed oxidation of substituted phenols by hydrogen peroxide

    KAUST Repository

    Cheneviere, Yohan

    2010-10-20

    Gold nanoparticles deposited on inorganic supports are efficient catalysts for the oxidation of various substituted phenols (2,6-di-tert-butyl phenol and 2,3,6-trimethyl phenol) with aqueous hydrogen peroxide. By contrast to more conventional catalysts such as Ti-containing mesoporous silicas, which convert phenols to the corresponding benzoquinones, gold nanoparticles are very selective to biaryl compounds (3,3′,5,5′-tetra-tert-butyl diphenoquinone and 2,2′,3,3′,5,5′-hexamethyl-4,4′- biphenol, respectively). Products yields and selectivities depend on the solvent used, the best results being obtained in methanol with yields >98%. Au offers the possibility to completely change the selectivity in the oxidation of substituted phenols and opens interesting perspectives in the clean synthesis of biaryl compounds for pharmaceutical applications. © 2010 Elsevier B.V. All rights reserved.

  14. The role of humic and fulvic acids in the phototransformation of phenolic compounds in seawater

    Energy Technology Data Exchange (ETDEWEB)

    Calza, P., E-mail: paola.calza@unito.it; Vione, D.; Minero, C.

    2014-09-15

    Humic substances (HS) are known to act as photosensitizers toward the transformation of pollutants in the surface layer of natural waters. This study focused on the role played by HS toward the transformation of xenobiotics in seawater, with the purpose of assessing the prevailing degradation routes. Phenol was chosen as model xenobiotic and its transformation was investigated under simulated sunlight in the presence of terrestrial or marine humic and fulvic acids, in pure water at pH 8, artificial seawater (ASW) or natural seawater (NSW). The following parameters were determined: (1) the phenol degradation rate; (2) the variation in HS concentration with irradiation time; (3) the production of transformation products; (4) the influence of iron species on the transformation process. Faster transformation of phenol was observed with humic acids (HA) compared to fulvic acids (SRFA), and transformation induced by both HA and SRFA was faster in ASW than that in pure water. These observations can be explained by assuming an interplay between different competing and sometimes opposite processes, including the competition between chloride, bromide and dissolved oxygen for reaction with HS triplet states. The analysis of intermediates formed in the different matrices under study showed the formation of several hydroxylated (hydroquinone, 1,4-benzoquinone, resorcinol) and condensed compounds (2,2′-bisphenol, 4,4′-bisphenol, 4-phenoxyphenol). Although 1,4-benzoquinone was the main transformation product, formation of condensed molecules was significant with both HA and SRFA. Experiments on natural seawater spiked with HS confirmed the favored formation of condensed products, suggesting a key role of humic matter in dimerization reactions occurring in saline water. - Highlights: • Phenol transformation in seawater can be photosensitized by humic substances. • Dimeric species are peculiar intermediates formed in the process. • Phenol degradation occurred faster with

  15. Evidence for strain-specific differences in benzene toxicity as a function of host target cell susceptibility.

    Science.gov (United States)

    Neun, D J; Penn, A; Snyder, C A

    1992-01-01

    It has long been recognized that benzene exposure produces disparate toxic responses among different species or even among different strains within the same species. There is ample evidence that species- or strain-dependent differences in metabolic activity correlate with the disparate responses to benzene. However, bone marrow cells (the putative targets of benzene toxicity) may also exhibit species- or strain-dependent differences in susceptibility to the toxic effects of benzene. To investigate this hypothesis, two sets of companion experiments were performed. First, two strains of mice, Swiss Webster (SW) and C57B1/6J (C57), were exposed to 300 ppm benzene via inhalation and the effects of the exposures were determined on bone marrow cellularity and the development of bone marrow CFU-e (Colony Forming Unit-erythroid, an early red cell progenitor). Second, bone marrow cells from the same strains were exposed in vitro to five known benzene metabolites (1,4 benzoquinone, catechol, hydroquinone, muconic acid, and phenol) individually and in binary combinations. Benzene exposure, in vivo, reduced bone marrow cellularity and the development of CFU-e in both strains; however, reductions in both these endpoints were more severe in the SW strain. When bone marrow cells from the two strains were exposed in vitro to the five benzene metabolites individually, benzoquinone, hydroquinone, and catechol reduced the numbers of CFU-e in both strains in dose-dependent responses, phenol weakly reduced the numbers of the C57 CFU-e only and in a non-dose-dependent manner, and muconic acid was without effect on cells from either strain.(ABSTRACT TRUNCATED AT 250 WORDS)

  16. Identification and characterization of another 4-nitrophenol degradation gene cluster, nps, in Rhodococcus sp. strain PN1.

    Science.gov (United States)

    Yamamoto, Kenta; Nishimura, Munehiro; Kato, Dai-ichiro; Takeo, Masahiro; Negoro, Seiji

    2011-06-01

    4-Nitrophenol (4-NP) is a toxic compound formed in soil by the hydrolysis of organophosphorous pesticides, such as parathion. We previously reported the presence of the 4-NP degradation gene cluster (nphRA1A2) in Rhodococcus sp. strain PN1, which encodes a two-component 4-NP hydroxylase system that oxidizes 4-NP into 4-nitrocatechol. In the current study, another gene cluster (npsC and npsRA2A1B) encoding a similar 4-NP hydroxylase system was cloned from strain PN1. The enzymes from this 4-NP hydroxylase system (NpsA1 and NpsA2) were purified as histidine-tagged (His-) proteins and then characterized. His-NpsA2 showed NADH/FAD oxidoreductase activity, and His-NpsA1 showed 4-NP oxidizing activity in the presence of His-NpsA2. In the 4-NP oxidation using the reconstituted enzyme system (His-NpsA1 and His-NpsA2), hydroquinone (35% of 4-NP disappeared) and hydroxyquinol (59% of 4-NP disappeared) were detected in the presence of ascorbic acid as a reducing reagent, suggesting that, without the reducing reagent, 4-NP was converted into their oxidized forms, 1,4-benzoquinone and 2-hydroxy-1,4-benzoquinone. In addition, in the cell extract of recombinant Escherichia coli expressing npsB, a typical spectral change showing conversion of hydroxyquinol into maleylacetate was observed. These results indicate that this nps gene cluster, in addition to the nph gene cluster, is also involved in 4-NP degradation in strain PN1.

  17. Crystal structure determination of thymoquinone by high-resolution X-ray powder diffraction.

    Science.gov (United States)

    Pagola, S; Benavente, A; Raschi, A; Romano, E; Molina, M A A; Stephens, P W

    2004-01-01

    The crystal structure of 2-isopropyl-5-methyl-1,4-benzoquinone (thymoquinone) and its thermal behavior--as necessary physical and chemical properties--were determined in order to enhance the current understanding of thymoquinone chemical action by using high resolution x-ray powder diffraction, Fourier transform infrared spectroscopy (FTIR), and 3 thermo-analytical techniques thermogravimetric analysis (TGA), differential thermal analysis (DTA), and differential scanning calorimetry (DSC). The findings obtained with high-resolution x-ray powder diffraction and molecular location methods based on a simulated annealing algorithm after Rietveld refinement showed that the triclinic unit cell was a = 6.73728(8) A, b = 6.91560(8) A, c = 10.4988(2) A, alpha = 88.864(2) degrees, beta = 82.449(1) degrees, gamma = 77.0299(9) degrees; cell volume = 472.52(1) A3, Z = 2, and space group P1. In addition, FTIR spectrum revealed absorption bands corresponding to the carbonyl and C-H stretching of aliphatic and vinylic groups characteristically observed in such p-benzoquinones. Also, a chemical decomposition process starting at 65 degrees C and ending at 213 degrees C was noted when TGA was used. DSC allowed for the determination of onset at 43.55 degrees C and a melting enthalpy value of DeltaH(m) = 110.6 J/g. The low value obtained for the fusion point displayed a van der Waals pattern for molecular binding, and the thermograms performed evidence that thymoquinone can only be found in crystalline triclinic form, as determined by DRX methods. PMID:15760086

  18. Delivery of phytochemical thymoquinone using molecular micelle modified poly(D, L lactide-co-glycolide) (PLGA) nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Ganea, Gabriela M; Warner, Isiah M [Department of Chemistry, Louisiana State University, 434 Choppin Hall, Baton Rouge, LA 70803 (United States); Fakayode, Sayo O [Department of Chemistry, Anderson Center Modular Unit 244-B, Winston-Salem State University, Winston Salem, NC 27110 (United States); Losso, Jack N [Food Science Department, Louisiana State University Agricultural Center, 111 Food Science Building, Baton Rouge, LA 70803 (United States); Van Nostrum, Cornelus F [Department of Pharmaceutics, Utrecht Institute of Pharmaceutical Sciences (UIPS), Utrecht University, Sorbonnelaan 16, 3508 TB Utrecht (Netherlands); Sabliov, Cristina M, E-mail: iwarner@lsu.edu [Biological and Agricultural Engineering Department, Louisiana State University Agricultural Center, 141 E B Doran Building, Baton Rouge, LA 70803 (United States)

    2010-07-16

    Continuous efforts have been made in the development of potent benzoquinone-based anticancer drugs aiming for improved water solubility and reduced adverse reactions. Thymoquinone is a liposoluble benzoquinone-based phytochemical that has been shown to have remarkable antioxidant and anticancer activities. In the study reported here, thymoquinone-loaded PLGA nanoparticles were synthesized and evaluated for physico-chemical, antioxidant and anticancer properties. The nanoparticles were synthesized by an emulsion solvent evaporation method using anionic molecular micelles as emulsifiers. The system was optimized for maximum entrapment efficiency using a Box-Behnken experimental design. Optimum conditions were found for 100 mg PLGA, 15 mg TQ and 0.5% w/v poly(sodium N-undecylenyl-glycinate) (poly-SUG). In addition, other structurally related molecular micelles such as poly(sodium N-heptenyl-glycinate) (poly-SHG), poly(sodium N-undecylenyl-leucinate) (poly-SUL), and poly(sodium N-undecylenyl-valinate) (poly-SUV) were also examined as emulsifiers. All investigated molecular micelles provided excellent emulsifier properties, leading to maximum optimized TQ entrapment efficiency, and monodispersed particle sizes below 200 nm. The release of TQ from molecular micelle modified nanoparticles was investigated by dialysis and reached lower levels than the free drug. The antioxidant activity of TQ-loaded nanoparticles, indicated by IC50 (mg ml{sup -1} TQ for 50% 2,2-diphenyl-1-picrylhydrazyl (DPPH) scavenging activity), was highest for poly-SUV emulsified nanoparticles (0.030 {+-} 0.002 mg ml{sup -1}) as compared to free TQ. In addition, it was observed that TQ-loaded nanoparticles emulsified with poly-SUV were more effective than free TQ against MDA-MB-231 cancer cell growth inhibition, presenting a cell viability of 16.0 {+-} 5.6% after 96 h.

  19. Air oxygenation chemistry of 4-TBC catalyzed by chloro bridged dinuclear copper(II) complexes of pyrazole based tridentate ligands: synthesis, structure, magnetic and computational studies.

    Science.gov (United States)

    Banerjee, Ishita; Samanta, Pabitra Narayan; Das, Kalyan Kumar; Ababei, Rodica; Kalisz, Marguerite; Girard, Adrien; Mathonière, Corine; Nethaji, M; Clérac, Rodolphe; Ali, Mahammad

    2013-02-01

    Four dinuclear bis(μ-Cl) bridged copper(II) complexes, [Cu(2)(μ-Cl)(2)(L(X))(2)](ClO(4))(2) (L(X) = N,N-bis[(3,5-dimethylpyrazole-1-yl)-methyl]benzylamine with X = H(1), OMe(2), Me(3) and Cl(4)), have been synthesized and characterized by the single crystal X-ray diffraction method. In these complexes, each copper(II) center is penta-coordinated with square-pyramidal geometry. In addition to the tridentate L(X) ligand, a chloride ion occupies the last position of the square plane. This chloride ion is also bonded to the neighboring Cu(II) site in its axial position forming an SP-I dinuclear Cu(II) unit that exhibits small intramolecular ferromagnetic interactions and supported by DFT calculations. The complexes 1-3 exhibit methylmonooxygenase (pMMO) behaviour and oxidise 4-tert-butylcatechol (4-TBCH(2)) with molecular oxygen in MeOH or MeCN to 4-tert-butyl-benzoquinone (4-TBQ), 5-methoxy-4-tert-butyl-benzoquinone (5-MeO-4-TBQ) as the major products along with 6,6'-Bu(t)-biphenyl-3,4,3',4'-tetraol and others as minor products. These are further confirmed by ESI- and FAB-mass analyses. A tentative catalytic cycle has been framed based on the mass spectral analysis of the products and DFT calculations on individual intermediates that are energetically feasible. PMID:23172025

  20. Delivery of phytochemical thymoquinone using molecular micelle modified poly(D, L lactide-co-glycolide) (PLGA) nanoparticles

    Science.gov (United States)

    Ganea, Gabriela M.; Fakayode, Sayo O.; Losso, Jack N.; van Nostrum, Cornelus F.; Sabliov, Cristina M.; Warner, Isiah M.

    2010-07-01

    Continuous efforts have been made in the development of potent benzoquinone-based anticancer drugs aiming for improved water solubility and reduced adverse reactions. Thymoquinone is a liposoluble benzoquinone-based phytochemical that has been shown to have remarkable antioxidant and anticancer activities. In the study reported here, thymoquinone-loaded PLGA nanoparticles were synthesized and evaluated for physico-chemical, antioxidant and anticancer properties. The nanoparticles were synthesized by an emulsion solvent evaporation method using anionic molecular micelles as emulsifiers. The system was optimized for maximum entrapment efficiency using a Box-Behnken experimental design. Optimum conditions were found for 100 mg PLGA, 15 mg TQ and 0.5% w/v poly(sodium N-undecylenyl-glycinate) (poly-SUG). In addition, other structurally related molecular micelles such as poly(sodium N-heptenyl-glycinate) (poly-SHG), poly(sodium N-undecylenyl-leucinate) (poly-SUL), and poly(sodium N-undecylenyl-valinate) (poly-SUV) were also examined as emulsifiers. All investigated molecular micelles provided excellent emulsifier properties, leading to maximum optimized TQ entrapment efficiency, and monodispersed particle sizes below 200 nm. The release of TQ from molecular micelle modified nanoparticles was investigated by dialysis and reached lower levels than the free drug. The antioxidant activity of TQ-loaded nanoparticles, indicated by IC50 (mg ml - 1 TQ for 50% 2,2-diphenyl-1-picrylhydrazyl (DPPH) scavenging activity), was highest for poly-SUV emulsified nanoparticles (0.030 ± 0.002 mg ml - 1) as compared to free TQ. In addition, it was observed that TQ-loaded nanoparticles emulsified with poly-SUV were more effective than free TQ against MDA-MB-231 cancer cell growth inhibition, presenting a cell viability of 16.0 ± 5.6% after 96 h.

  1. Hemizygosity of transsulfuration genes confers increased vulnerability against acetaminophen-induced hepatotoxicity in mice

    Energy Technology Data Exchange (ETDEWEB)

    Hagiya, Yoshifumi; Kamata, Shotaro; Mitsuoka, Saya; Okada, Norihiko; Yoshida, Saori; Yamamoto, Junya; Ohkubo, Rika [Department of Biochemistry, Keio University School of Pharmaceutical Sciences, Tokyo 105-8512 (Japan); Abiko, Yumi [Environmental Biology Laboratory, School of Medicine, University of Tsukuba, Ibaraki 305-8575 (Japan); Yamada, Hidenori [Jobu Hospital for Respiratory Diseases, Maebashi 371-0048 (Japan); Akahoshi, Noriyuki [Department of Immunology, Akita University Graduate School of Medicine, Akita 010-8543 (Japan); Kasahara, Tadashi [Department of Biochemistry, Keio University School of Pharmaceutical Sciences, Tokyo 105-8512 (Japan); Kumagai, Yoshito [Environmental Biology Laboratory, School of Medicine, University of Tsukuba, Ibaraki 305-8575 (Japan); Ishii, Isao, E-mail: isao-ishii@umin.ac.jp [Department of Biochemistry, Keio University School of Pharmaceutical Sciences, Tokyo 105-8512 (Japan)

    2015-01-15

    The key mechanism for acetaminophen hepatotoxicity is cytochrome P450 (CYP)-dependent formation of N-acetyl-p-benzoquinone imine, a potent electrophile that forms protein adducts. Previous studies revealed the fundamental role of glutathione, which binds to and detoxifies N-acetyl-p-benzoquinone imine. Glutathione is synthesized from cysteine in the liver, and N-acetylcysteine is used as a sole antidote for acetaminophen poisoning. Here, we evaluated the potential roles of transsulfuration enzymes essential for cysteine biosynthesis, cystathionine β-synthase (CBS) and cystathionine γ-lyase (CTH), in acetaminophen hepatotoxicity using hemizygous (Cbs{sup +/−} or Cth{sup +/−}) and homozygous (Cth{sup −/−}) knockout mice. At 4 h after intraperitoneal acetaminophen injection, serum alanine aminotransferase levels were highly elevated in Cth{sup −/−} mice at 150 mg/kg dose, and also in Cbs{sup +/−} or Cth{sup +/−} mice at 250 mg/kg dose, which was associated with characteristic centrilobular hepatocyte oncosis. Hepatic glutathione was depleted while serum malondialdehyde accumulated in acetaminophen-injected Cth{sup −/−} mice but not wild-type mice, although glutamate–cysteine ligase (composed of catalytic [GCLC] and modifier [GCLM] subunits) became more activated in the livers of Cth{sup −/−} mice with lower K{sub m} values for Cys and Glu. Proteome analysis using fluorescent two-dimensional difference gel electrophoresis revealed 47 differentially expressed proteins after injection of 150 mg acetaminophen/kg into Cth{sup −/−} mice; the profiles were similar to 1000 mg acetaminophen/kg-treated wild-type mice. The prevalence of Cbs or Cth hemizygosity is estimated to be 1:200–300 population; therefore, the deletion or polymorphism of either transsulfuration gene may underlie idiosyncratic acetaminophen vulnerability along with the differences in Cyp, Gclc, and Gclm gene activities. - Highlights: • Cbs{sup +/−}, Cth{sup +/−}, and

  2. Genes involved in degradation of para-nitrophenol are differentially arranged in form of non-contiguous gene clusters in Burkholderia sp. strain SJ98.

    Directory of Open Access Journals (Sweden)

    Surendra Vikram

    Full Text Available Biodegradation of para-Nitrophenol (PNP proceeds via two distinct pathways, having 1,2,3-benzenetriol (BT and hydroquinone (HQ as their respective terminal aromatic intermediates. Genes involved in these pathways have already been studied in different PNP degrading bacteria. Burkholderia sp. strain SJ98 degrades PNP via both the pathways. Earlier, we have sequenced and analyzed a ~41 kb fragment from the genomic library of strain SJ98. This DNA fragment was found to harbor all the lower pathway genes; however, genes responsible for the initial transformation of PNP could not be identified within this fragment. Now, we have sequenced and annotated the whole genome of strain SJ98 and found two ORFs (viz., pnpA and pnpB showing maximum identity at amino acid level with p-nitrophenol 4-monooxygenase (PnpM and p-benzoquinone reductase (BqR. Unlike the other PNP gene clusters reported earlier in different bacteria, these two ORFs in SJ98 genome are physically separated from the other genes of PNP degradation pathway. In order to ascertain the identity of ORFs pnpA and pnpB, we have performed in-vitro assays using recombinant proteins heterologously expressed and purified to homogeneity. Purified PnpA was found to be a functional PnpM and transformed PNP into benzoquinone (BQ, while PnpB was found to be a functional BqR which catalyzed the transformation of BQ into hydroquinone (HQ. Noticeably, PnpM from strain SJ98 could also transform a number of PNP analogues. Based on the above observations, we propose that the genes for PNP degradation in strain SJ98 are arranged differentially in form of non-contiguous gene clusters. This is the first report for such arrangement for gene clusters involved in PNP degradation. Therefore, we propose that PNP degradation in strain SJ98 could be an important model system for further studies on differential evolution of PNP degradation functions.

  3. Biochemical Characterization of 3-Methyl-4-nitrophenol Degradation in Burkholderia sp. Strain SJ98

    Science.gov (United States)

    Min, Jun; Lu, Yang; Hu, Xiaoke; Zhou, Ning-Yi

    2016-01-01

    Several strains have been reported to grow on 3-methyl-4-nitrophenol (3M4NP), the primary breakdown product of the excessively used insecticide fenitrothion. However, the microbial degradation of 3M4NP at molecular and biochemical levels remains unknown. Here, methyl-1,4-benzoquinone (MBQ) and methylhydroquinone (MHQ), rather than catechol proposed previously, were identified as the intermediates before ring cleavage during 3M4NP degradation by Burkholderia sp. strain SJ98. Real-time quantitative PCR analysis indicated that the pnpABA1CDEF cluster involved in para-nitrophenol (PNP) and 2-chloro-4-nitrophenol (2C4NP) catabolism was also likely responsible for 3M4NP degradation in this strain. Purified PNP 4-monooxygenase (PnpA) is able to catalyze the monooxygenation of 3M4NP to MBQ and exhibited an apparent Km value of 20.3 ± 2.54 μM for 3M4NP, and pnpA is absolutely necessary for the catabolism of 3M4NP by gene knock-out and complementation. PnpB, a 1,4-benzoquinone reductase catalyzes the reduction of MBQ to MHQ, and also found to enhance PnpA activity in vitro in the conversion of 3M4NP to MBQ. By sequential catalysis assays, PnpCD, PnpE, and PnpF were likely involved in the lower pathway of 3M4NP catabolism. Although NpcCD, NpcE, and NpcF are able to catalyze the sequential conversion of MHQ in vitro, these enzymes are unlikely involved in 3M4NP catabolism because their coding genes were not upregulated by 3M4NP induction in vivo. These results revealed that the enzymes involved in PNP and 2C4NP catabolism were also responsible for 3M4NP degradation in strain SJ98. This fills a gap in our understanding of the microbial degradation of 3M4NP at molecular and biochemical levels and also provides another example to illustrate the adaptive flexibility in microbial catabolism for structurally similar compounds. PMID:27252697

  4. Mesostructured Cu–Mn–Ce–O composites with homogeneous bulk composition for chlorobenzene removal: Catalytic performance and microactivation course

    Energy Technology Data Exchange (ETDEWEB)

    He, Chi, E-mail: chi_he@mail.xjtu.edu.cn [Department of Environmental Science and Engineering, School of Energy and Power Engineering, Xi' an Jiaotong University, Xi' an 710049 (China); Yu, Yanke [Key Lab of Urban Environment and Health, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021 (China); Shi, Jianwen [Center of Nanomaterials for Renewable Energy, State Key Laboratory of Electrical Insulation and Power Equipment, School of Electrical Engineering, Xi' an Jiaotong University, Xi' an 710049 (China); Shen, Qun [Research Center for Greenhouse Gases and Environmental Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210 (China); Chen, Jinsheng [Key Lab of Urban Environment and Health, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021 (China); Liu, Hongxia, E-mail: hxliu72@mail.xjtu.edu.cn [Department of Environmental Science and Engineering, School of Energy and Power Engineering, Xi' an Jiaotong University, Xi' an 710049 (China)

    2015-05-01

    Cu–Mn–Ce–O composites with enhanced surface area and developed mesoporosity were synthesized using a homogeneous coprecipitation (hcp) method, and were tested in the catalytic destruction of chlorobenzene (CB). X-ray diffraction (XRD), N{sub 2} adsorption/desorption, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction (H{sub 2}-TPR), temperature programmed desorption of CB/O{sub 2} (CB/O{sub 2}-TPD), and diffuse reflectance ultraviolet visible spectroscopy (DRUV-Vis) were used to characterize the structure and textural properties of catalysts. Mn and Cu enter CeO{sub 2} matrix with a fluorite-like structure, and produce large amounts of oxygen vacancies. Addition of manganese promotes the formation of reduced copper phase, and the presence of large numbers of high valence Mn{sup 4+} ions strongly enhances the redox couple of Cu{sup +}–Cu{sup 2+} in the composites. Both the synthesis protocol and metal doping amount significantly affect the catalyst reducibility, surface state and oxygen density. Cu{sub 0.15}Mn{sub 0.15}Ce{sub 0.85}O{sub x} synthesized via the hcp method exhibits the highest catalytic activity with 90% of chlorobenzene destructed at 255 °C (CO{sub 2} selectivity > 99.5%). Enriched surface oxygen, excellent active oxygen mobility and CB adsorption ability guarantee the superior activity and stability of Cu–Mn–Ce–O composite catalysts. Nucleophilic and electrophilic substitutions happen in sequence during chlorobenzene destruction, and the adsorbed Cl can be finally removed in the form of Cl{sub 2} via the Deacon reaction. Furthermore, the incorporation of CuO and MnO{sub x} phases can inhibit the formation of organic byproducts, such as phenolates, maleates, and o-benzoquinone-type species, especially at elevated reaction temperatures. - Highlights: • Cu–Mn–Ce–O mesoporous oxides possess enhanced surface oxygen

  5. Aqueous-phase chemistry and bactericidal effects from an air discharge plasma in contact with water: evidence for the formation of peroxynitrite through a pseudo-second-order post-discharge reaction of H2O2 and HNO2

    Science.gov (United States)

    Lukes, P.; Dolezalova, E.; Sisrova, I.; Clupek, M.

    2014-02-01

    The formation of transient species (OH·, NO2·, NO radicals) and long-lived chemical products (O3, H2O2, NO_{3}^{-} , NO_{2}^{-} ) produced by a gas discharge plasma at the gas-liquid interface and directly in the liquid was measured in dependence on the gas atmosphere (20% oxygen mixtures with nitrogen or with argon) and pH of plasma-treated water (controlled by buffers at pH 3.3, 6.9 or 10.1). The aqueous-phase chemistry and specific contributions of these species to the chemical and biocidal effects of air discharge plasma in water were evaluated using phenol as a chemical probe and bacteria Escherichia coli. The nitrated and nitrosylated products of phenol (4-nitrophenol, 2-nitrophenol, 4-nitrocatechol, 4-nitrosophenol) in addition to the hydroxylated products (catechol, hydroquinone, 1,4-benzoquinone, hydroxy-1,4-benzoquinone) evidenced formation of NO2·, NO· and OH· radicals and NO+ ions directly by the air plasma at the gas-liquid interface and through post-discharge processes in plasma-activated water (PAW) mediated by peroxynitrite (ONOOH). Kinetic study of post-discharge evolution of H2O2 and NO_{2}^{-} in PAW has demonstrated excellent fit with the pseudo-second-order reaction between H2O2 and NO_{2}^{-} . The third-order rate constant k = 1.1 × 103 M-2 s-1 for the reaction NO_{2}^{-} +H_{2}O_{2}+H^{+}\\to ONOOH+H_{2}O was determined in PAW at pH 3.3 with the rate of ONOOH formation in the range 10-8-10-9 M s-1. Peroxynitrite chemistry was shown to significantly participate in the antibacterial properties of PAW. Ozone presence in PAW was proved indirectly by pH-dependent degradation of phenol and detection of cis,cis-muconic acid, but contribution of ozone to the inactivation of bacteria by the air plasma was negligible.

  6. Combined atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and quartz crystal microbalance (QCM) studies of glucose oxidase (GOx) immobilised onto self-assembled monolayer on the gold film

    International Nuclear Information System (INIS)

    In fabrication of biosensors, self-assembled monolayers (SAM) are an attractive method of immobilising enzymes at electrode surface since it allows precise control over the amount and spatial distribution of the immobilized enzyme. The covalent attachment of glucose oxidase (GOx) to a carboxylic terminated SAM chemisorbed onto gold films was achieved via carbodiimide activation of the carboxylic acids to a reactive intermediate susceptible to nucleophilic attack by amines on free lysine chains of the enzyme. Atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and quartz crystal microbalance (QCM) measurements were used for characterisation of GOx modified gold surfaces. Tapping mode AFM studies have revealed that GOx molecules form slightly disordered arrays of pentagonal or hexagonal clusters. Observed features of immobilised GOx are distributed as a submonolayer on the SAM surface which has allowed visualisation of native and unfolded enzyme structure. The presence of the SAM and enzyme on the gold surface was detected by XPS spectroscopy. Spectra show typical peaks for the C 1s, O 1s and N 1s regions. A kinetic study of the adsorption of GOx onto activated SAM using in-situ QCM allowed determination the amount of immobilised GOx on the layer and consequently the optimal immobilisation conditions. Performance parameters of the biosensor such as sensitivity to glucose concentration as a function of enzyme loading were evaluated amperometrically using the redox mediator p-benzoquinone

  7. Bursting in the Belousov-Zhabotinsky Reaction added with Phenol in a Batch Reactor

    Energy Technology Data Exchange (ETDEWEB)

    Cadena, Ariel; Agreda, Jesus, E-mail: jaagredab@unal.edu.co [Departamento de Quimica, Facultad de Ciencias, Universidad Nacional de Colombia, Bogota (Colombia); Barragan, Daniel [Escuela de Quimica, Facultad de Ciencias, Universidad Nacional de Colombia, Medellin (Colombia)

    2013-12-01

    The classic Belousov-Zhabotinski reaction was modified by adding phenol as a second organic substrate that kinetically competes with the malonic acid in the reduction of Ce{sup 4+} to Ce{sup 3+} and in the removal of molecular bromine of the reaction mixture. The oscillating reaction of two substrates exhibited burst firing and an oscillatory period of long duration. Analysis of experimental data shows an increasing of the bursting phenomenon, with a greater spiking in the burst firing and with a longer quiescent state, as a function of the initial phenol concentration increase. It was hypothesized that the bursting phenomenon can be explained introducing a redox cycle between the reduced phenolic species (hydroxyphenols) and the oxidized ones (quinones). The hypothesis was experimentally and numerically tested and from the results it is possible to conclude that the bursting phenomenon exhibited by the oscillating reaction of two substrates is mainly driven by a p-di-hydroxy-benzene/p-benzoquinone redox cycle (author)

  8. 中药磨盘草的化学成分%Chemical constituents of Abutilon indicum ( L. ) Sweet

    Institute of Scientific and Technical Information of China (English)

    刘娜; 贾凌云; 孙启时

    2009-01-01

    目的 研究中药磨盘草的化学成分.方法 运用硅胶柱色谱及Sephadex LH-20柱色谱等方法分离磨盘草的化学成分,通过理化常数和1D-NMR等波谱数据鉴定化合物的结构.结果 从磨盘草中分离了7个化合物,鉴定了6个化合物,分别鉴定为:β-谷甾醇(β-sitosterol,1)、齐墩果酸(oleanic acid,2)、24R-5α豆甾烷-3,6-二酮((24R)-5α-stigmastane-3,6-dione,3)、胡萝卜苷(daucosterol,4)、2,6-二甲氧基对苯醌(2,6-dimethoxy-1,4-benzoquinone,5)、香草酸(vanillic acid,6),还有一个脂肪酸类成分.结论 化合物2-5均为首次从磨盘草中分得.

  9. Mononuclear non-heme iron(III) complexes of linear and tripodal tridentate ligands as functional models for catechol dioxygenases: Effect of -alkyl substitution on regioselectivity and reaction rate

    Indian Academy of Sciences (India)

    Mallayan Palaniandavar; Kusalendiran Visvaganesan

    2011-03-01

    Catechol dioxygenases are responsible for the last step in the biodegradation of aromatic molecules in the environment. The iron(II) active site in the extradiol-cleaving enzymes cleaves the C-C bond adjacent to the hydroxyl group, while the iron(III) active site in the intradiol-cleaving enzymes cleaves the C-C bond in between two hydroxyl groups. A series of mononuclear iron(III) complexes of the type [Fe(L)Cl3], where L is the linear -alkyl substituted bis(pyrid-2-ylmethyl)amine, -alkyl substituted -(pyrid-2-ylmethyl)ethylenediamine, linear tridentate 3N ligands containing imidazolyl moieties and tripodal ligands containing pyrazolyl moieties have been isolated and studied as structural and functional models for catechol dioxygenase enzymes. All the complexes catalyse the cleavage of catechols using molecular oxygen to afford both intra- and extradiol cleavage products. The rate of oxygenation depends on the solvent and the Lewis acidity of iron(III) center as modified by the sterically demanding -alkyl groups. Also, our studies reveal that stereo-electronic factors like the Lewis acidity of the iron(III) center and the steric demand of ligands, as regulated by the -alkyl substituents, determine the regioselectivity and the rate of dioxygenation. In sharp contrast to all these complexes, the pyrazole-containing tripodal ligand complexes yield mainly the oxidized product benzoquinone.

  10. Design of a mediated enzymatic fuel cell to generate power from renewable fuel sources.

    Science.gov (United States)

    Korkut, Seyda; Kilic, Muhammet Samet

    2016-01-01

    The present work reported a compartment-less enzymatic fuel cell (EFC) based on newly synthesized Poly(pyrrole-2-carboxylic acid-co-3-thiophene acetic acid) film containing glucose oxidase and laccase effectively wired by p-benzoquinone incorporated into the copolymer structure. The resulting system generated a power density of 18.8 µW/cm(2) with 30 mM of glucose addition at +0.94 V at room temperature. Improvements to maximize the power output were ensured with step-by-step optimization of electrode fabrication design and operational parameters for operating the system with renewable fuel sources. We demonstrated that the improved fuel cell could easily harvest glucose produced during photosynthesis to produce electrical energy in a simple, renewable and sustainable way by generating a power density of 10 nW/cm(2) in the plant leaf within 2 min. An EFC for the first time was successfully operated in municipal wastewater which contained glycolytic substances to generate electrical energy with a power output of 3.3 µW/cm(2).

  11. Sewage-sludge-derived carbonaceous materials for catalytic wet hydrogen peroxide oxidation of m-cresol in batch and continuous reactors.

    Science.gov (United States)

    Yu, Yang; Wei, Huangzhao; Yu, Li; Wang, Wei; Zhao, Ying; Gu, Bin; Sun, Chenglin

    2016-01-01

    In this study, four sewage-sludge-derived carbonaceous materials (SWs) were evaluated for their catalytic wet hydrogen peroxide oxidation (CWPO) performance of m-cresol in batch reactor and continuous reactor, respectively. The SWs were produced by carbonization (SW); carbonization with the addition of CaO (CaO-SW); HNO3 pretreatment (HNO3-SW) and steam activation (Activated-SW). The properties of SW catalysts were assessed by thermogravimetric analysis, Brunauer-Emmett-Teller, Fourier Transform Infrared Spectroscopy, X-ray Fluorescence, Scanning electron microscopy, energy dispersive X-ray analysis and zeta potential. The results showed that SW treated by HNO3 (HNO3-SW) had a high conversion of m-cresol in batch reactor and continuous reactor, respectively. Under the conditions of batch reaction (Cm-cresol = 100 mg L(-1), CH2O2 = 15.7 mmol L(-1), initial pH=7.0, 0.5 g L(-1) catalyst, 80°C, 180 min adsorption and 210 min oxidation), the conversion of m-cresol reached 100% and total organic carbon removal was 67.1%. It had a high catalytic activity and stability on the treatment of m-cresol in CWPO for more than 1100 h. Furthermore, a possible reaction mechanism for the oxidation of m-cresol to 2-methyl-p-benzoquinone by CWPO was proposed. PMID:26109374

  12. Photocatalytic degradation of 4-chlorophenol under P-modified TiO2/UV system: kinetics, intermediates, phytotoxicity and acute toxicity.

    Science.gov (United States)

    Elghniji, Kais; Hentati, Olfa; Mlaik, Najwa; Mahfoudh, Ayman; Ksibi, Mohamed

    2012-01-01

    A series of phosphorus-modified titanium dioxide samples with varying P/Ti atomic ratio were conveniently prepared via a conventional solgel route. The effects of phosphorus content and calcination temperature on the crystalline structure, grain growth, surface area, and the photocatalytic activity of P-modified TiO2 were investigated. The XRD results showed that P species slow down the particle growth of anatase and increase the anatase-to-rutile phase transformation temperature to more than 900 degrees C. Kinetic studies on the P-modified TiO2 to degraded 4-chlorophenol had found that the TP5(500) prepared by adopting a P/Ti atomic ratio equal to 0.05 and calcined at 500 degrees C had an apparent rate constant equal to 0.0075 min(-1), which is superior to the performance of a commercial photocatalyst Degussa P25 K(app) = 0.0045 min(-1) and of unmodified TiO2 (TP0(500)) K(app) = 0.0022 min(-1). From HPLC analyses, various hydroxylated intermediates formed during oxidation had been identified, including hydroquinone (HQ), benzoquinone (BQ) and (4CC) 4-chlorocatechol as main products. Phytotoxicity was assessed before and after irradiation against seed germination of tomato (Lycopersicon esculentum) whereas acute toxicity was assessed by using Folsomia candida as the test organism. Intermediates products were all less toxic than 4-chlorophenol and a significant removal of the overall toxicity was accomplished. PMID:22655362

  13. Electrodeposition of chitosan-glucose oxidase biocomposite onto Pt-Pb nanoparticles modified stainless steel needle electrode for amperometric glucose biosensor.

    Science.gov (United States)

    Guo, Meiqing; Fang, Haidong; Wang, Rui; Yang, Zhiqiang; Xu, Xinhua

    2011-08-01

    A glucose biosensor was fabricated by electrodepositing chitosan (CS)-glucose oxidase(GOD) biocomposite onto the stainless steel needle electrode (SSN electrode) modified by Pt-Pb nanoparticles (Pt-Pb/SSN electrode). Firstly, Pt-Pb nanoparticles were deposited onto the SSN electrode and then CS-GOD biocomposite was co-electrodeposited onto the Pt-Pb/SSN electrode in a mixed solution containing p-benzoquinone (p-BQ), CS and GOD. The electrochemical results showed that the Pt-Pb nanoparticles can accelerate the electron transfer and improve the effective surface area of the SSN electrode. As a result, the detection range of the proposed biosensor was from 0.03 to 9 mM with a current sensitivity of 0.4485 μA/mM and a response time of 15 s. The Michaelis constant value was calculated to be 4.9837 mM. The cell test results indicated that the electrodes have a low cytotoxicity. This work provided a suitable technology for the fabrication of the needle-type glucose biosensor. PMID:21671000

  14. Ultrasensitive electrochemical immunosensor employing glucose oxidase catalyzed deposition of gold nanoparticles for signal amplification.

    Science.gov (United States)

    Zhang, Jie; Pearce, Mark C; Ting, Boon Ping; Ying, Jackie Y

    2011-09-15

    This paper describes a novel enzymatic amplification strategy for ultrasensitive electrochemical immunosensing. This approach utilizes glucose oxidase for the enzymatic deposition of gold nanoparticles onto an indium tin oxide (ITO) electrode surface using a novel gold developer solution consisting of 20 mM of glucose, 20 mM of NaSCN, 0.5 M of p-benzoquinone (PBQ) and 1 mM of AuCl(4)(-) dissolved in 0.1 M of pH 7.5 phosphate buffer solution. The amount of gold deposited was quantified electrochemically by monitoring the reduction of gold oxide in an aqueous solution of 0.5 M of H(2)SO(4), which was correlated to the amount of antigens in the solution. The effectiveness of this strategy was demonstrated experimentally through the construction of an immunosensor for the detection of mouse IgG using a sandwich immunoassay in a linear dynamic range of 5 pg/ml to 50 ng/ml. A good mean apparent recovery in the range of 88-102% was obtained over the entire linear dynamic range of the sensor response in the serum samples. This suggested that the immunosensor would be useful for the testing of proteins in real clinical samples. PMID:21782410

  15. Widespread ability of fungi to drive quinone redox cycling for biodegradation.

    Science.gov (United States)

    Krueger, Martin C; Bergmann, Michael; Schlosser, Dietmar

    2016-06-01

    Wood-rotting fungi possess remarkably diverse extracellular oxidation mechanisms, including enzymes, such as laccase and peroxidases, and Fenton chemistry. The ability to biologically drive Fenton chemistry by the redox cycling of quinones has previously been reported to be present in both ecologically diverging main groups of wood-rotting basidiomycetes. Therefore, we investigated whether it is even more widespread among fungal organisms. Screening of a diverse selection of a total of 18 ascomycetes and basidiomycetes for reduction of the model compound 2,6-dimethoxy benzoquinone revealed that all investigated strains were capable of reducing it to its corresponding hydroquinone. In a second step, depolymerization of the synthetic polymer polystyrene sulfonate was used as a proxy for quinone-dependent Fenton-based biodegradation capabilities. A diverse subset of the strains, including environmentally ubiquitous molds, white-rot fungi, as well as peatland and aquatic isolates, caused substantial depolymerization indicative for the effective employment of quinone redox cycling as biodegradation tool. Our results may also open up new paths to utilize diverse fungi for the bioremediation of recalcitrant organic pollutants. PMID:27190290

  16. Acetaminophen/paracetamol: A history of errors, failures and false decisions.

    Science.gov (United States)

    Brune, K; Renner, B; Tiegs, G

    2015-08-01

    Acetaminophen/paracetamol is the most widely used drug of the world. At the same time, it is probably one of the most dangerous compounds in medical use, causing hundreds of deaths in all industrialized countries due to acute liver failure (ALF). Publications of the last 130 years found in the usual databases were analyzed. Personal contacts existed to renowned researchers having contributed to the medical use of paracetamol and its precursors as H.U. Zollinger, S. Moeschlin, U. Dubach, J. Axelrod and others. Further information is found in earlier reviews by Eichengrün, Rodnan and Benedek, Sneader, Brune; comp. references. The history of the discovery of paracetamol starts with an error (active against worms), continues with a false assumption (paracetamol is safer than phenacetin), describes the first side-effect 'epidemy' (phenacetin nephropathy, drug-induced interstitial nephritis) and ends with the discovery of second-generation problems due to the unavoidable production of a highly toxic metabolite of paracetamol N-acetyl-p-benzoquinone imine (NAPQI) that may cause not only ALF and kidney damage but also impaired development of the fetus and the newborn child. It appears timely to reassess the risk/benefit ratio of this compound. PMID:25429980

  17. Geldanamycin and its anti-cancer activities.

    Science.gov (United States)

    Fukuyo, Yayoi; Hunt, Clayton R; Horikoshi, Nobuo

    2010-04-01

    Geldanamycin is a benzoquinone ansamycin antibiotic that manifests anti-cancer activity through the inhibition of HSP90-chaperone function. The HSP90 molecular chaperone is expressed at high levels in a wide variety of human cancers including melanoma, leukemia, and cancers in colon, prostate, lung, and breast. In cancer cells dependent upon mutated and/or over-expressed oncogene proteins, HSP90 is thought to have a critical role in regulating the stability, folding, and activity of HSP90-associated proteins, so-called "client proteins". These client proteins include the growth-stimulating proteins and kinases that support malignant transformation. Recently, oncogenic activating BRAF mutants have been identified in variety of cancers where constitutive activation of the MEK/ERK MAPK signaling pathway is the key for tumorigenesis, and they have been shown to be client proteins for HSP90. Accordingly, HSP90 inhibition can suppress certain cancer-causing client proteins and therefore represents an important therapeutic target. The molecular mechanism underlying the anti-cancer effect of HSP90 inhibition is complicated. Geldanamycin and its derivatives have been shown to induce the depletion of mutationally-activated BRAF through several mechanisms. In this review, we will describe the HSP90-inhibitory mechanism, focusing on recent progress in understanding HSP90 chaperone structure-function relationships, the identification of new HSP90 client proteins and the development of HSP90 inhibitors for clinical applications.

  18. Mineralization of 4-Chlorophenol under Visible Light Irradiation in the Presence of Aluminum and Zinc Phthalocyaninesulfonates

    Institute of Scientific and Technical Information of China (English)

    许宜铭; 胡美琴; 陈祖栩; 曾冬云

    2003-01-01

    Photosensitized oxidation of 4-chlorophenol (4CP) by the title complexes (AIPcS and ZnPcS) in aerated aqueous solution uponvisible light irradiation(λ=450nm) has been investigated using methanol as a disassociating reagent.It is confirmed that the monomeric species of the sesitizer is more active than the corresponding dimer in singlet oxygen generation for 4CP oxidation.However,the monomer is also the main component found in the sensitlzer's photobleaching, In this reload, AIPcS is much more stable than ZnPcS, and the Dhotoble~hlno is observed to proceed via singlet and triplet oxygen, respectlvely.The final products of 4CP oxidation in alkaline solution are carbon dioxide and chloride ions.while at pH=7 and pH=3 the p-benzoquinone is the product.The temperature is found to have influence on both the photosensitized degradation of methyl orange and ZnPcS photobleaching,with an activation energy of 15.8 and 24.2kJ/mol,respectively.

  19. Formation of polychlorinated dibenzodioxins, benzenes and phenols from thermal degradation of 2-chlorophenol promoted by CuCl2

    Energy Technology Data Exchange (ETDEWEB)

    Visez, N.; Baillet, C.; Sawerysyn, J.P. [Lille-1 Univ. (France). Physicochimie des Processus de Combustion et de l' Atmosphere - UMR-CNRS

    2004-09-15

    processes of PCDD/Fs from chlorophenols as precursors. These investigations have shown that other organic byproducts, potentially toxic, could also be formed with PCDD/Fs. Born et al. have studied the formation of PCDD/Fs from isomers of monochlorophenol on model and real fly ashes using a fixed bed reactor. The reaction products observed were carbon monoxide, carbon dioxide, 2,4- dichlorophenol, 2,6-dichlorophenol, 2,4,6-trichlorophenol, PCDDs, monobenzofuran, polychlorodiphenylethers, polychlorobenzenes, methylene chloride and tetrachloroethylene. By investigating the PCDD/Fs formation from ortho-chlorinated phenols and copper chloride, Ryu and Mulholland have identified the following products: chlorophenols, chlorobenzenes, PCDD/Fs, tetrachloroethylene and benzoquinones Hell et al. have studied the reaction of 2,4,6-trichlorophenol on real and model fly ash using a fixed bed reactor. They have observed that polychlorobenzenes formation was favored when time and temperature were increased. This work is aimed at highlighting the organic compounds formed by thermal degradation of 2-chlorophenol (2CP) promoted by copper chloride using sealed tubes as closed reactors. It is clear that this experimental method is unrealistic when compared to conditions of industrial processes. However, it enables us to use residence times (from minutes to hours) long enough to get more informations on reactions pathways responsible for PCCD/Fs formation and degradation which would be difficult to obtain from experiments with much smaller residence times.

  20. Mechanism and kinetics of 2-chlorophenol decomposition using coupled ultrasound and electrocatalysis

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    A coupled ultrasound/electrocatalysis(US/EC) process was used to enhance the decomposition effi-ciency of organics.The synergetic kinetics and the mechanism of 2-chlorophenol(2-CP) decomposi-tion with coupled US/EC were studied.It was found that in a US/EC process 2-CP is attacked by active radicals(such as hydroxyl radicals) to form 2-chloro-p-benzoquinone,and the latter is oxidized to simple organic acids when the ring is opened.The enhancement factor expressed by the apparent rate constant of 2-CP decomposition with coupled US/EC is 1.324 at a current density of 20 mA·cm-2,an ultrasonic frequency of 20 kHz,an ultrasonic intensity of 0.27 W·cm-2,and a 2-CP initial concentration of 200 mg·L-1,which means that a synergetic effect exists.A model derived from Langmuir adsorption theory of solid surface and reaction kinetics equations can describe exactly the decomposition of 2-CP with coupled US/EC.The numerical values are in good agreement with the experimental data.The model parameters are associated with reaction conditions.

  1. Structural and Kinetic Analyses of Macrophage Migration Inhibitory Factor Active Site Interactions

    Energy Technology Data Exchange (ETDEWEB)

    Crichlow, G.; Lubetsky, J; Leng, L; Bucala, R; Lolis, E

    2009-01-01

    Macrophage migration inhibitory factor (MIF) is a secreted protein expressed in numerous cell types that counters the antiinflammatory effects of glucocorticoids and has been implicated in sepsis, cancer, and certain autoimmune diseases. Interestingly, the structure of MIF contains a catalytic site resembling the tautomerase/isomerase sites of microbial enzymes. While bona fide physiological substrates remain unknown, model substrates have been identified. Selected compounds that bind in the tautomerase active site also inhibit biological functions of MIF. It had previously been shown that the acetaminophen metabolite, N-acetyl-p-benzoquinone imine (NAPQI), covalently binds to the active site of MIF. In this study, kinetic data indicate that NAPQI inhibits MIF both covalently and noncovalently. The structure of MIF cocrystallized with NAPQI reveals that the NAPQI has undergone a chemical alteration forming an acetaminophen dimer (bi-APAP) and binds noncovalently to MIF at the mouth of the active site. We also find that the commonly used protease inhibitor, phenylmethylsulfonyl fluoride (PMSF), forms a covalent complex with MIF and inhibits the tautomerase activity. Crystallographic analysis reveals the formation of a stable, novel covalent bond for PMSF between the catalytic nitrogen of the N-terminal proline and the sulfur of PMSF with complete, well-defined electron density in all three active sites of the MIF homotrimer. Conclusions are drawn from the structures of these two MIF-inhibitor complexes regarding the design of novel compounds that may provide more potent reversible and irreversible inhibition of MIF.

  2. First enantiospecific syntheses of marine merosesquiterpenes neopetrosiquinones a and B: evaluation of biological activity.

    Science.gov (United States)

    Chayboun, Ikram; Boulifa, Ettahir; Mansour, Ahmed Ibn; Rodriguez-Serrano, Fernando; Carrasco, Esther; Alvarez, Pablo Juan; Chahboun, Rachid; Alvarez-Manzaneda, Enrique

    2015-05-22

    The first enantiospecific syntheses of neopetrosiquinones A (6) and B (7), two merosesquiterpenes isolated from the deep-water sponge Neopetrosia cf. proxima, from the labdane diterpene trans-communic acid (10) have been achieved. A key step of the synthetic sequence is the simultaneous aromatization of the C ring and the benzylic oxidation on C-7 of an advanced intermediate, mediated by the oxygen-DDQ system. The in vitro antiproliferative activities of neopetrosiquinone B (7) and of the synthetic intermediates 8 and 9 against human breast (MCF-7), lung (A-549), and colon (T-84) tumor cell lines have been assayed. The most potent was compound 9 (IC50 = 4.1 μM), which was twice as active as natural compound 7 (IC50 = 8.3 μM) against A-549 cells. In addition, the treatment with these compounds resulted in an induction of apoptosis. These findings indicate that the terpene benzoquinones reported here might be potentially useful as anticancer agents. PMID:25906329

  3. Photocatalytic degradation of 4-chlorophenol under P-modified TiO2/UV system: Kinetics, intermediates, phytotoxicity and acute toxicity

    Institute of Scientific and Technical Information of China (English)

    Kais Elghniji; Olfa Hentati; Najwa Mlaik; Ayman Mahfoudh; Mohamed Ksibi

    2012-01-01

    A series of phosphorus-modified titanium dioxide samples with varying P/Ti atomic ratio were conveniently prepared via a conventional solgel route.The effects of phosphorus content and calcination temperature on the crystalline structure,grain growth,surface area,and the photocatalytic activity of P-modified TiO2 were investigated.The XRD results showed that P species slow down the particle growth of anatase and increase the anatase-to-rutile phase transformation temperature to more than 900℃.Kinetic studies on the P-modified TiO2 to degraded 4-chlorophenol had found that the TP5500 prepared by adopting a P/Ti atomic ratio equal to 0.05 and calcined at 500℃ had an apparent rate constant equal to 0.0075 min-1,which is superior to the performance of a commercial photocatalyst Degussa P25 Kapp =0.0045 min-1 and of unmodified TiO2(TP(0)500)Kapp =0.0022 min-1.From HPLC analyses,various hydroxylated intermediates formed during oxidation had been identified,including hydroquinone(HQ),benzoquinone(BQ)and(4CC)4-chlorocatechol as main products.Phytotoxicity was assessed before and after irradiation against seed germination of tomato(Lycopersicon esculentum)whereas acute toxicity was assessed by using Folsomia candida as the test organism.Intermediates products were all less toxic than 4-chlorophenol and a significant removal of the overall toxicity was accomplished.

  4. Vanillic Acid Inhibits Inflammatory Pain by Inhibiting Neutrophil Recruitment, Oxidative Stress, Cytokine Production, and NFκB Activation in Mice.

    Science.gov (United States)

    Calixto-Campos, Cássia; Carvalho, Thacyana T; Hohmann, Miriam S N; Pinho-Ribeiro, Felipe A; Fattori, Victor; Manchope, Marília F; Zarpelon, Ana C; Baracat, Marcela M; Georgetti, Sandra R; Casagrande, Rubia; Verri, Waldiceu A

    2015-08-28

    Vanillic acid (1) is a flavoring agent found in edible plants and fruits. It is an oxidized form of vanillin. Phenolic compounds form a substantial part of plant foods used as antioxidants with beneficial biological activities. These compounds have received considerable attention because of their role in preventing human diseases. Especially, 1 presents antibacterial, antimicrobial, and chemopreventive effects. However, the mechanisms by which 1 exerts its anti-inflammatory effects in vivo are incompletely understood. Thus, the effect of 1 was evaluated in murine models of inflammatory pain. Treatment with 1 inhibited the overt pain-like behavior induced by acetic acid, phenyl-p-benzoquinone, the second phase of the formalin test, and complete Freund's adjuvant (CFA). Treatment with 1 also inhibited carrageenan- and CFA-induced mechanical hyperalgesia, paw edema, myeloperoxidase activity, and N-acetyl-β-D-glucosaminidase activity. The anti-inflammatory mechanisms of 1 involved the inhibition of oxidative stress, pro-inflammatory cytokine production, and NFκB activation in the carrageenan model. The present study demonstrated 1 presents analgesic and anti-inflammatory effects in a wide range of murine inflammation models, and its mechanisms of action involves antioxidant effects and NFκB-related inhibition of pro-inflammatory cytokine production. PMID:26192250

  5. Redetermined structure, inter-molecular inter-actions and absolute configuration of royleanone.

    Science.gov (United States)

    Fun, Hoong-Kun; Chantrapromma, Suchada; Salae, Abdul Wahab; Razak, Ibrahim Abdul; Karalai, Chatchanok

    2011-05-01

    The structure of the title diterpenoid, C(20)H(28)O(3), {systematic name: (4bS,8aS)-3-hy-droxy-2-isopropyl-4b,8,8-trimethyl-4b,5,6,7,8,8a,9,10-octa-hydro-phenanthrene-1,4-dione} is confirmed [Eugster et al. (1993 ▶). Private communication (refcode HACGUN). CCDC, Union Road, Cambridge] and its packing is now described. Its absolute structure was established by refinement against data collected with Cu radiation: the two stereogenic centres both have S configurations. One cyclo-hexane ring adopts a chair conformation whereas the other cyclo-hexane ring is in a half-chair conformation and the benzoquinone ring is slightly twisted. An intra-molecular O-H⋯O hydrogen bond generates an S(5) ring motif. In the crystal, mol-ecules are linked into chains along [010] by O-H⋯O hydrogen bonds and weak C-H⋯O inter-actions. The packing also features C⋯O [3.131 (3) Å] short contacts.

  6. Chemical constituents from Chirita longgangensis var. hongyao with inhibitory activity against porcine respiratory and reproductive syndrome virus

    Energy Technology Data Exchange (ETDEWEB)

    Su, Yao; Wang, Yue-Hu; Tan, Ying; Yang, Jun; Liu, Hong-Xin; Gu, Wei; Long, Chun-Lin, E-mail: long@mail.kib.ac.cn [Key Laboratory of Economic Plants and Biotechnology, Kunming Institute of Botany, Chinese Academy of Sciences (China); Bi, Jun-Long; Yin, Ge-Fen, E-mail: yingefen383@sohu.com [College of Animal Science and Technology, Yunnan Agricultural University (China)

    2012-10-15

    Two new quinonoids chiritalone A and B, and a new neolignan 7'E-4,9-dihydroxy- 3,3',5'-trimethoxy-8,4'-oxyneolign-7'-en-9'-al, along with known (-)-8-hydroxy-{alpha}-dunnione, digiferruginol, 2,5-dimethoxy-1,4-benzoquinone and hederagenin, were isolated from the stems of Chirita longgangensis var. hongyao. The structures of the new compounds were elucidated by detailed analysis from NMR (nuclear magnetic resonance) and MS (mass spectrometry) data, and the absolute configuration of chiritalone A was determined by single crystal X-ray diffraction analysis using the Flack parameter. The inhibitory activity of compounds against porcine respiratory and reproductive syndrome virus (PRRSV) was measured by the cytopathic effect (CPE) method. Digiferruginol and hederagenin showed weak effect on PRRSV with an IC{sub 50} value of 80.5 {+-} 16.9 {mu}mol L{sup -1} (SI = 19.9) and 43.2 {+-} 7.4 {mu}mol L{sup -1} (SI = 13.1), respectively. (author)

  7. Redetermined structure, intermolecular interactions and absolute configuration of royleanone

    Directory of Open Access Journals (Sweden)

    Hoong-Kun Fun

    2011-05-01

    Full Text Available The structure of the title diterpenoid, C20H28O3, {systematic name: (4bS,8aS-3-hydroxy-2-isopropyl-4b,8,8-trimethyl-4b,5,6,7,8,8a,9,10-octahydrophenanthrene-1,4-dione} is confirmed [Eugster et al. (1993. Private communication (refcode HACGUN. CCDC, Union Road, Cambridge] and its packing is now described. Its absolute structure was established by refinement against data collected with Cu radiation: the two stereogenic centres both have S configurations. One cyclohexane ring adopts a chair conformation whereas the other cyclohexane ring is in a half-chair conformation and the benzoquinone ring is slightly twisted. An intramolecular O—H...O hydrogen bond generates an S(5 ring motif. In the crystal, molecules are linked into chains along [010] by O—H...O hydrogen bonds and weak C—H...O interactions. The packing also features C...O [3.131 (3 Å] short contacts.

  8. Geldanamycin inhibits proliferation and motility of Her2/neu-overexpressing SK-Br3 breast cancer cells

    Institute of Scientific and Technical Information of China (English)

    Ren Yu; Wang Ke; He Jianjun; Chen Wuke; Ma Qingyong

    2008-01-01

    Objective Benzoquinone ansamycin antibiotic, geldanamycin (GA), is a new anticancer agent that could inhibit Hsp90 by occupying its NH2-terminal ATP-binding site. This study was to investigate the antitumor efficacy of GA on Her2/neu tyrosine kinase overexpressing human breast cancer cell line SKBr3. Methods The degradation of Her2/neu tyrosine kinase was analyzed by Western blotting, the proliferation index was determined by MTT assay,cell cycle distribution was detected by flow cytometry, Cyclin D1 mRNA transcription was measured by RT-PCR and real-time PCR, and cell motility was evaluated by the cell culture insert model. Results GA induced a dose- and a time-dependent degradation of the Her2/neu tyrosine kinase protein and concurrently, the inhibition of cancer cell proliferation. The antitumor effects mediated by GA included: GA treatment decreased the survival rates of cancer cells,and led to a dase-dependent G1 arrest. Furthermore, this antitumor effect was proved to be related to declined transcription of Cyclin D1. Concurrently, the motility of cancer cells was reduced by GA. Conclusion GA treatment could induce the degradation of Her2/neu tyrnsine kinase efficiently, inhibit cancer cell proliferation and reduce motility in Her2/nen tyrosine kinase overexpressed human breast cancer cell line SKBr3.

  9. Combining Research Projects for Organic Chemistry Teaching:Taking the Synthesis of Rubrene Derivatives as an Example%结合科研课题进行有机化学教学--以红荧烯衍生物的合成为例

    Institute of Scientific and Technical Information of China (English)

    刘涛; 夏宏宇; 杜荣斌; 孔学军; 徐衡

    2015-01-01

    红荧烯衍生物是一种新型功能性荧光材料,有着潜在的应用前景。以对苯醌为原料,经九步反应合成了红荧烯衍生物,其中涉及Diels-Alder反应、氧化、脱水、卤代、水解、亲核加成及缩合反应等。在教学中结合荧烯衍生物合成的实例,渗透到相关反应,拓宽了学生的视野,激发了学生对有机合成的兴趣,有较好的教学效果。%Rubrene derivatives are a kind of novel functional fluorescent materials, and have potential applications.P -benzoquinone as raw material, by nine-step reaction, rubrene derivatives were synthesized, which involves the Diels-Alder re-action, oxidation, dehydration, halogenation, hydrolysis, nucleophilic addition and condensation reactions, and so on.In organic chemistry teaching, combining with the examples of rubrene derivatives synthesis, penetration into related reactions broadened the students'vision,stimulated students'interest in organic synthesis and achieved better teaching effect.

  10. Study on Nitrogen Forms in Phenolic Polymers Incorporating Protien by 15N CP—MAS NMR

    Institute of Scientific and Technical Information of China (English)

    CHENGLILI; WENQIXIAO; 等

    1996-01-01

    Phenolic polymers synthesized by reactions by reactions of p-benzoquinone with 15N-labelled protein or (15NH4)2SO4 were studied by using 15N CP-MAS NMR technique in combination with chemical approaches.Results showed that more than 80% of nitrogen in quinone-protein polymers was in the form of amide with some present as aromatic and /or aliphatic amine and less than 10% of nitrogen occurred as heterocyclic N.The nitrogen distribution in the non-hydrolyzable residue of the quinone-protein polymers was basically similar to that of soil humic acid reported in literature with the exception that a higher proportion of N as heterocyclic N and aromatic amine and a lower proportion of N as amide and aliphatic amine were found in the former than in the latter,More than 70% of total nitrogen in quinone-(NH4)2OS4 polymer was acid resistant ,of which about 53% occurred as pyrrole,nitrile and imion type N.The possible roles of the reactions of phenols or quinones with proteins in the formation of humic acid.especially the non-hydrolyzable nitrogen in humicacid,are discussed.

  11. Thermal and Cure Kinetics of Epoxy Molding Compounds Cured with Thermal Latency Accelerators

    Directory of Open Access Journals (Sweden)

    Chean-Cheng Su

    2013-01-01

    Full Text Available The cure kinetics and mechanisms of a biphenyl type epoxy molding compounds (EMCs with thermal latency organophosphine accelerators were studied using differential scanning calorimetry (DSC. Although the use of triphenylphosphine-1,4-benzoquinone (TPP-BQ and triphenylphosphine (TPP catalysts in biphenyl type EMCs exhibited autocatalytic mechanisms, thermal latency was higher in the TPP-BQ catalyst in EMCs than in the TPP catalyst in EMCs. Analyses of thermal characteristics indicated that TPP-BQ is inactive at low temperatures. At high temperatures, however, TPP-BQ increases the curing rate of EMC in dynamic and isothermal curing experiments. The reaction of EMCs with the TPP-BQ latent catalyst also had a higher temperature sensitivity compared to the reaction of EMCs with TPP catalyst. In resin transfer molding, EMCs containing the TPP-BQ thermal latency accelerator are least active at a low temperature. Consequently, EMCs have a low melt viscosity before gelation, and the resins and filler are evenly mixed in the kneading process. Additionally, flowability is increased before the EMCs form a network structure in the molding process. The proposed kinetic model adequately describes curing behavior in EMCs cured with two different organophosphine catalysts up to the rubber state in the progress of curing.

  12. Ultra pressure liquid chromatography-negative electrospray ionization mass spectrometry determination of twelve halobenzoquinones at ng/L levels in drinking water.

    Science.gov (United States)

    Huang, Rongfu; Wang, Wei; Qian, Yichao; Boyd, Jessica M; Zhao, Yuli; Li, Xing-Fang

    2013-05-01

    We report here the characterization of twelve halobenzoquinones (HBQs) using electrospray ionization (ESI) high resolution quadrupole time-of-flight mass spectrometry. The high resolution negative ESI spectra of the twelve HBQs formed two parent ions, [M + H(+) + 2e(-)], and the radical M(-•). The intensities of these two parent ions are dependent on their chemical structures and on instrumental parameters such as the source temperature and flow rate. The characteristic ions of the HBQs were used to develop an ultra pressure liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method. At the UPLC flow rate (400 μL/min) and under the optimized ESI conditions, eleven HBQs showed the stable and abundant transitions [M + H(+) + 2e(-)] → X(-) (X(-) representing Cl(-), Br(-), or I(-)), while dibromo-dimethyl-benzoquinone (DBDMBQ) showed only the transition of M(-•) → Br(-). The UPLC efficiently separates all HBQs including some HBQ isomers, while the MS/MS offers exquisite limits of detection (LODs) at subng/mL levels for all HBQs except DBDMBQ. Combined with solid phase extraction (SPE), the method LOD is down to ng/L. The results from analysis of authentic samples demonstrated that the SPE-UPLC-MS/MS method is reliable, fast, and sensitive for the identification and quantification of the twelve HBQs in drinking water.

  13. 2D/2D nano-hybrids of γ-MnO₂ on reduced graphene oxide for catalytic ozonation and coupling peroxymonosulfate activation.

    Science.gov (United States)

    Wang, Yuxian; Xie, Yongbing; Sun, Hongqi; Xiao, Jiadong; Cao, Hongbin; Wang, Shaobin

    2016-01-15

    Two-dimensional reduced graphene oxide (2D rGO) was employed as both a shape-directing medium and support to fabricate 2D γ-MnO2/2D rGO nano-hybrids (MnO2/rGO) via a facile hydrothermal route. For the first time, the 2D/2D hybrid materials were used for catalytic ozonation of 4-nitrophenol. The catalytic efficiency of MnO2/rGO was much higher than either MnO2 or rGO only, and rGO was suggested to play the role for promoting electron transfers. Quenching tests using tert-butanol, p-benzoquinone, and sodium azide suggested that the major radicals responsible for 4-nitrophenol degradation and mineralization are O2(-) and (1)O2, but not ·OH. Reusability tests demonstrated a high stability of the materials in catalytic ozonation with minor Mn leaching below 0.5 ppm. Degradation mechanism, reaction kinetics, reusability and a synergistic effect between catalytic ozonation and coupling peroxymonosulfate (PMS) activation were also discussed.

  14. Bioassay-guided evaluation of anti-inflammatory and antinociceptive activities of pistachio, Pistacia vera L.

    Science.gov (United States)

    Orhan, I; Küpeli, E; Aslan, M; Kartal, M; Yesilada, E

    2006-04-21

    The ethanolic and aqueous extracts prepared from different parts of Pistacia vera L. (Anacardiaceae) as well as its oleoresin were evaluated for their in vivo anti-inflammatory and antinociceptive activities. Among the extracts screened, only the oleoresin was shown to possess a marked anti-inflammatory activity against carrageenan-induced hind paw edema model in mice without inducing any gastric damage at both 250 and 500 mg/kg doses whereas the rest of the extracts were totally inactive. While the oleoresin was found to display significant antinociceptive activity at 500 mg/kg dose, the ethanolic and aqueous extracts belonging to fruit, leaf, branch and peduncle of Pistacia vera did not exhibit any noticeable antinociception in p-benzoquinone-induced abdominal contractions in mice. Fractionation of the oleoresin indicated the n-hexane fraction to be active, which further led to recognition of some monoterpenes, mainly alpha-pinene (77.5%) by capillary gas chromatography-mass spectrometry (GC-MS) as well as the oleoresin itself. alpha-Pinene was also assessed for its antinociceptive and anti-inflammatory activities in the same manner and exerted a moderate anti-inflammatory effect at 500 mg/kg dose.

  15. Methyltransferase activity assay based on the use of exonuclease III, the hemin/G-quadruplex system and reduced graphene oxide on a gold electrode, and a study on enzyme inhibition

    International Nuclear Information System (INIS)

    We describe an electrochemical bioassay for the detection of the activity of methyltransferase (MTase), and for screening this enzyme’s inhibitors. The assay is based on the conjugation of a hemin to a G-quadruplex that enables enzymatic signal amplification with the aid of exonuclease III (ExoIII). In the first step, double-stranded DNA containing the quadruplex-forming oligomer is assembled on the surface of a gold electrode and then methylated by DNA adenine methyltransferase (DAM). After cleaved by endonuclease DpnI, the methylated DNA is digested by ExoIII and the quadruplex-forming oligomers are liberated. This leads to the formation of a hemin/G-quadruplex (in presence of hemin and of potassium ions). The hemin/G-quadruplex catalyzes the oxidization of hydroquinone by H2O2 and the benzoquinone was formed to generate electrochemical signal. Finally, the gold electrode modified with reduced graphene oxide was used as working electrode for performing differential pulse voltammetry. The method has a detection limit of 0.31 unit · mL−1. A study on the inhibition of MTase showed it was inhibited by epicatechin with an IC50 value of 157 μM. (author)

  16. Formation of hydrogen peroxide and degradation of phenol in synergistic system of pulsed corona discharge combined with TiO2 photocatalysis.

    Science.gov (United States)

    Wang, Huijuan; Li, Jie; Quan, Xie; Wu, Yan; Li, Guofeng; Wang, Fangzheng

    2007-03-01

    In the present work, a synergistic system of pulsed corona discharge combined with TiO(2) photocatalysis has been developed to investigate the degradation rate of phenol solutions by varying experimental conditions of gas bubbling varieties (air, O(2), and Ar), solution pH values, and radical scavenger additives. The hydrogen peroxide (H(2)O(2)) concentration, which indicated the amount of hydroxyl radicals (OH) in the reaction system under different conditions of gas bubbling varieties and scavenger species, was also reviewed. The obtained results revealed that degradation efficiency of phenol could be increased by the addition of TiO(2) in pulsed discharge system. The gas of Ar and O(2) bubbled into the reaction system was found to be favorable for phenol degradation and H(2)O(2) formation. Both in air bubbling and in O(2) bubbling reaction system, the higher degradation rate of phenol occurred in the case of acidic solution. The addition of sodium carbonate or n-butanol in the solution displayed a negative effect for phenol removal, while the H(2)O(2) concentration showed different changing trend by adding different radical scavengers. The most effective degradation of the three main intermediates of catechol, 1,4-hydroquinone, and 1,4-benzoquinone formed during phenol decomposition existed in the synergistic system of pulsed corona discharge and TiO(2) photocatalysis bubbled with O(2). PMID:16920259

  17. Evaluation of the potential of soil remediation by direct multi-channel pulsed corona discharge in soil.

    Science.gov (United States)

    Wang, Tie Cheng; Qu, Guangzhou; Li, Jie; Liang, Dongli

    2014-01-15

    A novel approach, named multi-channel pulsed corona discharge in soil, was developed for remediating organic pollutants contaminated soil, with p-nitrophenol (PNP) as the model pollutant. The feasibility of PNP degradation in soil was explored by evaluating effects of pulse discharge voltage, air flow rate and soil moisture on PNP degradation. Based on roles of chemically active species and evolution of degradation intermediates, PNP degradation processes were discussed. Experimental results showed that about 89.4% of PNP was smoothly degraded within 60min of discharge treatment at pulse discharge voltage 27kV, soil moisture 5% and air flow rate 0.8Lmin(-1), and the degradation process fitted the first-order kinetic model. Increasing pulse discharge voltage was found to be favorable for PNP degradation, but not for energy yield. There existed appropriate air flow rate and soil moisture for obtaining gratifying PNP degradation efficacy. Roles of radical scavenger and measurement of active species suggested that ozone, H2O2, and OH radicals played very important roles in PNP degradation. CN bond in PNP molecule was cleaved, and the main intermediate products such as hydroquinone, benzoquinone, catechol, phenol, acetic acid, formic acid, oxalic acid, NO2(-) and NO3(-) were identified. Possible pathway of PNP degradation in soil in such a system was proposed. PMID:24295768

  18. Enrichment of humic material with hydroxybenzene moieties intensifies its physiological effects on the nematode Caenorhabditis elegans.

    Science.gov (United States)

    Menzel, Ralph; Menzel, Stefanie; Tiedt, Sophie; Kubsch, Georg; Stösser, Reinhardt; Bährs, Hanno; Putschew, Anke; Saul, Nadine; Steinberg, Christian E W

    2011-10-15

    Dissolved humic substances are taken up by organisms and interact on various molecular and biochemical levels. In the nematode Caenorhabditis elegans, such material can promote longevity and increase its reproductive capacity; moreover, the worms tend to stay for longer in humic-enriched environments. Here, we tested the hypothesis that the chemical enrichment of humic substances with hydroxybenzene moieties intensifies these physiological effects. Based on the leonardite humic acid HuminFeed (HF), we followed a polycondensation reaction in which this natural humic substance and a dihydroxybenzene (hydroquinone or benzoquinone) served as reaction partners. Several analytical methods showed the formation of the corresponding copolymers. The chemical modification boosted the antioxidant properties of HF both in vitro and in vivo. Humic substances enriched with hydroxybenzene moieties caused a significantly increased tolerance to thermal stress in C. elegans and extended its lifespan. Exposed nematodes showed delayed linear growth and onset of reproduction and a stronger pumping activity of the pharynx. Thus, treated nematodes act younger than they really are. In this feature the modified HF replicated the biological impact of hydroquinone-homopolymers and various plant polyphenol monomers, thereby supporting the hydroxybenzene moieties of humic substances as major effective structures for the physiological effects observed in C. elegans. PMID:21902274

  19. Geldanamycin induces production of heat shock protein 70 and partially attenuates ototoxicity caused by gentamicin in the organ of Corti explants

    Directory of Open Access Journals (Sweden)

    Haupt Heidemarie

    2009-09-01

    Full Text Available Abstract Background Heat shock protein 70 (HSP70 protects inner ear cells from damage and death induced by e.g. heat or toxins. Benzoquinone ansamycin antibiotic geldanamycin (GA was demonstrated to induce the expression of HSP70 in various animal cell types. The aim of our study was to investigate whether GA induces HSP70 in the organ of Corti (OC, which contains the auditory sensory cells, and whether GA can protect these cells from toxicity caused by a common aminoglycoside antibiotic gentamicin. Methods To address these questions, we used the OC explants isolated from p3-p5 rats. As a read-out, we used RT-PCR, ELISA and immunofluorescence. Results We found that GA at the concentration of 2 μM efficiently induced HSP70 expression on mRNA and protein level in the OC explants. Confocal microscopy revealed that HSP70 induced by GA is expressed by hair cells and interdental cells of spiral limbus. Preincubation of explants with 2 μM GA prior to adding gentamicin (500 μM significantly reduced the loss of outer but not inner hair cells, suggesting different mechanisms of otoprotection needed for these two cell types. Conclusion GA induced HSP70 in the auditory sensory cells and partially protected them from toxicity of gentamicin. Understanding the molecular mechanisms of GA otoprotection may provide insights for preventative therapy of the hearing loss caused by aminoglycoside antibiotics.

  20. On the Catalytic Effect of Water in the Intramolecular Diels–Alder Reaction of Quinone Systems: A Theoretical Study

    Directory of Open Access Journals (Sweden)

    Jorge Soto-Delgado

    2012-11-01

    Full Text Available The mechanism of the intramolecular Diels–Alder (IMDA reaction of benzoquinone 1, in the absence and in the presence of three water molecules, 1w, has been studied by means of density functional theory (DFT methods, using the M05-2X and B3LYP functionals for exploration of the potential energy surface (PES. The energy and geometrical results obtained are complemented with a population analysis using the NBO method, and an analysis based on the global, local and group electrophilicity and nucleophilicity indices. Both implicit and explicit solvation emphasize the increase of the polarity of the reaction and the reduction of activation free energies associated with the transition states (TSs of this IMDA process. These results are reinforced by the analysis of the reactivity indices derived from the conceptual DFT, which show that the increase of the electrophilicity of the quinone framework by the hydrogen-bond formation correctly explains the high polar character of this intramolecular process. Large polarization at the TSs promoted by hydrogen-bonds and implicit solvation by water together with a high electrophilicity-nucleophilicity difference consistently explains the catalytic effects of water molecules.

  1. Oxidation and nitration of mononitrophenols by a DyP-type peroxidase.

    Science.gov (United States)

    Büttner, Enrico; Ullrich, René; Strittmatter, Eric; Piontek, Klaus; Plattner, Dietmar A; Hofrichter, Martin; Liers, Christiane

    2015-05-15

    Substantial conversion of nitrophenols, typical high-redox potential phenolic substrates, by heme peroxidases has only been reported for lignin peroxidase (LiP) so far. But also a dye-decolorizing peroxidase of Auricularia auricula-judae (AauDyP) was found to be capable of acting on (i) ortho-nitrophenol (oNP), (ii) meta-nitrophenol (mNP) and (iii) para-nitrophenol (pNP). The pH dependency for pNP oxidation showed an optimum at pH 4.5, which is typical for phenol conversion by DyPs and other heme peroxidases. In the case of oNP and pNP conversion, dinitrophenols (2,4-DNP and 2,6-DNP) were identified as products and for pNP additionally p-benzoquinone. Moreover, indications were found for the formation of random polymerization products originating from initially formed phenoxy radical intermediates. Nitration was examined using (15)N-labeled pNP and Na(14)NO2 as an additional source of nitro-groups. Products were identified by HPLC-MS, and mass-to-charge ratios were evaluated to clarify the origin of nitro-groups. The additional nitrogen in DNPs formed during enzymatic conversion was found to originate both from (15)N-pNP and (14)NO2Na. Based on these results, a hypothetical reaction scheme and a catalytically responsible confine of the enzyme's active site are postulated. PMID:25796533

  2. Coenzyme Q Biosynthesis: Evidence for a Substrate Access Channel in the FAD-Dependent Monooxygenase Coq6.

    Directory of Open Access Journals (Sweden)

    Alexandre Ismail

    2016-01-01

    Full Text Available Coq6 is an enzyme involved in the biosynthesis of coenzyme Q, a polyisoprenylated benzoquinone lipid essential to the function of the mitochondrial respiratory chain. In the yeast Saccharomyces cerevisiae, this putative flavin-dependent monooxygenase is proposed to hydroxylate the benzene ring of coenzyme Q (ubiquinone precursor at position C5. We show here through biochemical studies that Coq6 is a flavoprotein using FAD as a cofactor. Homology models of the Coq6-FAD complex are constructed and studied through molecular dynamics and substrate docking calculations of 3-hexaprenyl-4-hydroxyphenol (4-HP6, a bulky hydrophobic model substrate. We identify a putative access channel for Coq6 in a wild type model and propose in silico mutations positioned at its entrance capable of partially (G248R and L382E single mutations or completely (a G248R-L382E double-mutation blocking access to the channel for the substrate. Further in vivo assays support the computational predictions, thus explaining the decreased activities or inactivation of the mutated enzymes. This work provides the first detailed structural information of an important and highly conserved enzyme of ubiquinone biosynthesis.

  3. Synthetic Phenolic Antioxidants and Their Metabolites in Indoor Dust from Homes and Microenvironments.

    Science.gov (United States)

    Wang, Wei; Asimakopoulos, Alexandros G; Abualnaja, Khalid O; Covaci, Adrian; Gevao, Bondi; Johnson-Restrepo, Boris; Kumosani, Taha A; Malarvannan, Govindan; Minh, Tu Binh; Moon, Hyo-Bang; Nakata, Haruhiko; Sinha, Ravindra K; Kannan, Kurunthachalam

    2016-01-01

    Synthetic phenolic antioxidants (SPAs), including 2,6-di-tert-butyl-4-hydroxytoluene (BHT), are extensively used in food, cosmetic and plastic industries. Nevertheless, limited information is available on human exposures, other than the dietary sources, to SPAs. In this study, occurrence of 9 SPAs and their metabolites/degradation products was determined in 339 indoor dust collected from 12 countries. BHT was found in 99.5% of indoor dust samples from homes and microenvironments at concentrations that ranged from BHT metabolites in house dust (0.01-35.1 μg/g) and their concentrations accounted for 9.2-58% of the sum concentrations (∑SPAs). 3,5-di-tert-butyl-4-hydroxybenzaldehyde (BHT-CHO), 2,6-di-tert-butyl-4-(hydroxymethyl)phenol (BHT-OH), 2,6-di-tert-butyl-1,4-benzoquinone (BHT-Q) were the major derivatives of BHT found in dust samples. The concentrations of gallic acid esters (gallates) in dust from homes and microenvironments ranged from BHT via house dust ingestion ranged from 0.40 to 222 ng/kg/d (95th percentile). PMID:26629709

  4. Pyranose Dehydrogenase from Agaricus campestris and Agaricus xanthoderma: Characterization and Applications in Carbohydrate Conversions

    Directory of Open Access Journals (Sweden)

    Clemens K. Peterbauer

    2013-08-01

    Full Text Available Pyranose dehydrogenase (PDH is a flavin-dependent sugar oxidoreductase that is limited to a rather small group of litter-degrading basidiomycetes. The enzyme is unable to utilize oxygen as an electron acceptor, using substituted benzoquinones and (organo metal ions instead. PDH displays a broad substrate specificity and intriguing variations in regioselectivity, depending on substrate, enzyme source and reaction conditions. In contrast to the related enzyme pyranose 2-oxidase (POx, PDHs from several sources are capable of oxidizing α- or β-1→4-linked di- and oligosaccharides, including lactose. PDH from A. xanthoderma is able to perform C-1 and C-2 oxidation, producing, in addition to lactobionic acid, 2-dehydrolactose, an intermediate for the production of lactulose, whereas PDH from A. campestris oxidizes lactose nearly exclusively at the C-1 position. In this work, we present the isolation of PDH-encoding genes from A. campestris (Ac and A. xanthoderma (Ax and a comparison of other so far isolated PDH-sequences. Secretory overexpression of both enzymes in Pichia pastoris was successful when using their native signal sequences with yields of 371 U·L−1 for AxPDH and 35 U·L−1 for AcPDH. The pure enzymes were characterized biochemically and tested for applications in carbohydrate conversion reactions of industrial relevance.

  5. Crystal structures of Pseudomonas syringae pv. tomato DC3000 quinone oxidoreductase and its complex with NADPH

    Energy Technology Data Exchange (ETDEWEB)

    Pan, Xiaowei [National Laboratory of Biomacromolecules, Institute of Biophysics, Chinese Academy of Sciences, 15 Datun Road, Chaoyang District, Beijing 100101 (China); Graduate University of the Chinese Academy of Sciences, Beijing 100049 (China); Zhang, Hongmei; Gao, Yu; Li, Mei [National Laboratory of Biomacromolecules, Institute of Biophysics, Chinese Academy of Sciences, 15 Datun Road, Chaoyang District, Beijing 100101 (China); Chang, Wenrui, E-mail: wrchang@sun5.ibp.ac.cn [National Laboratory of Biomacromolecules, Institute of Biophysics, Chinese Academy of Sciences, 15 Datun Road, Chaoyang District, Beijing 100101 (China)

    2009-12-18

    Zeta-crystallin-like quinone oxidoreductase is NAD(P)H-dependent and catalyzes one-electron reduction of certain quinones to generate semiquinone. Here we present the crystal structures of zeta-crystallin-like quinone oxidoreductase from Pseudomonas syringae pv. tomato DC3000 (PtoQOR) and its complexes with NADPH determined at 2.4 and 2.01 A resolutions, respectively. PtoQOR forms as a homologous dimer, each monomer containing two domains. In the structure of the PtoQOR-NADPH complex, NADPH locates in the groove between the two domains. NADPH binding causes obvious conformational changes in the structure of PtoQOR. The putative substrate-binding site of PtoQOR is wider than that of Escherichia coli and Thermus thermophilus HB8. Activity assays show that PtoQOR has weak 1,4-benzoquinone catalytic activity, and very strong reduction activity towards large substrates such as 9,10-phenanthrenequinone. We propose a model to explain the conformational changes which take place during reduction reactions catalyzed by PtoQOR.

  6. Old treatments for new insights and strategies: proposed management in adults and children with alkaptonuria.

    Science.gov (United States)

    Arnoux, Jean-Baptiste; Le Quan Sang, Kim-Hanh; Brassier, Anais; Grisel, Coraline; Servais, Aude; Wippf, Julien; Dubois, Sandrine; Sireau, Nicolas; Job-Deslandre, Chantal; Ranganath, Lakshminarayan; de Lonlay, Pascale

    2015-09-01

    Alkaptonuria (AKU) is caused by deficiency of the enzyme homogentisate 1,2 dioxygenase. It results in an accumulation of homogentisate which oxidizes spontaneously to benzoquinone acetate, a highly oxidant compound, which polymerises to a melanin-like structure, in a process called ochronosis. Asymptomatic during childhood, this accumulation will lead from the second decade of life to a progressive and severe spondylo-arthopathy, associated with multisystem involvement: osteoporosis/fractures, stones (renal, prostatic, gall bladder, salivary glands), ruptures of tendons/muscle/ligaments, renal failure and aortic valve disease. The pathophysiological mechanisms of AKU remain poorly understood, but recent advances lead us to reconsider the treatment strategy in AKU patients. Besides the supporting therapies (pain killers, anti-inflammatory drugs, physiotherapy, joints replacements and others), specific therapies have been considered (anti-oxidant, low protein diet, nitisinone), but clinical studies have failed to prove efficiency on the rheumatological lesions of the disease. Here we propose a treatment strategy for children and adults with AKU, based on a review of the latest findings on AKU and lessons from other aminoacipathies, especially tyrosinemias. PMID:25860819

  7. Artemisinin inhibits chloroplast electron transport activity: mode of action.

    Directory of Open Access Journals (Sweden)

    Adyasha Bharati

    Full Text Available Artemisinin, a secondary metabolite produced in Artemisia plant species, besides having antimalarial properties is also phytotoxic. Although, the phytotoxic activity of the compound has been long recognized, no information is available on the mechanism of action of the compound on photosynthetic activity of the plant. In this report, we have evaluated the effect of artemisinin on photoelectron transport activity of chloroplast thylakoid membrane. The inhibitory effect of the compound, under in vitro condition, was pronounced in loosely and fully coupled thylakoids; being strong in the former. The extent of inhibition was drastically reduced in the presence of uncouplers like ammonium chloride or gramicidin; a characteristic feature described for energy transfer inhibitors. The compound, on the other hand, when applied to plants (in vivo, behaved as a potent inhibitor of photosynthetic electron transport. The major site of its action was identified to be the Q(B; the secondary quinone moiety of photosystemII complex. Analysis of photoreduction kinetics of para-benzoquinone and duroquinone suggest that the inhibition leads to formation of low pool of plastoquinol, which becomes limiting for electron flow through photosystemI. Further it was ascertained that the in vivo inhibitory effect appeared as a consequence of the formation of an unidentified artemisinin-metabolite rather than by the interaction of the compound per se. The putative metabolite of artemisinin is highly reactive in instituting the inhibition of photosynthetic electron flow eventually reducing the plant growth.

  8. Characterization of platinum-iron catalysts supported on MCM-41 synthesized with rice husk silica and their performance for phenol hydroxylation

    International Nuclear Information System (INIS)

    Mesoporous material RH-MCM-41 was synthesized with rice husk silica by a hydrothermal method. It was used as a support for bimetallic platinum-iron catalysts Pt-Fe/RH-MCM-41 for phenol hydroxylation. The catalysts were prepared by co-impregnation with Pt and Fe at amounts of 0.5 and 5.0 wt.%, respectively. The RH-MCM-41 structure in the catalysts was studied with x-ray diffraction, and their surface areas were determined by nitrogen adsorption. The oxidation number of Fe supported on RH-MCM-41 was + 3, as determined by x-ray absorption near edge structure (XANES) analysis. Transmission electron microscopy (TEM) images of all the catalysts displayed well-ordered structures, and metal nanoparticles were observed in some catalysts. All the catalysts were active for phenol hydroxylation using H2O2 as the oxidant at phenol : H2O2 mole ratios of 2 : 1, 2 : 2, 2 : 3 and 2 : 4. The first three ratios produced only catechol and hydroquinone, whereas the 2 : 4 ratio also produced benzoquinone. The 2 : 3 ratio gave the highest phenol conversion of 47% at 70 deg. C. The catalyst prepared by co-impregnation with Pt and Fe was more active than that prepared using a physical mixture of Pt/RH-MCM-41 and Fe/RH-MCM-41.

  9. Fotodegradasi Fenol dengan Katalis Titanium Oksida dan Tinanium Silikat Mesopori- Mesostruktur

    Directory of Open Access Journals (Sweden)

    ARISWAN

    2006-11-01

    Full Text Available The objective of this research is to study the fotodegradation of phenol by titanium dioxide and titanium silicate mesoporous-mesostructure accelerated by hydrogen peroxide (H2O2. Photodegradations were carried out in stirred slurries of mesoporous-mesostructure titanium dioxide and titanium silicate: 0.15 g TiO2-layered macrostructure, 0.35 g TiO2/MCM-41 and 0,5 g Ti-MCM-41 in deionized water respectively. Phenol solution (0,5 g/L was illuminated by 160 W from mercury lamp at times various: 20, 40, 60 and 80 minute. The results show that TiO2-layered mesostructure followed by TiO2/MCM-41 are the two most active photocatalyst, while Ti- MCM-41 is not active photocatalyst. Organic substances produced from phenol fotodegradation include phenol → p-benzoquinon, hydroquinon → catecol → maleic acid → acetic acid and formic acid → water and carbon dioxide.

  10. Characterization of platinum–iron catalysts supported on MCM-41 synthesized with rice husk silica and their performance for phenol hydroxylation

    Directory of Open Access Journals (Sweden)

    Jitlada Chumee, Nurak Grisdanurak, Arthit Neramittagapong and Jatuporn Wittayakun

    2009-01-01

    Full Text Available Mesoporous material RH-MCM-41 was synthesized with rice husk silica by a hydrothermal method. It was used as a support for bimetallic platinum−iron catalysts Pt–Fe/RH-MCM-41 for phenol hydroxylation. The catalysts were prepared by co-impregnation with Pt and Fe at amounts of 0.5 and 5.0 wt.%, respectively. The RH-MCM-41 structure in the catalysts was studied with x-ray diffraction, and their surface areas were determined by nitrogen adsorption. The oxidation number of Fe supported on RH-MCM-41 was + 3, as determined by x-ray absorption near edge structure (XANES analysis. Transmission electron microscopy (TEM images of all the catalysts displayed well-ordered structures, and metal nanoparticles were observed in some catalysts. All the catalysts were active for phenol hydroxylation using H2O2 as the oxidant at phenol : H2O2 mole ratios of 2 : 1, 2 : 2, 2 : 3 and 2 : 4. The first three ratios produced only catechol and hydroquinone, whereas the 2 : 4 ratio also produced benzoquinone. The 2 : 3 ratio gave the highest phenol conversion of 47% at 70 °C. The catalyst prepared by co-impregnation with Pt and Fe was more active than that prepared using a physical mixture of Pt/RH-MCM-41 and Fe/RH-MCM-41.

  11. Solvent Effects on the Photophysicochemical Properties of Tetra(tert-butylphenoxy)phthalocyaninato Zinc(Ⅱ)%ZnTBPPc光物理化学性质的溶剂化效应

    Institute of Scientific and Technical Information of China (English)

    OGUNSIPE Abimbola; NYOKONG Tebello

    2011-01-01

    The solvent viscosity dependence of the photophysical and photochemical properties of tetra(tert-butylphenoxy)phthalocyaninato zinc(Ⅱ) (ZnTBPPc) is presented. The fluorescence quantum yields (φF) and Stern-Volmer's constant (KSV) for ZnTBPPc fluorescence quenching by benzoquinone in all the solutions followed a semi-empirical law that depends only on the solvent viscosity. φF values vary between 0.08 in tetrahydrofuran (THF) and 0.14 in dimethylsulphoxide (DMSO). Triplet quantum yields ( φT) and lifetimes (TT) also exhibit clear solvent viscosity dependence with the values being higher in the most viscous solvents. The interaction of the ZnTBPPc triplet state with oxygen was found to be diffusion- controlled, but higher rate constants were observed in low-viscosity solvents like THF and toluene. Absolute values of singlet oxygen quantum yields ( φA) were determined, and the values are comparable in all the solvents, which is attributed to the proximity of the ZnTBPPc triplet energies in different solvents.

  12. Destruction of 4-phenolsulfonic acid in water by anodic contact glow discharge electrolysis

    Institute of Scientific and Technical Information of China (English)

    Haiming Yang; Baigang An; Shaoyan Wang; Lixiang Li; Wenjie Jin; Lihua Li

    2013-01-01

    Destruction of 4-phenolsulfonic acid (4-PSA) in water was carried out using anodic contact glow discharge electrolysis.Accompanying the decay of 4-PSA,the amount of total organic carbon (TOC) in water correspondingly decreased,while the sulfonate group of 4-PSA was released as sulfate ion.Oxalate and formate were obtained as minor by-products.Additionally,phenol,1,4-hydroquinone,hydroxyquinol and 1,4-benzoquinone were detected as primary intermediates in the initial stages of decomposition of 4-PSA.A reaction pathway involving successive attacks of hydroxyl and hydrogen radicals was assumed on the basis of the observed products and kinetics.It was revealed that the decay of both 4-PSA and TOC obeyed a first-order rate law.The effects of different Fe ions and initial concentrations of 4-PSA on the degradation rate were investigated.It was found that the presence of Fe ions could increase the degradation rate of 4-PSA,while initial concentrations lower than 80 mmol/L had no significant effect on kinetic behaviour.The disappearance rate of 4-PSA was significantly affected by pH.

  13. Effects of long-wavelength ultraviolet (UV-A) radiation on the growth of Anacystis Nidulans

    International Nuclear Information System (INIS)

    The growth of Anacystis nidulans cells which had been grown under visible light only (>390 nm) was suppressed by long-wavelength ultraviolet (UV-A, 320-390 nm) radiation. The growth resumed after 24 h. Cells grown under UV-A supplemented light contained less chlorophyll and phycocyanin and more carotenoid than control cells. The finding that UV-A radiation inhibited the rate of delta-aminolevulinic acid synthesis indicated that the decreases in the photosynthetic pigments were mainly due to the inhibition of their biosynthesis rather than to photodestruction of pigments by UV-A radiation. The primary cause of the inhibitory effects seems to be the inhibition of the photosynthetic process which can be measured as the rho-benzoquinone Hill reaction. Previous exposure to UV-A radiation conferred some resistance on the cells to this inhibitory radiation. Thus UV-A radiation itself may activate a system that repairs damage caused by UV-A radiation and/or protects against the radiation. (author)

  14. Activation of peroxymonosulfate by base: Implications for the degradation of organic pollutants.

    Science.gov (United States)

    Qi, Chengdu; Liu, Xitao; Ma, Jun; Lin, Chunye; Li, Xiaowan; Zhang, Huijuan

    2016-05-01

    Increasing attention has been paid to environmentally friendly activation methods of peroxymonosulfate (PMS) in advanced oxidation processes (AOPs) for organic pollutant elimination. This work demonstrates that Base can be applied as a novel activator for PMS. The Base/PMS system, at ambient temperature, was able to degrade a variety of organic pollutants, including acid orange 7 (AO7), phenol and bisphenol A. In subsequent experiments with AO7, the decolorization rates for AO7 followed pseudo-first-order kinetics, with rate constant values ranging from 0.0006 to 0.1749 min(-1) depending on the operating parameters (initial PMS, Base, AO7 concentrations and reaction temperature). Furthermore, the mechanism for PMS activation by the Base was elucidated by radical scavenger (tert-butyl alcohol, methanol, sodium azide and p-benzoquinone) and electron spin resonance trapping studies. The results revealed that superoxide anion radical and singlet oxygen other than sulfate radical were the primary reactive oxygen species in the Base/PMS system. The findings of this study present a new pathway for PMS activation and provide useful information for the treatment of wastewater. PMID:26946115

  15. Electrochemical incineration of sulfanilic acid at a boron-doped diamond anode.

    Science.gov (United States)

    El-Ghenymy, Abdellatif; Arias, Conchita; Cabot, Pere Lluís; Centellas, Francesc; Garrido, José Antonio; Rodríguez, Rosa María; Brillas, Enric

    2012-06-01

    The anodic oxidation of sulfanilic acid solutions has been studied in acidic medium using a divided cell with a boron-doped diamond (BDD) anode and a stainless steel cathode. Overall mineralization was achieved under all experimental conditions tested due to the efficient destruction of sulfanilic acid and all its by-products with hydroxyl radicals generated at the BDD anode from water oxidation. The alternative use of an undivided cell with the same electrodes gave rise to the coating of the cathode with polymeric compounds, thus preventing the complete electrochemical incineration of sulfanilic acid. The solutions treated in the anodic compartment of the divided cell were degraded at similar rate under pH regulation within the pH interval 2.0-6.0. The mineralization current efficiency was enhanced when the applied current decreased and the initial substrate concentration increased. The decay of sulfanilic acid was followed by reversed-phase HPLC, showing a pseudo first-order kinetics. Hydroquinone and p-benzoquinone were identified as aromatic intermediates by gas chromatography-mass spectrometry and/or reversed-phase HPLC. Maleic, acetic, formic, oxalic and oxamic acids were detected as generated carboxylic acids by ion-exclusion HPLC. Ionic chromatographic analysis of electrolyzed solutions revealed that the N content of sulfanilic acid was mainly released as NH(4)(+) ion and in much smaller proportion as NO(3)(-) ion.

  16. Fenton degradation of sulfanilamide in the presence of Al,Fe-pillared clay: Catalytic behavior and identification of the intermediates.

    Science.gov (United States)

    Khankhasaeva, Sesegma Ts; Dambueva, Darima V; Dashinamzhilova, Elvira Ts; Gil, Antonio; Vicente, Miguel A; Timofeeva, Maria N

    2015-08-15

    Liquid phase catalytic degradation of sulfanilamide with H2O2 was carried out in the presence of Fe,Al/M-pillared clay (Fe,Al/M-MM, M=Na(+), Ca(2+) and Ba(2+)) as heterogeneous Fenton type catalyst. Fe,Al/M-MMs were prepared by swelling of layered aluminosilicate (90-95 wt.% montmorillonite) from a bed located in Mukhortala (Buryatia, Russia) in Na(+), Ca(2+) and Ba(2+) forms by means of the exchange of these cations with bulky Fe,Al-polyoxocations prepared at Al/Fe=10/1 and OH/(Al+Fe)=2.0, and then calcinated at 500°C. XRD method and chemical analysis demonstrated that the rate of crystalline swelling was dependent on the interlayer cations and decreased in the order: Fe,Al-/Na-MM>Fe,Al/Ca-MM>Fe,Al/Ba-MM. It was found that the catalytic properties of Fe,Al/M-MMs depended on the type of exchangeable cations. The effect of the H2O2/sulfanilamide molar ratio, the catalyst content, the reaction temperature and the reaction pH on the removal rate of sulfanilamide has been studied in the presence of Fe,Al/Na-MM. The catalyst can be applied for degradation of sulfanilamide with H2O2 for at least three successive cycles without loss of activity. HPLC analyses pointed out that the main degradation intermediate products were sulfanilic acid, benzenesulfonic acid, p-benzoquinone and aliphatic carboxylic acids.

  17. Electro-fenton and photoelectro-fenton degradation of sulfanilic acid using a boron-doped diamond anode and an air diffusion cathode.

    Science.gov (United States)

    El-Ghenymy, Abdellatif; Garrido, José Antonio; Centellas, Francesc; Arias, Conchita; Cabot, Pere Lluís; Rodríguez, Rosa María; Brillas, Enric

    2012-04-01

    The mineralization of sulfanilic acid has been studied by electro-Fenton (EF) and photoelectro-Fenton (PEF) reaction with UVA light using an undivided electrochemical cell with a boron-doped diamond (BDD) anode and an air diffusion cathode able to generate H(2)O(2). Organics were then oxidized by hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton's reaction between generated H(2)O(2) and added Fe(2+). The UVA irradiation in PEF enhanced the production of hydroxyl radicals in the bulk, accelerating the removal of organics and photodecomposed intermediates like Fe(III)-carboxylate complexes. Partial decontamination of 1.39 mM sulfanilic acid solutions was achieved by EF until 100 mA cm(-2) at optimum conditions of 0.4 mM Fe(2+) and pH 3.0. The increase in current density and substrate content led to an almost total mineralization. In contrast, the PEF process was more powerful, yielding almost complete mineralization in less electrolysis time under comparable conditions. The kinetics for sulfanilic acid decay always followed a pseudo-first-order reaction. Hydroquinone and p-benzoquinone were detected as aromatic intermediates, whereas acetic, maleic, formic, oxalic, and oxamic acids were identified as generated carboxylic acids. NH(4)(+) ion was preferentially released in both treatments, along with NO(3)(-) ion in smaller proportion.

  18. Evidence of superoxide radical contribution to demineralization of sulfamethoxazole by visible-light-driven Bi2O3/Bi2O2CO3/Sr6Bi2O9 photocatalyst.

    Science.gov (United States)

    Ding, Shiyuan; Niu, Junfeng; Bao, Yueping; Hu, Lijuan

    2013-11-15

    Photocatalytic degradation of sulfamethoxazole (SMX) was investigated using Bi2O3/Bi2O2CO3/Sr6Bi2O9 (BSO) photocatalyst under visible light (>420 nm) irradiation. The photochemical degradation of SMX followed pseudo-first-order kinetics. The reaction kinetics was determined as a function of initial SMX concentrations (5-20 mg L(-1)), initial pH (3-11) and BSO concentrations (6-600 mg L(-1)). Approximately, 90% of SMX (10 mg L(-1)) degradation and 36% of TOC reduction were achieved at pH 7.0 after 120 min irradiation. The main mineralization products, including NH4(+), NO3(-), SO4(2-) and CO2, as well as intermediates 3-amino-5-methylisoxazole (AMI), p-benzoquinone (BZQ), and sulfanilic acid (SNA) were detected in aqueous solution. The formation of O2(*-) radical was evidenced by using electron spin resonance and a chemiluminescent probe, luminal. A possible degradation mechanism involving excitation of BSO, followed by charge injection into the BSO conduction band and formation of reactive superoxide radical (O2(*-)) was proposed for the mineralization of SMX. During the reaction, the O2(*-) radical attacks the sulfone moiety and causes the cleavage of the SN bond, which leads to the formation of two sub-structure analogs, AMI and SNA.

  19. Chemical Bonding and Structural Information of Black CarbonReference Materials and Individual Carbonaceous AtmosphericAerosols

    Energy Technology Data Exchange (ETDEWEB)

    Hopkins, Rebecca J.; Tivanski, Alexei V.; Marten, Bryan D.; Gilles, Mary K.

    2007-04-25

    The carbon-to-oxygen ratios and graphitic nature of a rangeof black carbon standard reference materials (BC SRMs), high molecularmass humic-like substances (HULIS) and atmospheric particles are examinedusing scanning transmission X-ray microscopy (STXM) coupled with nearedge X-ray absorption fine structure (NEXAFS) spectroscopy. UsingSTXM/NEXAFS, individual particles with diameter>100 nm are studied,thus the diversity of atmospheric particles collected during a variety offield missions is assessed. Applying a semi-quantitative peak fittingmethod to the NEXAFS spectra enables a comparison of BC SRMs and HULIS toparticles originating from anthropogenic combustion and biomass burns,thus allowing determination of the suitability of these materials forrepresenting atmospheric particles. Anthropogenic combustion and biomassburn particles can be distinguished from one another using both chemicalbonding and structural ordering information. While anthropogeniccombustion particles are characterized by a high proportion ofaromatic-C, the presence of benzoquinone and are highly structurallyordered, biomass burn particles exhibit lower structural ordering, asmaller proportion of aromatic-C and contain a much higher proportion ofoxygenated functional groups.

  20. Synthesis of f metal coordination polymers: properties and conversion into inorganic solids

    International Nuclear Information System (INIS)

    Coordination polymers (CP) are of great academic and industrial interest due to flexible structure and composition and offer prospects for original chemical (catalysis, soft-hard materials conversion..) and physical properties (magnetism, optics..). The major interest of these studies is to check the transfer of the structure, meso-structure and composition from the CP to the ceramic via a thermal treatment. In this context, this thesis describes studies on conversion of coordination polymers obtained by self-assembly of 4f and 5f metal ions with 2,5-dihydroxy-1,4-benzoquinone (DHBQ). Aqueous and anhydrous synthetic ways were developed, which yielded different kinds of CPs (4f, 4f-4f, 4f-5f); solid solutions were obtained with the mixed compounds. The products were characterized and their behaviour under thermal treatment was studied. The main results show that the DHBQ-based precursors obtained by aqueous way have a micrometric meso-structure, formed by the assembly of micro-crystalline subunits which all posses the same crystallographic structure. The study of the assembly of the meso-structure allowed controlling the morphology of the elementary grain (cylinder, cube, disk...) with very good size distribution. The implementation of anhydrous systems in a controlled atmosphere allowed yielded a wider range of micro-structural parameters (surface area, porosity...). For all CP-type compounds, the thermal conversion to ceramic has barely altered the morphology of the materials. The microstructural aspects could be controlled via the method of synthesis. (author)

  1. Ultrahigh-pressure liquid chromatography triple-quadrupole tandem mass spectrometry quantitation of polyphenols and secoiridoids in california-style black ripe olives and dry salt-cured olives.

    Science.gov (United States)

    Melliou, Eleni; Zweigenbaum, Jerry A; Mitchell, Alyson E

    2015-03-11

    The chemical composition of finished table olive products is influenced by the olive variety and the processing method used to debitter or cure table olives. Herein, a rapid ultrahigh-pressure liquid chromatography triple-quadrupole tandem mass spectrometry method, using dynamic multiple reaction monitoring, was developed for the quantitation of 12 predominant phenolic and secoiridoid compounds in olive fruit, including hydroxytyrosol, oleuropein, hydroxytyrosol-4-O-glucoside, luteolin-7-O-glucoside, rutin, verbascoside, oleoside-11-methyl ester, 2,6-dimethoxy-p-benzoquinone, phenolic acids (chlorogenic and o-coumaric acids), oleuropein aglycone, and ligstroside aglycone. Levels of these compounds were measured in fresh and California-style black ripe processed Manzanilla olives and two dry salt-cured olive varieties (Mission from California and Throuba Thassos from Greece). Results indicate that the variety and debittering processing method have strong impact on the profile of phenolic and secoiridoid compounds in table olives. The dry salt-cured olives contained higher amounts of most compounds studied, especially oleuropein (1459.5 ± 100.1 μg/g), whereas California-style black ripe olives had a significant reduction or loss of these bioactive compounds (e.g., oleuropein level at 36.7 ± 3.1 μg/g). PMID:25668132

  2. Mesopolymer modified with palladium phthalocyaninesulfonate as a versatile photocatalyst for phenol and bisphenol A degradation under visible light irradiation.

    Science.gov (United States)

    Xing, Rong; Wu, Lin; Fei, Zhenghao; Wu, Peng

    2013-08-01

    A novel versatile photocatalyst, FDU-PdPcS, was prepared by immobilizing palladium phthalocyaninesulfonate (PdPcS) onto the FDU-15 mesopolymer via multi-step chemical modification processes involving chloromethylation of the FDU-15 mesopolymer first with chloromethyl methyl ether, a subsequent amination reaction with ethylenediamine, and finally modification with palladium phthalocyaninesulfonate via ionic interaction. The obtained FDU-PdPcS photocatalyst was characterized by the X-ray diffraction (XRD), UV-Vis spectrosopy and inductively coupled plasma (ICP) techniques. This photocatalyst not only affords a high dispersion of monomeric PdPcS molecules, which may further be stabilized by the pi-electron of benzene rings of FDU-15, but also provides a number of diamino groups inside the mesopores, which could be advantageous for the photodegradation of phenolic pollutants. In photodegradation studies of phenolic pollutants, the FDU-PdPcS catalyst exhibited excellent visible light photocatalytic activity and reusability. The photodegradation products of phenol and bisphenol A were investigated by the gas chromatoghraphy-mass spectrometry (GC-MS) technique. The results showed that the photodegradation products were composed of carboxylic acids and CO2. Isopropanol, sodium azide and benzoquinone were used as hydroxyl radical (OH*), singlet oxygen (1O2) and superoxide radical (O2*-) scavengers, respectively. The results suggested that 1O2 and O2*- were the prominent active species during the photodegradation process. A possible mechanism for the photodegradation of phenol was also discussed.

  3. Pyridine-H5PMo10V2O40 hybrid catalysts for liquid-phase hydroxylation of benzene to phenol with molecular oxygen

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Pyridine(Py)-modified Keggin-type vanadium-substituted heteropoly acids(PynPMo10V2O40,n=1 to 5) were prepared by a precipitation method as organic/inorganic hybrid catalysts for direct hydroxylation of benzene to phenol in a pressured batch reactor and their structures were detected by FT-IR.Among various catalysts,Py3PMo10V2O40 exhibits the highest catalytic activity(yield of phenol,11.5%),without observing the formation of catechol,hydroquinone and benzoquinone in the reaction with 80 vol% aqueous acetic acid,molecular oxygen and ascorbic acid used as the solvent,oxidant and reducing reagent,respectively.Influences of reaction temperature,reaction time,oxygen pressure,amount of ascorbic acid and catalyst on yield of phenol were investigated to obtain the optimal reaction conditions for phenol formation.Pyridine can greatly promote the catalytic activity of the Py-free catalyst(H5PMo10V2O40),mostly because the organic π electrons in the hybrid catalyst may extend their conjugation to the inorganic framework of heteropoly acid and dramatically modify the redox properties,at the same time,pyridine adsorbed on heteropoly acids can promote the effect of "pseudo-liquid phase",thus accounting for the enhancement of phenol yield.

  4. para-Nitrophenol 4-monooxygenase and hydroxyquinol 1,2-dioxygenase catalyze sequential transformation of 4-nitrocatechol in Pseudomonas sp. strain WBC-3.

    Science.gov (United States)

    Wei, Min; Zhang, Jun-Jie; Liu, Hong; Zhou, Ning-Yi

    2010-11-01

    Pseudomonas sp. strain WBC-3 utilizes para-nitrophenol (PNP) as a sole source of carbon, nitrogen and energy. PnpA (PNP 4-monooxygenase) and PnpB (para-benzoquinone reductase) were shown to be involved in the initial steps of PNP catabolism via hydroquinone. We demonstrated here that PnpA also catalyzed monooxygenation of 4-nitrocatechol (4-NC) to hydroxyquinol, probably via hydroxyquinone. It was the first time that a single-component PNP monooxygenase has been shown to catalyze this conversion. PnpG encoded by a gene located in the PNP degradation cluster was purified as a His-tagged protein and identified as a hydroxyquinol dioxygenase catalyzing a ring-cleavage reaction of hydroxyquinol. Although all the genes necessary for 4-NC metabolism seemed to be present in the PNP degradation cluster in strain WBC-3, it was unable to grow on 4-NC as a sole source of carbon, nitrogen and energy. This was apparently due to the substrate's inability to trigger the expression of genes involved in degradation. Nevertheless, strain WBC-3 could completely degrade both PNP and 4-NC when PNP was used as the inducer, demonstrating its potential in bioremediation of the environment polluted by both 4-NC and PNP.

  5. Bioassay-guided evaluation of anti-inflammatory and antinociceptive activities of pistachio, Pistacia vera L.

    Science.gov (United States)

    Orhan, I; Küpeli, E; Aslan, M; Kartal, M; Yesilada, E

    2006-04-21

    The ethanolic and aqueous extracts prepared from different parts of Pistacia vera L. (Anacardiaceae) as well as its oleoresin were evaluated for their in vivo anti-inflammatory and antinociceptive activities. Among the extracts screened, only the oleoresin was shown to possess a marked anti-inflammatory activity against carrageenan-induced hind paw edema model in mice without inducing any gastric damage at both 250 and 500 mg/kg doses whereas the rest of the extracts were totally inactive. While the oleoresin was found to display significant antinociceptive activity at 500 mg/kg dose, the ethanolic and aqueous extracts belonging to fruit, leaf, branch and peduncle of Pistacia vera did not exhibit any noticeable antinociception in p-benzoquinone-induced abdominal contractions in mice. Fractionation of the oleoresin indicated the n-hexane fraction to be active, which further led to recognition of some monoterpenes, mainly alpha-pinene (77.5%) by capillary gas chromatography-mass spectrometry (GC-MS) as well as the oleoresin itself. alpha-Pinene was also assessed for its antinociceptive and anti-inflammatory activities in the same manner and exerted a moderate anti-inflammatory effect at 500 mg/kg dose. PMID:16337351

  6. Superoxide radical-mediated photocatalytic oxidation of phenolic compounds over Ag⁺/TiO₂: Influence of electron donating and withdrawing substituents.

    Science.gov (United States)

    Xiao, Jiadong; Xie, Yongbing; Han, Qingzhen; Cao, Hongbin; Wang, Yujiao; Nawaz, Faheem; Duan, Feng

    2016-03-01

    A comparative study was constructed to correlate the electronic property of the substituents with the degradation rates of phenolic compounds and their oxidation pathways under UV with Ag(+)/TiO2 suspensions. It was verified that a weak electron withdrawing substituent benefited photocatalytic oxidation the most, while an adverse impact appeared when a substituent was present with stronger electron donating or withdrawing ability. The addition of p-benzoquinone dramatically blocked the degradation, confirming superoxide radicals (O2(-)) as the dominant photooxidant, rather than hydroxyl radicals, singlet oxygen or positive holes, which was also independent of the substituent. Hammett relationship was established based on pseudo-first-order reaction kinetics, and it revealed two disparate reaction patterns between O2(-) and phenolic compounds, which was further verified by the quantum chemical computation on the frontier molecular orbitals and Mulliken charge distributions of O2(-) and phenolic compounds. It was found that electron donating group (EDG) substituted phenols were more likely nucleophilically attacked by O2(-), while O2(-) preferred to electrophilically assault electron withdrawing group (EWG) substituted phenols. Exceptionally, electrophilic and nucleophilic attack by O2(-) could simultaneously occur in p-chlorophenol degradation, consequently leading to its highest rate constant. Possible reactive positions on the phenolic compounds were also detailedly uncovered. PMID:26547621

  7. Study of fluorescence characteristics of the charge-transfer reaction of quinolone agents with bromanil

    Science.gov (United States)

    Li, Wen-Ying; Chen, Xiao-Fang; Xuan, Chun-Sheng

    2009-01-01

    A spectrofluorimetric method was discussed for the determination of three antibacterial quinolone derivatives, ofloxacin (OFL), norfloxacin (NOR) and ciprofloxacin (CIP) through charge-transfer complexation (CTC) with 2,3,5,6-tetrabromo-1,4-benzoquinone (bromanil, TBBQ). The method was based on the reaction of these drugs as n-electron donors with the π-acceptor TBBQ. TBBQ was found to react with these drugs to produce a kind of yellow complexes and the fluorescence intensities of the complexes were enhanced by 29-36 times more than those of the corresponding monomers. UV-vis, 1H NMR and XPS techniques were used to study the complexes formed. The various experimental parameters affecting the fluorescence intensity were studied and optimized. Under optimal reaction conditions, the rectilinear calibration graphs were obtained in the concentration range of 0.021-2.42 μg mL -1, 0.017-2.63 μg mL -1 and 0.019-2.14 μg mL -1 for OFL, NOR and CIP, respectively. The methods developed were applied successfully to the determination of the subject drugs in their pharmaceutical dosage forms with good precision and accuracy compared to official and reported methods as revealed by t- and F-tests.

  8. Application of several advanced oxidation processes for the destruction of terephthalic acid (TPA)

    International Nuclear Information System (INIS)

    Terephthalic acid (TPA) is widely applied as a raw material in making polyester fiber, polyethylene terephthalate (PET) bottles, polyester films, etc. TPA is toxic and is known to act as endocrine disruptor. TPA wastewater is traditionally treated by biological process and this study aims to evaluate the effectiveness of several advanced oxidation processes on TPA removal. The oxidation processes studied were: UV-TiO2, UV-H2O2, UV-H2O2-Fe, O3, O3/Fe, O3/TiO2, UV-O3-H2O2-Fe and UV-O3-H2O2-Fe-TiO2. The results indicate that the time required for the complete destruction of 50 ppm of TPA can be minimized from 10 h using UV-TiO2 system, to less than 10 min by UV-H2O2-Fe-O3 system. Some of the likely organic intermediates identified during TPA destruction include, benzoquinone, benzene, maleic acid and oxalic acid. Possible destruction pathway of TPA has been proposed. TPA degradation by various systems was also analyzed based on the reaction kinetics and operating costs

  9. pks63787, a Polyketide Synthase Gene Responsible for the Biosynthesis of Benzenoids in the Medicinal Mushroom Antrodia cinnamomea.

    Science.gov (United States)

    Yu, Po-Wei; Chang, Ya-Chih; Liou, Ruey-Fen; Lee, Tzong-Huei; Tzean, Shean-Shong

    2016-06-24

    Antrodia cinnamomea, a unique resupinate basidiomycete endemic to Taiwan, has potent medicinal activities. The reddish basidiocarps and mycelia generally exhibit abundant metabolites and higher biological activity. To investigate the pigments of A. cinnamomea, polyketide synthase (PKS) genes were characterized based on its partially deciphered genome and the construction of a fosmid library. Furthermore, a gene disruption platform was established via protoplast transformation and homologous recombination. Of four putative polyketide synthase genes, pks63787 was selected and disrupted in the monokaryotic wild-type (wt) strain f101. Transformant Δpks63787 was deficient in the synthesis of several aromatic metabolites, including five benzenoids and two benzoquinone derivatives. Based on these results, a biosynthetic pathway for benzenoid derivatives was proposed. The pks63787 deletion mutant not only displayed a reduced red phenotype compared to the wt strain but also displayed less 1,1-biphenyl-2-picrylhydrazyl free radical scavenging activity. This finding suggests that PKS63787 is responsible for the biosynthesis of pigments and metabolites related to the antioxidant activity of A. cinnamomea. The present study focuses on the functional characterization of the PKS gene, the fluctuations of its profile of secondary metabolites, and interpretation of the biosynthesis of benzenoids. PMID:27227778

  10. A Novel Photoelectrochemical Biosensor for Tyrosinase and Thrombin Detection

    Directory of Open Access Journals (Sweden)

    Jiexia Chen

    2016-01-01

    Full Text Available A novel photoelectrochemical biosensor for step-by-step assay of tyrosinase and thrombin was fabricated based on the specific interactions between the designed peptide and the target enzymes. A peptide chain with a special sequence which contains a positively charged lysine-labeled terminal, tyrosine at the other end and a cleavage site recognized by thrombin between them was designed. The designed peptide can be fixed on surface of the CdTe quantum dots (QDs-modified indium-tin oxide (ITO electrode through electrostatic attraction to construct the photoelectrochemical biosensor. The tyrosinase target can catalyze the oxidization of tyrosine by oxygen into ortho-benzoquinone residues, which results in a decrease in the sensor photocurrent. Subsequently, the cleavage site could be recognized and cut off by another thrombin target, restoring the sensor photocurrent. The decrease or increase of photocurrent in the sensor enables us to assay tyrosinase and thrombin. Thus, the detection of tyrosinase and thrombin can be achieved in the linear range from 2.6 to 32 μg/mL and from 4.5 to 100 μg/mL with detection limits of 1.5 μg/mL and 1.9 μg/mL, respectively. Most importantly, this strategy shall allow us to detect different classes of enzymes simultaneously by designing various enzyme-specific peptide substrates.

  11. The analysis of aqueous mixtures using liquid chromatography-electrospray mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, S.

    1999-02-12

    The focus of this dissertation is the use of chromatographic methods coupled with electrospray mass spectrometry (ES-MS) for the determination of both organic and inorganic compounds in aqueous solutions. The combination of liquid chromatography (LC) methods and ES-MS offers one of the foremost methods for determining compounds in complex aqueous solutions. In this work, LC-ES-MS methods are devised using ion exclusion chromatography, reversed phase chromatography, and ion exchange chromatography, as well as capillary electrophoresis (CE). For an aqueous sample, these LC-ES-MS and CE-ES-MS techniques require no sample preparation or analyte derivatization, which makes it possible to observe a wide variety of analytes as they exist in solution. The majority of this work focuses on the use of LC-ES-MS for the determination of unknown products and intermediates formed during electrochemical incineration (ECI), an experimental waste remediation process. This report contains a general introduction to the project and the general conclusions. Four chapters have been removed for separate processing. Titles are: Chapter 2: Determination of small carboxylic acids by ion exclusion chromatography with electrospray mass spectrometry; Chapter 3: Electrochemical incineration of benzoquinone in aqueous media using a quaternary metal oxide electrode in the absence of a soluble supporting electrolyte; Chapter 4: The determination of electrochemical incineration products of 4-chlorophenol by liquid chromatography-electrospray mass spectrometry; and Chapter 5: Determination of small carboxylic acids by capillary electrophoresis with electrospray mass spectrometry.

  12. Characterization of a new aryl-alcohol oxidase secreted by the phytopathogenic fungus Ustilago maydis.

    Science.gov (United States)

    Couturier, Marie; Mathieu, Yann; Li, Ai; Navarro, David; Drula, Elodie; Haon, Mireille; Grisel, Sacha; Ludwig, Roland; Berrin, Jean-Guy

    2016-01-01

    The discovery of novel fungal lignocellulolytic enzymes is essential to improve the breakdown of plant biomass for the production of second-generation biofuels or biobased materials in green biorefineries. We previously reported that Ustilago maydis grown on maize secreted a diverse set of lignocellulose-acting enzymes including hemicellulases and putative oxidoreductases. One of the most abundant proteins of the secretome was a putative glucose-methanol-choline (GMC) oxidoreductase. The phylogenetic prediction of its function was hampered by the few characterized members within its clade. Therefore, we cloned the gene and produced the recombinant protein to high yield in Pichia pastoris. Functional screening using a library of substrates revealed that this enzyme was able to oxidize several aromatic alcohols. Of the tested aryl-alcohols, the highest oxidation rate was obtained with 4-anisyl alcohol. Oxygen, 1,4-benzoquinone, and 2,6-dichloroindophenol can serve as electron acceptors. This GMC oxidoreductase displays the characteristics of an aryl-alcohol oxidase (E.C.1.1.3.7), which is suggested to act on the lignin fraction in biomass.

  13. High catalytic activity of magnetic CuFe2O4/graphene oxide composite for the degradation of organic dyes under visible light irradiation

    Science.gov (United States)

    Chen, Peng; Xing, Xiang; Xie, Huifang; Sheng, Qi; Qu, Hongxia

    2016-09-01

    Magnetic CuFe2O4/graphene oxide composite (CuFe2O4/GO) has been synthesized by hydrothermal method and showed excellent visible-light-photocatalytic activity for the degradation of different dyes as Rhodamine B (RhB) and acid orange II (AO7) with no need of H2O2. The Structure and morphology were investigated by XRD, FTIR and TEM and the performance of the catalyst was systematically investigated under various experimental conditions as pH, the dosage of catalyst, dye initial concentration, etc. The dyes degradation on CuFe2O4/GO was also remained in a level in the presence of OH2- radical scavenger (2-propanol), while it decreased in the presence of O2- radical scavenger (benzoquinone) and h+ radical scavenger (ammonium oxalate), indicating that O2- and h+ radicals were responsible for the dye degradation. The magnetic CuFe2O4/GO composite shows potential applications in organic dye water treatment due to its magnetically recyclability and powerful visible-light-photocatalytic activity.

  14. Design of a mediated enzymatic fuel cell to generate power from renewable fuel sources.

    Science.gov (United States)

    Korkut, Seyda; Kilic, Muhammet Samet

    2016-01-01

    The present work reported a compartment-less enzymatic fuel cell (EFC) based on newly synthesized Poly(pyrrole-2-carboxylic acid-co-3-thiophene acetic acid) film containing glucose oxidase and laccase effectively wired by p-benzoquinone incorporated into the copolymer structure. The resulting system generated a power density of 18.8 µW/cm(2) with 30 mM of glucose addition at +0.94 V at room temperature. Improvements to maximize the power output were ensured with step-by-step optimization of electrode fabrication design and operational parameters for operating the system with renewable fuel sources. We demonstrated that the improved fuel cell could easily harvest glucose produced during photosynthesis to produce electrical energy in a simple, renewable and sustainable way by generating a power density of 10 nW/cm(2) in the plant leaf within 2 min. An EFC for the first time was successfully operated in municipal wastewater which contained glycolytic substances to generate electrical energy with a power output of 3.3 µW/cm(2). PMID:26102352

  15. Crystal structures of Pseudomonas syringae pv. tomato DC3000 quinone oxidoreductase and its complex with NADPH

    International Nuclear Information System (INIS)

    Zeta-crystallin-like quinone oxidoreductase is NAD(P)H-dependent and catalyzes one-electron reduction of certain quinones to generate semiquinone. Here we present the crystal structures of zeta-crystallin-like quinone oxidoreductase from Pseudomonas syringae pv. tomato DC3000 (PtoQOR) and its complexes with NADPH determined at 2.4 and 2.01 A resolutions, respectively. PtoQOR forms as a homologous dimer, each monomer containing two domains. In the structure of the PtoQOR-NADPH complex, NADPH locates in the groove between the two domains. NADPH binding causes obvious conformational changes in the structure of PtoQOR. The putative substrate-binding site of PtoQOR is wider than that of Escherichia coli and Thermus thermophilus HB8. Activity assays show that PtoQOR has weak 1,4-benzoquinone catalytic activity, and very strong reduction activity towards large substrates such as 9,10-phenanthrenequinone. We propose a model to explain the conformational changes which take place during reduction reactions catalyzed by PtoQOR.

  16. Widespread ability of fungi to drive quinone redox cycling for biodegradation.

    Science.gov (United States)

    Krueger, Martin C; Bergmann, Michael; Schlosser, Dietmar

    2016-06-01

    Wood-rotting fungi possess remarkably diverse extracellular oxidation mechanisms, including enzymes, such as laccase and peroxidases, and Fenton chemistry. The ability to biologically drive Fenton chemistry by the redox cycling of quinones has previously been reported to be present in both ecologically diverging main groups of wood-rotting basidiomycetes. Therefore, we investigated whether it is even more widespread among fungal organisms. Screening of a diverse selection of a total of 18 ascomycetes and basidiomycetes for reduction of the model compound 2,6-dimethoxy benzoquinone revealed that all investigated strains were capable of reducing it to its corresponding hydroquinone. In a second step, depolymerization of the synthetic polymer polystyrene sulfonate was used as a proxy for quinone-dependent Fenton-based biodegradation capabilities. A diverse subset of the strains, including environmentally ubiquitous molds, white-rot fungi, as well as peatland and aquatic isolates, caused substantial depolymerization indicative for the effective employment of quinone redox cycling as biodegradation tool. Our results may also open up new paths to utilize diverse fungi for the bioremediation of recalcitrant organic pollutants.

  17. Effect of titanium dioxide nanoparticles on gamma-ray treatment of phenol in different matrices: implications in toxicity toward Daphnia magna.

    Science.gov (United States)

    Kang, Sung-Wook; Shim, Seung-Bo; Yoo, Jisu; Jung, Jinho

    2012-10-01

    Gamma-ray treatment of phenol was studied in terms of both chemical degradation and toxicological change. About 90% of phenol (5.0 × 10(-4) M) in ultrapure water (UW) was eliminated by gamma-irradiation at a dose of 10 kGy, but acute toxicity was dramatically increased, particularly for dose of 1 kGy, due to the formation of more toxic by-products such as hydroquinone, benzoquinone, resorcinol and catechol. The addition of TiO(2) nanoparticles had little effect on the removal of phenol in UW, but substantially enhanced the mineralization of phenol compared with gamma-irradiation alone. Additionally, degradation of phenol by gamma-irradiation was inhibited in a wastewater effluent (WE) matrix, likely due to the presence of dissolved organic carbon (22.06 mg L(-1)). Furthermore, lower concentrations of toxic by-products were generated both in WE and in the presence of TiO(2) nanoparticles, resulting in reduction of toxicity increase by gamma-irradiation. Meanwhile, the toxicity of gamma-ray treated phenol in WE was well estimated with simple summation of individual toxicity of phenol and by-products (R (2) = 0.9678). PMID:22875283

  18. Activation of peroxymonosulfate by BiVO4 under visible light for degradation of Rhodamine B

    Science.gov (United States)

    Liu, Yang; Guo, Hongguang; Zhang, Yongli; Tang, Weihong; Cheng, Xin; Liu, Hongwei

    2016-06-01

    A photocatalytic system involving visible light and BiVO4 (Vis/BiVO4) in the presence of peroxymonosulfate (PMS) has been developed to oxidize the target pollutant Rhodamine B (RhB) in aqueous solution. It was found that PMS could enhance the photocatalytic efficiency of BiVO4 and could be activated to promote the removal of RhB with sulfate radicals, hydroxyl radicals and superoxide radicals. Critical impacting factors in the Vis/BiVO4/PMS system were investigated concerning the influence of PMS concentration, solution pH, catalyst dosage, initial concentration of RhB and the presence of anions (Cl- and CO32-). In addition, by using isopropanol, tert-butanol, 1,4-benzoquinone and ethylenediamine tetraacetic acid disodium salt as probe compounds, the main active species were demonstrated including radSO4-, radOH and radO2- in the system, and a detail photocatalytic mechanism for the Vis/BiVO4/PMS system was proposed. Finally, up to 10 intermediate products of RhB were identified by GC/MS, included benzenoid organic compounds, organic acids and three nitrogenous organic compounds. This study provides a feasible way to degrade organic pollutants in wastewater using BiVO4 with PMS under visible light.

  19. Development and Validation of Selective Spectrophotometric Methods for the Determination of Pregabalin in Pharmaceutical Preparation

    Institute of Scientific and Technical Information of China (English)

    ARMA(G)AN,(O)nal

    2009-01-01

    Three simple,quick and sensitive methods are described for the spectrophotometric determination of pregabalin (Pgb) in pharmaceutical preparations.Among them,the first two methods are based on the reaction of Pgb as n-electron donors with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) as π-acceptors to give highly colored complex species.The colored products were quantitated spectrophotometrically at 494 and 841 nm for DDQ and TCNQ,respectively.Optimization of the different experimental conditions was conducted.Beer's law was obeyed in the concentration ranges 2.0-30.0 and 1.5-10 μg·mL-1 for DDQ and TCNQ methods,respectively.The third method is based on the interaction of ninhydrin (NN) with primary amine present in the pregabaline.This reaction produces a blue coloured product in N,N-dimethylformamide (DMF) medium,which absorbs maximally at 573 nm.Beer's law was found in the concentration range 40.0-180.0 μg·mL-1.The methods were applied successfully to the determination of this drug in pharmaceutical dosage forms.

  20. Phenol Oxidation by Combined Cavitation Water Jet and Hydrogen Peroxide

    Institute of Scientific and Technical Information of China (English)

    卢义玉; 刘勇; 夏彬伟; 左伟芹

    2012-01-01

    The paper presents results of phenol oxidized under the conditions of high temperature created during collapse of cavitation bubbles.The degradation efficiency has been greatly improved by using cavitation water jets combined with H2O2 as demonstrated in laboratory tests.Various factors affecting phenol removal ratio were ex-amined and the degradation mechanism was revealed by high performance liquid chromatography(HPLC).The re-sults showed that 99.85% of phenol was mineralized when phenol concentration was 100 mg·L-1 with pH value of 3.0,H2O2 concentration of 300 mg·L-1,confining pressure of 0.5 MPa,and pumping pressure of 20 MPa.The in-termediate products after phenol oxidation were composed of catechol,hydroquinone and p-benzoquinone.Finally,phenol was degraded into maleic acid and acetic acid.Furthermore,a dynamic model of phenol oxidation via cavi-tation water jets combined with H2O2 has been developed.

  1. SYNTHESIS, CHARACTERIZATION AND SPECTROSCOPIC INVESTIGATION OF PYRAZINOPORPHYRAZINE NETWORK POLYMER-SUPPORTED METAL (Ⅱ)-BASED CATALYSTS

    Institute of Scientific and Technical Information of China (English)

    H.H.Abdel-Razik; B.H.Asghar; E.Kenawy

    2013-01-01

    Chloranil through condensation reaction with vicinal diamine such as diaminomaleonitrile produced heterocyclic monomer,p-benzoquinonebis[2,3-b; 2',3'-b']pyrazine-5,6-dinitrile.The tetranitrile monomer was cyclo-tetramerised using lithium/pentanol and acetic acid affording the corresponding tetra p-benzoquinone bis[2,3-b; 2',3'-b']pyrazinoporphyrazine)]-based network polymer (2H-Pz).The tetranitril monomer was cyclo-tetramerised using metal salt and quinoline affording the corresponding porphyrazinato-metal Ⅱ-based network polymers (M-Pz),M =Co,Ni or Cu.Elemental analytical results,IR and NMR spectral data of the prepared molecules are consistent with their assigned formulations.Molecular masses and metal contents of the synthesized polymers proved to be of high molecular masses which confirm the efficiency of tetramerization polymerization and complexation reactions.The prepared pyrazinoporphyrazines were used as efficient catalysts for the oxidation of thiophenol and benzylthiol to their disulfides in the presence of air atmosphere.The results of oxidation of thiophenol and benzylthiol show that after 15 min the maximum yield of the corresponding disulfides reached 95%,91%,respectively.

  2. Naked-Eye Coulometric Sensor Using a Longitudinally Oriented Ag Band Electrode in a Microfluidic Channel.

    Science.gov (United States)

    Oh, Jung-Min; Chow, Kwok-Fan

    2016-05-01

    In this Article, we report a coulometric sensing platform that is capable of sensing analytes on a working electrode and providing a visual readout of the analyte concentration on a silver (Ag) band counter electrode in a microchannel. The display mechanism relies on the electro-oxidation of metallic Ag as a complementary reaction to the sensing reduction reaction. The Ag band counter electrode is arranged longitudinally in a microchannel while the frontal tip of the band electrode directly faces a gold (Au) working electrode, which lies across the microchannel. The Ag oxidation always occurs at the band electrode's tip region that faces the working electrode due to the Ohmic potential drop across the solution in the microchannel. The decrement of the Ag electrode, which is clearly measurable with the naked eye, correlates linearly with an analyte concentration (e.g., 0.1-2.5 mM p-benzoquinone) and with an analyte feeding rate (i.e., a sample solution flow rate of 1.0-75.0 μL min(-1)). The platform design is also effective for a model analyte of horseradish peroxidase (HRP)-avidin in the dynamic range of 0.1-3.0 μg mL(-1). PMID:27064358

  3. Subcellular localization of H2O2 production in human neutrophils stimulated with particles and an effect of cytochalasin-B on the cells

    International Nuclear Information System (INIS)

    The ultrastructural localization of H2O2 production in suspended polymorphonuclear leukocytes (PMN) stimulated with particles was studied using CeCl3 technique. PMN stimulated with opsonized zymosan or polystylene latex with or without IgG were incubated in 0.1 M Tris-maleate buffer with 1 mM CeCl3 and 10 mM aminotriazole. Cells were then fixed and embedded in a resin for electron microscopy. The reaction product of cerium perhydroxide was observed on the phagosomal membranes and on the areas of the plasma membrane engulfing the particles. Catalase or ferricytochrome-c decreased the deposits. p-Benzoquinone (O2- scavenger) inhibited the formation of the deposits, but KCN or NaN3 enhanced it. Pretreatment with p-diazobenzenesulfonic acid inhibited the reaction. In some PMN pretreated with cytochalasin-B, cellular aggregation was observed. The H2O2 production in these cells were observed on the membrane adherent to the particles and on the contact surface of the membrane of adjoining PMN. The plasma membrane was damaged and the electron-dense product was diffused into the cytoplasm. These results clearly show that H2O2 production is initiated at the area of the plasma membrane adherent to the particles and that H2O2 is released before the completion of phagocytosis

  4. Anodic oxidation of o-nitrophenol on BDD electrode: Variable effects and mechanisms of degradation

    Energy Technology Data Exchange (ETDEWEB)

    Rabaaoui, Nejmeddine, E-mail: chimie_tunisie@yahoo.fr [Materials, Environment and Energy Laboratory (06/UR/12-01), Science Faculty of Gafsa, 2112, University of Gafsa (Tunisia); Saad, Mohamed El Khames [Materials, Environment and Energy Laboratory (06/UR/12-01), Science Faculty of Gafsa, 2112, University of Gafsa (Tunisia); Moussaoui, Younes [Materials, Environment and Energy Laboratory (06/UR/12-01), Science Faculty of Gafsa, 2112, University of Gafsa (Tunisia); Physical Organic Chemistry Laboratory, Science Faculty of Sfax, University of Sfax (Tunisia); Allagui, Mohamed Salah [Science Faculty of Gafsa, University of Gafsa (Tunisia); Bedoui, Ahmed [Materials, Environment and Energy Laboratory (06/UR/12-01), Science Faculty of Gafsa, 2112, University of Gafsa (Tunisia); Science Faculty of Gabes, 6072, University of Gabes (Tunisia); Elaloui, Elimame [Materials, Environment and Energy Laboratory (06/UR/12-01), Science Faculty of Gafsa, 2112, University of Gafsa (Tunisia); Science Faculty of Gafsa, University of Gafsa (Tunisia)

    2013-04-15

    Highlights: ► Anodic oxidation is an effective method for degrading o-nitrophenol. ► The effect of operating parameters on the degradation was investigated. ► The main intermediate products were determined by HPLC technique. ► A plausible degradation pathway of o-nitrophenol was proposed. -- Abstract: The electrochemical oxidation of pesticide, o-nitrophenol (ONP) as one kind of pesticide that is potentially dangerous and biorefractory, was studied by galvanostatic electrolysis using boron-doped diamond (BDD) as anode. The influence of several operating parameters, such as applied current density, supporting electrolyte, and initial pH value, was investigated. The best degradation occurred in the presence of Na{sub 2}SO{sub 4} (0.05 M) as conductive electrolyte. After 8 h, nearly complete degradation of o-nitrophenol was achieved (92%) using BDD electrodes at pH 3 and at current density equals 60 mA cm{sup −2}. The decay kinetics of o-nitrophenol follows a pseudo-first-order reaction. Aromatic intermediates such as catechol, resorcinol, 1,2,4-trihydroxybenzene, hydroquinone and benzoquinone and carboxylic acids such as maleic glycolic, malonic, glyoxilic and oxalic, have been identified and followed during the ONP treatment by chromatographic techniques. From these anodic oxidation by-products, a plausible reaction sequence for ONP mineralization on BDD anodes is proposed.

  5. Redetermination of pyridine-4-carbonitrile–chloranilic acid (1/1 at 180 K

    Directory of Open Access Journals (Sweden)

    Hiroyuki Ishida

    2008-07-01

    Full Text Available In the crystal structure of the title compound, C6H4N2·C6H2Cl2O4, two chloranilic acid (systematic name: 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone molecules are connected by O—H...O hydrogen bonds to form a dimeric unit. The pyridine-4-carbonitrile molecules are linked on both sides of the dimer via N...H...O hydrogen bonds to give a centrosymmetric 2:2 complex of pyridine-4-carbonitrile and chloranilic acid. The H atom in the N...H...O hydrogen bond is disordered over two positions with approximately equal occupancies. The pyridine ring makes a dihedral angle of 61.54 (14° with the chloranilic acid plane. The 2:2 units are further linked by intermolecular C—H...O and C—H...Cl hydrogen bonds. This determination presents a siginficantly higher precision crystal structure than the previously published structure [Tomura & Yamasshita (2008. X-ray Struct. Anal. Online, 24, x31–x32].

  6. Photosynthetic redox imbalance influences flavonoid biosynthesis in Lemna gibba.

    Science.gov (United States)

    Akhtar, Tariq A; Lees, Hazel A; Lampi, Mark A; Enstone, Daryl; Brain, Richard A; Greenberg, Bruce M

    2010-07-01

    Plants accumulate flavonoids in response to a myriad of environmental challenges, especially when exposed to ultraviolet (UV) radiation or situations causing oxidative stress. However, the origin and nature of the signal triggering their accumulation remain obscure. In this study, a group of flavonoids belonging to the flavone class was identified in Lemna gibba (duckweed). These flavones accumulated upon exposure to UV radiation, low temperature, copper and the photosynthetic electron transport (PET) inhibitors 2,5-dibromo-3-methyl-6-isopropyl-p-benzoquinone (DBMIB) and 1,2-dihydroxyanthraquinone (DHATQ). All of these stressors were also shown to promote PET chain (PETC) reduction; however, in the co-presence of 3-(3,4-dichlorophenyl)-1,1-dimethyl urea (DCMU) or a light regime that oxidized the PETC, flavonoid accumulation ceased. Chloroplast-derived reactive oxygen species (ROS) were not associated with all of the stress conditions that promoted both PETC reduction and flavonoid synthesis, indicating that ROS were not a strict requisite for flavonoid accumulation. Transcripts for the flavonoid biosynthetic genes, chalcone synthase (CHS) and chalcone isomerase, were similarly responsive to the PETC redox state, as were a panel of transcripts revealed by differential display PCR. Collectively, these results provide evidence that PETC redox status is one of the factors affecting flavonoid biosynthesis. PMID:20199616

  7. Hydrogen bonded NHO chains formed by chloranilic acid (CLA) with 4,4‧-di-t-butyl-2,2‧-bipyridyl (dtBBP) in the solid state

    Science.gov (United States)

    Bator, G.; Sawka-Dobrowolska, W.; Sobczyk, L.; Owczarek, M.; Pawlukojć, A.; Grech, E.; Nowicka-Scheibe, J.

    2012-01-01

    In crystalline state 2,5-dichloro-3,6-dihydroxy-p-benzoquinone (chloranilic acid, CLA) forms with 4,4'-di-t-butyl-2,2'-bipyridyl (dtBBP) the hydrogen bonded chains along the b-axis. From one side of the CLA molecule the proton transfer takes place and the hydrogen bond length is very short (2.615 Å). A continuous infrared absorption is observed for dtBBP·CLA in the wavenumber range between 3100 and 800 cm -1 also indicating the strong hydrogen bonds. The DSC measurements show a weak, close to continuous, phase transition at 414 K. The complex dielectric permittivity for a single crystal sample was measured in the temperature range 100-440 K and at frequencies between 200 Hz and 2 MHz. The dielectric response is a combination of semiconducting properties and a relaxation process most probably connected with the proton dynamics in the hydrogen bonds. The mechanism of the structural phase transition is discussed.

  8. Electric response in the antiferroelectric crystal of 4,4′-di-t-butyl-2,2′-bipyridyl with chloranilic acid

    International Nuclear Information System (INIS)

    Highlights: • The semiconducting properties of the crystals were disclosed in the organic complex. • Dielectric relaxation and dc conductivity were investigated. • Activation energy for the thermally activated processes of the σdc was estimated. • The effect of hydrogen bonds on the mechanism of the phase transition and the electric properties of the crystal was discussed. - Abstract: The electric response was analyzed in the vicinity of the structural phase transition at 412 K in the single crystals of 2,5-dichloro-3,6-dihydroxy-p-benzoquinone (chloranilic acid, CLA) with 4,4′-di-t-butyl-2,2′-bipyridyl (dtBBP). The dielectric permittivity of the complex measured along the b direction between 300 and 440 K and at frequencies ranging from 500 Hz to 2 MHz indicates two phenomena. At low frequencies, dielectric losses are ascribed to the electric conductivity of the crystal, while at high frequencies, to the dielectric relaxation described by means of the Cole–Cole relationship. The parameters of the dielectric response: the relaxation time, τ, the dielectric increment, εο − ε∞, and the distribution parameter of the relaxation time, α, were estimated and analyzed. The low-temperature structure of the crystals indicates the antiferroelectric arrangement of the supramolecular hydrogen bonds. The dielectric results also presented for the deuterated crystals of dtBBP·CLA proved that the dynamics of protons in the hydrogen bonds are responsible for the mechanism of phase transition

  9. Geometry and quadratic nonlinearity of charge transfer complexes in solution: a theoretical study.

    Science.gov (United States)

    Mukhopadhyay, S; Pandey, Ravindra; Das, Puspendu K; Ramasesha, S

    2011-01-28

    In this paper, we have computed the quadratic nonlinear optical (NLO) properties of a class of weak charge transfer (CT) complexes. These weak complexes are formed when the methyl substituted benzenes (donors) are added to strong acceptors like chloranil (CHL) or di-chloro-di-cyano benzoquinone (DDQ) in chloroform or in dichloromethane. The formation of such complexes is manifested by the presence of a broad absorption maximum in the visible range of the spectrum where neither the donor nor the acceptor absorbs. The appearance of this visible band is due to CT interactions, which result in strong NLO responses. We have employed the semiempirical intermediate neglect of differential overlap (INDO∕S) Hamiltonian to calculate the energy levels of these CT complexes using single and double configuration interaction (SDCI). The solvent effects are taken into account by using the self-consistent reaction field (SCRF) scheme. The geometry of the complex is obtained by exploring different relative molecular geometries by rotating the acceptor with respect to the fixed donor about three different axes. The theoretical geometry that best fits the experimental energy gaps, β(HRS) and macroscopic depolarization ratios is taken to be the most probable geometry of the complex. Our studies show that the most probable geometry of these complexes in solution is the parallel displaced structure with a significant twist in some cases.

  10. Protective effects of hydrogen sulfide anions against acetaminophen-induced hepatotoxicity in mice.

    Science.gov (United States)

    Ishii, Isao; Kamata, Shotaro; Hagiya, Yoshifumi; Abiko, Yumi; Kasahara, Tadashi; Kumagai, Yoshito

    2015-12-01

    The key mechanism for hepatotoxicity resulting from acetaminophen (APAP) overdose is cytochrome P450-dependent formation of N-acetyl-p-benzoquinone imine (NAPQI), a potent electrophilic metabolite that forms protein adducts. The fundamental roles of glutathione in the effective conjugation/clearance of NAPQI have been established, giving a molecular basis for the clinical use of N-acetylcysteine as a sole antidote. Recent evidence from in vitro experiments suggested that sulfide anions (S(2-)) to yield hydrogen sulfide anions (HS(-)) under physiological pH could effectively react with NAPQI. This study evaluated the protective roles of HS(-) against APAP-induced hepatotoxicity in mice. We utilized cystathionine γ-lyase-deficient (Cth(-/-)) mice that are highly sensitive to acetaminophen toxicity. Intraperitoneal injection of acetaminophen (150 mg/kg) into Cth(-/-) mice resulted in highly elevated levels of serum alanine/aspartate aminotransferases and lactate dehydrogenase associated with marked increases in oncotic hepatocytes; all of which were significantly inhibited by intraperitoneal preadministration of sodium hydrosulfide (NaHS). NaHS preadministration significantly suppressed APAP-induced serum malondialdehyde level increases without abrogating APAP-induced rapid depletion of hepatic glutathione. These results suggest that exogenous HS(-) protects hepatocytes by directly scavenging reactive NAPQI rather than by increasing cystine uptake and thereby elevating intracellular glutathione levels, which provides a novel therapeutic approach against acute APAP poisoning.

  11. Predictive toxicology using systemic biology and liver microfluidic “on chip” approaches: Application to acetaminophen injury

    Energy Technology Data Exchange (ETDEWEB)

    Prot, Jean-Matthieu [CNRS UMR 6600, Laboratoire de Biomécanique et Bio ingénierie, Université de Technologie de Compiègne, Centre de Recherche de Royallieu, BP20529, F-60205 (France); Bunescu, Andrei; Elena-Herrmann, Bénédicte [Université de Lyon, Centre de RMN à Très Hauts Champs, CNRS/ENS Lyon/UCB Lyon 1, 5 rue de la Doua, F-69100 Villeurbanne (France); Aninat, Caroline [Inserm, UMR991, Liver Metabolisms and Cancer, F-35033 Rennes (France); Université de Rennes 1, F-35043 Rennes (France); Snouber, Leila Choucha [CNRS UMR 6600, Laboratoire de Biomécanique et Bio ingénierie, Université de Technologie de Compiègne, Centre de Recherche de Royallieu, BP20529, F-60205 (France); Griscom, Laurent; Razan, Florence [CNRS-UMR 8029, SATIE, Ecole Normale Supérieure de Cachan-Bretagne, Campus de Ker Lann, Bruz (France); Bois, Frederic Y. [Institut National de l' Environnement Industriel et des Risques (INERIS), Unité Modèles pour l' Ecotoxicologie et la Toxicologie, Parc ALATA, BP2, F-60550 Verneuil en Halatte (France); Legallais, Cécile [CNRS UMR 6600, Laboratoire de Biomécanique et Bio ingénierie, Université de Technologie de Compiègne, Centre de Recherche de Royallieu, BP20529, F-60205 (France); and others

    2012-03-15

    We have analyzed transcriptomic, proteomic and metabolomic profiles of hepatoma cells cultivated inside a microfluidic biochip with or without acetaminophen (APAP). Without APAP, the results show an adaptive cellular response to the microfluidic environment, leading to the induction of anti-oxidative stress and cytoprotective pathways. In presence of APAP, calcium homeostasis perturbation, lipid peroxidation and cell death are observed. These effects can be attributed to APAP metabolism into its highly reactive metabolite, N-acetyl-p-benzoquinone imine (NAPQI). That toxicity pathway was confirmed by the detection of GSH-APAP, the large production of 2-hydroxybutyrate and 3-hydroxybutyrate, and methionine, cystine, and histidine consumption in the treated biochips. Those metabolites have been reported as specific biomarkers of hepatotoxicity and glutathione depletion in the literature. In addition, the integration of the metabolomic, transcriptomic and proteomic collected profiles allowed a more complete reconstruction of the APAP injury pathways. To our knowledge, this work is the first example of a global integration of microfluidic biochip data in toxicity assessment. Our results demonstrate the potential of that new approach to predictive toxicology. -- Highlights: ► We cultivated liver cells in microfluidic biochips ► We integrated transcriptomic, proteomic and metabolomics profiles ► Pathways reconstructions were proposed in control and acetaminophen treated cultures ► Biomarkers were identified ► Comparisons with in vivo studies were proposed.

  12. The effect of propylene glycol on the P450-dependent metabolism of acetaminophen and other chemicals in subcellular fractions of mouse liver

    Energy Technology Data Exchange (ETDEWEB)

    Snawder, J.E.; Benson, R.W.; Leakey, J.E.A.; Roberts, D.W. (National Center for Toxicological Research, Jefferson, AR (United States))

    1993-01-01

    Propylene glycol (PG) decreases the hepatotoxicity of acetominophen (APAP). To elucidate the mechanism for this response, the authors measured the effect of PG on the in vitro metabolism of APAP by subcellular liver fractions from 6-10 week-old male B6C3F1 mice. The fractions were assayed for their ability to bioactivate APAP to N-acetyl-p-benzoquinone imine, which was trapped as APAP-glutathione conjugates or APAP-protein adducts, and for dimethyl-nitrosamine-N-demethylase (DMN), 4-nitrophenol hydroxylase (4-NPOH), and phenacetin-O-deethylase (PAD) activities. Activity in the crude mitochondrial-rich (10,000 [times] g pellet) fraction was low and PG had no effect. PG inhibited DMN and 4-NPOH, indicators of IIE1-dependent activity, and the formation of APAP-glutathione conjugates and APAP-protein adducts in both heavy (15,000 [times] g pellet) and light (100,000 [times] g pellet) microsomes. PAD, a measure of IA2-dependent activity, was not inhibited. These data demonstrate that PG selectively inhibits IIE1 activity, including the bioactivation of APAP, and implicates this as the mechanism for PG-mediated protection of APAP hepatotoxicity in mice. 27 refs., 1 fig., 1 tab.

  13. Controlled Defects of Zinc Oxide Nanorods for Efficient Visible Light Photocatalytic Degradation of Phenol

    Directory of Open Access Journals (Sweden)

    Jamal Al-Sabahi

    2016-03-01

    Full Text Available Environmental pollution from human and industrial activities has received much attention as it adversely affects human health and bio-diversity. In this work we report efficient visible light photocatalytic degradation of phenol using supported zinc oxide (ZnO nanorods and explore the role of surface defects in ZnO on the visible light photocatalytic activity. ZnO nanorods were synthesized on glass substrates using a microwave-assisted hydrothermal process, while the surface defect states were controlled by annealing the nanorods at various temperatures and were characterized by photoluminescence and X-ray photoelectron spectroscopy. High performance liquid chromatography (HPLC was used for the evaluation of phenol photocatalytic degradation. ZnO nanorods with high surface defects exhibited maximum visible light photocatalytic activity, showing 50% degradation of 10 ppm phenol aqueous solution within 2.5 h, with a degradation rate almost four times higher than that of nanorods with lower surface defects. The mineralization process of phenol during degradation was also investigated, and it showed the evolution of different photocatalytic byproducts, such as benzoquinone, catechol, resorcinol and carboxylic acids, at different stages. The results from this study suggest that the presence of surface defects in ZnO nanorods is crucial for its efficient visible light photocatalytic activity, which is otherwise only active in the ultraviolet region.

  14. Idebenone protects against retinal damage and loss of vision in a mouse model of Leber's hereditary optic neuropathy.

    Directory of Open Access Journals (Sweden)

    Fabrice D Heitz

    Full Text Available Leber's hereditary optic neuropathy (LHON is an inherited disease caused by mutations in complex I of the mitochondrial respiratory chain. The disease is characterized by loss of central vision due to retinal ganglion cell (RGC dysfunction and optic nerve atrophy. Despite progress towards a better understanding of the disease, no therapeutic treatment is currently approved for this devastating disease. Idebenone, a short-chain benzoquinone, has shown promising evidence of efficacy in protecting vision loss and in accelerating recovery of visual acuity in patients with LHON. It was therefore of interest to study suitable LHON models in vitro and in vivo to identify anatomical correlates for this protective activity. At nanomolar concentrations, idebenone protected the rodent RGC cell line RGC-5 against complex I dysfunction in vitro. Consistent with the reported dosing and observed effects in LHON patients, we describe that in mice, idebenone penetrated into the eye at concentrations equivalent to those which protected RGC-5 cells from complex I dysfunction in vitro. Consequently, we next investigated the protective effect of idebenone in a mouse model of LHON, whereby mitochondrial complex I dysfunction was caused by exposure to rotenone. In this model, idebenone protected against the loss of retinal ganglion cells, reduction in retinal thickness and gliosis. Furthermore, consistent with this protection of retinal integrity, idebenone restored the functional loss of vision in this disease model. These results support the pharmacological activity of idebenone and indicate that idebenone holds potential as an effective treatment for vision loss in LHON patients.

  15. Idebenone: A Review in Leber's Hereditary Optic Neuropathy.

    Science.gov (United States)

    Lyseng-Williamson, Katherine A

    2016-05-01

    Idebenone (Raxone(®)), a short-chain benzoquinone, is the only disease-specific drug approved to treat visual impairment in adolescents and adults with Leber's hereditary optic neuropathy (LHON), a rare genetic mitochondrial disease that causes rapid and progressive bilateral vision loss. The mechanism of action of idebenone involves its antioxidant properties and ability to act as a mitochondrial electron carrier. Idebenone overcomes mitochondrial complex I respiratory chain deficiency in patients with LHON by transferring electrons directly to mitochondrial complex III (by-passing complex I), thereby restoring cellular energy (ATP) production and re-activating inactive-but-viable retinal ganglion cells, which ultimately prevents further vision loss and promotes vision recovery. The approval of idebenone in the treatment of LHON was based on the overall data from a randomized clinical trial, a follow-up study and real-world data. Taken together, these studies provide convincing evidence that oral idebenone 900 mg/day for 24 weeks has persistent beneficial effects in preventing further vision impairment and promoting vision recovery in patients with LHON relative to the natural course of the disease. Therefore, idebenone is a valuable agent to treat visual impairment in adolescents and adults with LHON.

  16. Idebenone protects against retinal damage and loss of vision in a mouse model of Leber's hereditary optic neuropathy.

    Science.gov (United States)

    Heitz, Fabrice D; Erb, Michael; Anklin, Corinne; Robay, Dimitri; Pernet, Vincent; Gueven, Nuri

    2012-01-01

    Leber's hereditary optic neuropathy (LHON) is an inherited disease caused by mutations in complex I of the mitochondrial respiratory chain. The disease is characterized by loss of central vision due to retinal ganglion cell (RGC) dysfunction and optic nerve atrophy. Despite progress towards a better understanding of the disease, no therapeutic treatment is currently approved for this devastating disease. Idebenone, a short-chain benzoquinone, has shown promising evidence of efficacy in protecting vision loss and in accelerating recovery of visual acuity in patients with LHON. It was therefore of interest to study suitable LHON models in vitro and in vivo to identify anatomical correlates for this protective activity. At nanomolar concentrations, idebenone protected the rodent RGC cell line RGC-5 against complex I dysfunction in vitro. Consistent with the reported dosing and observed effects in LHON patients, we describe that in mice, idebenone penetrated into the eye at concentrations equivalent to those which protected RGC-5 cells from complex I dysfunction in vitro. Consequently, we next investigated the protective effect of idebenone in a mouse model of LHON, whereby mitochondrial complex I dysfunction was caused by exposure to rotenone. In this model, idebenone protected against the loss of retinal ganglion cells, reduction in retinal thickness and gliosis. Furthermore, consistent with this protection of retinal integrity, idebenone restored the functional loss of vision in this disease model. These results support the pharmacological activity of idebenone and indicate that idebenone holds potential as an effective treatment for vision loss in LHON patients.

  17. Development and Validation of Spectrophotometric Methods for the Determination of Rasagiline in Pharmaceutical Preparations

    Directory of Open Access Journals (Sweden)

    Serife Evrim Kepekci Tekkeli

    2013-01-01

    Full Text Available This study presents three simple, rapid, and accurate spectrophotometric methods for the determination of Rasagiline (RSG in pharmaceutical preparations. The determination procedures depend on the reaction of RSG with chloranilic acid for method A, tetrachloro-1,4-benzoquinone for method B, and 7,7,8,8-tetracyanoquinodimethane for method C. The colored products were quantitated spectrophotometrically at 524, 535, and 843 nm for methods A, B, and C, respectively. Different variables affecting the reaction were optimized. Linearity ranges of the methods with good correlation coefficients (0.9988–0.9996 were observed as 25–300 µg mL−1, 25–350 µg mL−1, and 50–500 µg mL−1 for methods A, B, and C, respectively. The formation of products takes place through different mechanisms. The sites of interaction were confirmed by elemental analysis using IR and 1H-NMR spectroscopy. The validation of the methods was carried out in terms of specificity, linearity, accuracy, precision, robustness, limit of detection, and limit of quantitation. No interference was observed from concomitants usually present in dosage forms. The methods were applied successfully to the determination of RSG in pharmaceutical preparations.

  18. [Development and application of electroanalytical methods in biomedical fields].

    Science.gov (United States)

    Kusu, Fumiyo

    2015-01-01

    To summarize our electroanalytical research in the biomedical field over the past 43 years, this review describes studies on specular reflection measurement, redox potential determination, amperometric acid sensing, HPLC with electrochemical detection, and potential oscillation across a liquid membrane. The specular reflection method was used for clarifying the adsorption of neurotransmitters and their related drugs onto a gold electrode and the interaction between dental alloys and compound iodine glycerin. A voltammetric screening test using a redox potential for the antioxidative effect of flavonoids was proposed. Amperometric acid sensing based on the measurement of the reduction prepeak current of 2-methyl-1,4-naphthoquinone (VK3) or 3,5-di-tert-buty1-1,2-benzoquinone (DBBQ) was applied to determine acid values of fats and oils, titrable acidity of coffee, and enzyme activity of lipase, free fatty acids (FFAs) in serum, short-chain fatty acids in feces, etc. The electrode reactions of phenothiazines, catechins, and cholesterol were applied to biomedical analysis using HPLC with electrochemical detection. A three-channel electrochemical detection system was utilized for the sensitive determination of redox compounds in Chinese herbal medicines. The behavior of barbituric acid derivatives was examined based on potential oscillation measurements.

  19. Electric response in the antiferroelectric crystal of 4,4‧-di-t-butyl-2,2‧-bipyridyl with chloranilic acid

    Science.gov (United States)

    Rok, M.; Piecha-Bisiorek, A.; Szklarz, P.; Bator, G.; Sobczyk, L.

    2015-05-01

    The electric response was analyzed in the vicinity of the structural phase transition at 412 K in the single crystals of 2,5-dichloro-3,6-dihydroxy-p-benzoquinone (chloranilic acid, CLA) with 4,4‧-di-t-butyl-2,2‧-bipyridyl (dtBBP). The dielectric permittivity of the complex measured along the b direction between 300 and 440 K and at frequencies ranging from 500 Hz to 2 MHz indicates two phenomena. At low frequencies, dielectric losses are ascribed to the electric conductivity of the crystal, while at high frequencies, to the dielectric relaxation described by means of the Cole-Cole relationship. The parameters of the dielectric response: the relaxation time, τ, the dielectric increment, εο - ε∞, and the distribution parameter of the relaxation time, α, were estimated and analyzed. The low-temperature structure of the crystals indicates the antiferroelectric arrangement of the supramolecular hydrogen bonds. The dielectric results also presented for the deuterated crystals of dtBBP·CLA proved that the dynamics of protons in the hydrogen bonds are responsible for the mechanism of phase transition.

  20. Overexpression of the human HAP1 protein sensitizes cells to the lethal effect of bioreductive drugs.

    Science.gov (United States)

    Prieto-Alamo, M J; Laval, F

    1999-03-01

    Abasic sites (AP sites) are generated in DNA either directly by DNA-damaging agents or by DNA glycosylases acting during base excision repair. These sites are repaired in human cells by the HAP1 protein, which, besides its AP-endonuclease activity, also possesses a redox function. To investigate the ability of HAP1 protein to modulate cell resistance to DNA-damaging agents, CHO cells were transfected with HAP1 cDNA, resulting in stable expression of the protein in the cell nuclei. The sensitivity of the transfected cells to the toxic effect of various agents, e.g. methylmethane sulfonate, bleomycin and H2O2, was not modified. However, the transfected cells became more sensitive to killing by mitomycin C, porfiromycin, daunorubicin and aziridinyl benzoquinone, drugs that are activated by reduction. To test whether the redox function of HAP1 protein was involved in this increased cytotoxicity, we have constructed a mutated HAP1 protein endowed with normal AP-endonuclease activity but deleted for redox function. When this mutated protein was expressed in the cells, elevated AP-endonuclease activity was measured, but sensitization to the lethal effects of compounds requiring bioreduction was no longer observed. These results suggest that HAP1 protein, besides its involvement in DNA repair, is able to activate bioreduction of alkylating drugs used in cancer chemotherapy. PMID:10190555

  1. Self-assembled arene-ruthenium-based rectangles for the selective sensing of multi-carboxylate anions.

    Science.gov (United States)

    Vajpayee, Vaishali; Song, Young Ho; Lee, Min Hyung; Kim, Hyunuk; Wang, Ming; Stang, Peter J; Chi, Ki-Whan

    2011-07-01

    Novel arene-ruthenium [2+2] metalla-rectangles 4 and 5 have been synthesized by self-assembly using dipyridyl amide ligand 3 and arene-ruthenium acceptors (arene: benzoquinone (1), naphthacenedione (2)) and characterized by NMR spectroscopy and ESI-MS. The solid-state structure of 5 was determined by X-ray diffraction and shows encapsulated diethyl ether molecule in the rectangular cavity of 5. The luminescent 5 was further used for anion sensing with the amidic linkage serving as a hydrogen-bond donor site for anions and the ruthenium moiety serving as a signaling unit. A UV/Vis titration study demonstrated that although 5 interacts very weakly with common monoanions as well as with flexible dicarboxylate anions such as malonate and succinate, it displays significant binding affinity (K>10(3) in MeOH) for rigid multi-carboxylate anions such as oxalate, citrate, and tartrate, exhibiting a 1:1 stoichiometry. It has been suggested that 1:1 bidentate hydrogen bonding assisted by appropriate geometrical complementarity is mainly responsible for the increased affinity of 5 towards such anions. A fluorescence titration study revealed a large fluorescence enhancement of 5 upon binding to multi-carboxylate anions, which can be attributed to the blocking of the photoinduced electron-transfer process from the arene-Ru moiety to the amidic donor in 5 as a result of hydrogen bonding between the donor and the anion.

  2. Microwave enhanced electroanalysis of formulations: processes in micellar media at glassy carbon and at platinum electrodes.

    Science.gov (United States)

    Ghanem, Mohamed A; Compton, Richard G; Coles, Barry A; Canals, Antonio; Marken, Frank

    2005-10-01

    The direct electroanalysis of complex formulations containing alpha-tocopherol (vitamin E) is possible in micellar solution and employing microwave-enhanced voltammetry. In the presence of microwave radiation substantial heating and current enhancement effects have been observed at 330 microm diameter glassy carbon electrodes placed into a micellar aqueous solution and both hydrophilic and highly hydrophobic redox systems are detected. For the water soluble Fe(CN)(6)(3-/4-) redox system in micellar aqueous solutions of 0.1 M NaCl and 0.1 M sodium dodecylsulfate (SDS) at low to intermediate microwave power, thermal effects and convection effects are observed. At higher microwave power, thermal cavitation is induced and dominates the mass transport at the electrode surface. For the micelle-soluble redox systems tert-butylferrocene and 2,5-di-tert-butyl-1,4-benzoquinone, strong and concentration dependent current responses are observed only in the presence of microwave radiation. For the oxidation of micelle-soluble alpha-tocopherol current responses at glassy carbon electrodes are affected by adsorption and desorption processes whereas at platinum electrodes, analytical limiting currents are obtained over a wide range of alpha-tocopherol concentrations. However, for the determination of alpha-tocopherol in a commercial formulation interference from proteins is observed at platinum electrodes and direct measurements are possible only over a limited concentration range and at glassy carbon electrodes.

  3. Bioelectrocatalytic and biosensing properties of horseradish peroxidase covalently immobilized on (3-aminopropyl)trimethoxysilane-modified titanate nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Sovic, David [Laboratory for General and Inorganic Chemistry and Electroanalysis, Faculty of Food Technology and Biotechnology, University of Zagreb, Pierottijeva 6, HR-10000 Zagreb (Croatia); Gajovic, Andreja [Molecular Physics Laboratory, Ruder Boskovic Institute, Bijenicka 54, HR-10000 Zagreb (Croatia); Ivekovic, Damir, E-mail: divekov@pbf.hr [Laboratory for General and Inorganic Chemistry and Electroanalysis, Faculty of Food Technology and Biotechnology, University of Zagreb, Pierottijeva 6, HR-10000 Zagreb (Croatia)

    2011-11-30

    Titanate nanotubes (TiNT) surface modified with (3-aminopropyl)trimethoxysilane were employed as a support for covalent immobilization of horseradish peroxidase (HRP) by using 1,4-benzoquinone as a coupling agent. Composite film-electrodes consisting of HRP-modified TiNT embedded into the porous carbon powder/Nafion matrix were fabricated and their applicability in direct bioelectrocatalytic reduction of H{sub 2}O{sub 2} and H{sub 2}O{sub 2} biosensing were investigated. An efficient direct electron transfer between the immobilized HRP molecules and the electrode was observed in the presence of H{sub 2}O{sub 2} at potentials lower than 600 mV (vs. Hg/Hg{sub 2}Cl{sub 2}/3.5 M KCl). For the HRP-TiNT-modified electrodes polarized at 0 mV, a linear dependence of the bioelectrocatalytic current on the concentration of H{sub 2}O{sub 2} was observed up to the concentration of H{sub 2}O{sub 2} equal to 10 {mu}M, with the sensitivity of (1.10 {+-} 0.01) AM{sup -1} cm{sup -2} and the detection limit of 35 nM.

  4. Pyridine-H5PMo10V2O40 hybrid catalysts for liquid-phase hydroxylation of benzene to phenol with molecular oxygen

    Institute of Scientific and Technical Information of China (English)

    GE HanQing; LENG Yan; ZHANG FuMin; PIAO JiaRui; ZHOU ChangJiang; WANG Jun

    2009-01-01

    Pyridine(Py)-modified Keggin-type vanadium-substituted heteropoly acids (PynPMo10V2O40,n=1 to 5) were prepared by a precipitation method as organic/inorganic hybrid catalysts for direct hydroxylation of benzene to phenol in a pressured batch reactor and their structures were detected by FT-IR.Among various catalysts,Py3PMo10V2O40 exhibits the highest catalytic activity (yield of phenol,11.5%),without observing the formation of catechol,hydroquinone and benzoquinone in the reaction with 80 vol% aqueous acetic acid,molecular oxygen and ascorbic acid used as the solvent,oxidant and reducing reagent,respectively.Influences of reaction temperature,reaction time,oxygen pressure,amount of ascorbic acid and catalyst on yield of phenol were investigated to obtain the optimal reaction conditions for phenol formation.Pyridine can greatly promote the catalytic activity of the Py-free catalyst (H5PMo10V2O40),mostly because the organic π electrons in the hybrid catalyst may extend their conjugation to the inorganic framework of heteropoly acid and dramatically modify the redox properties,at the same time,pyridine adsorbed on heteropoly acids can promote the effect of "pseudo-liquid phase",thus accounting for the enhancement of phenol yield.

  5. Electrochemical studies of redox probes in self-organized lyotropic liquid crystalline systems

    Indian Academy of Sciences (India)

    P Suresh Kumar; V Lakshminarayanan

    2009-09-01

    Lyotropic liquid crystalline phases formed by surfactants are of special importance due to their close resemblance to biological systems. The redox reactions in such ordered media are of fundamental interest in understanding several complex processes occurring in the biological media, where the former can act as model systems. In this work, we have carried out the redox reactions of benzoquinone| hydroquinone, methyl viologen and ferrocenemethanol probes in a lyotropic hexagonal columnar phase (H1 phase) using cyclic voltammetry and electrochemical impedance spectroscopic studies. The liquid crystalline phase we have studied is made up of the non-ionic surfactant, Triton X-100 and water. Polarizing optical microscopic examination confirmed that the columnar hexagonal phase is retained even after the addition of redox probe as well as the supporting electrolyte. Our studies show a significant shift in the half-peak potentials of the redox probes in the H1 phase as compared to the solvent phase. The diffusion coefficient values for different redox probes in the H1 phase were also found to be significantly reduced when compared to the corresponding solvent media.

  6. Interaction of 2-aminopyrimidine with σ- and π-acceptors involving chemical reactions via initial charge transfer complexation

    Science.gov (United States)

    Rabie, U. M.; Abou-El-Wafa, M. H.; Mohamed, R. A.

    2007-12-01

    Interaction of 2-aminopyrimidine (AP) with iodine as a typical σ-type acceptor and with a typical π-type acceptor, 2,3,5,6-tetrachloro-1,4-benzoquinone, p-chloranil (CHL) have been studied spectrophotometrically. Electronic absorption spectra of the system AP-I 2 in several organic solvents of different polarities have performed clear charge transfer (CT) band(s). Formation constants ( KCT) and molar absorption coefficients ( ɛCT) and thermodynamic properties, Δ H, Δ S, and Δ G, of this system in various organic solvents were determined and discussed. Interaction of AP with the π-acceptor has shown unique behaviors. Chemical reaction has occurred via prior or initial formation of the outer-sphere CT complex followed by formation of the corresponding anion radicals, CHL rad - , as intermediates. UV-vis, 1H NMR, Mass, and FT-IR spectra in addition to the elemental analysis were used to confirm the proposed occurrence of the chemical reaction and to investigate the synthesized solid products.

  7. Antioxidant compounds from the stem bark of Garcinia atroviridis.

    Science.gov (United States)

    Tan, Wen-Nee; Khairuddean, Melati; Wong, Keng-Chong; Tong, Woei-Yenn; Ibrahim, Darah

    2016-08-01

    A new xanthone, namely garcinexanthone G (1), along with eight known compounds, stigmasta-5,22-dien-3β-ol (2), stigmasta-5,22-dien-3-O-β-glucopyranoside (3), 3β-acetoxy-11α,12α-epoxyoleanan-28,13β-olide (4), 2,6-dimethoxy-p-benzoquinone (5), 1,3,5-trihydroxy-2-methoxyxanthone (6), 1,3,7-trihydroxyxanthone (7), kaempferol (8) and quercetin (9), were isolated from the stem bark of Garcinia atroviridis. Their structures were elucidated based on spectroscopic methods including nuclear magnetic resonance (NMR-1D and 2D), UV, IR, and mass spectrometry. All the isolated compounds were evaluated for their antioxidant properties based on the DPPH radical scavenging activities. Results showed that 1,3,7-trihydroxyxanthone and quercetin showed significant antioxidant activities with EC50 values of 16.20 and 12.68 μg/ml, respectively, as compared to the control, ascorbic acid (7.4 μg/ml). PMID:26999039

  8. Pyranose 2-oxidase from Phanerochaete chrysosporium--expression in E. coli and biochemical characterization.

    Science.gov (United States)

    Pisanelli, Ines; Kujawa, Magdalena; Spadiut, Oliver; Kittl, Roman; Halada, Petr; Volc, Jindrich; Mozuch, Michael D; Kersten, Philip; Haltrich, Dietmar; Peterbauer, Clemens

    2009-06-15

    The presented work reports the isolation and heterologous expression of the p2ox gene encoding the flavoprotein pyranose 2-oxidase (P2Ox) from the basidiomycete Phanerochaete chrysosporium. The p2ox cDNA was inserted into the bacterial expression vector pET21a(+) and successfully expressed in Escherichia coli. We obtained active, fully flavinylated recombinant P2Ox in yields of approximately 270 mg/l medium. The recombinant enzyme was provided with an N-terminal T7-tag and a C-terminal His(6)-tag to facilitate simple one-step purification. We obtained an apparently homogenous enzyme preparation with a specific activity of 16.5 U/mg. Recombinant P2Ox from P. chrysosporium was characterized in some detail with respect to its physical and catalytic properties, both for electron donor (sugar substrates) and - for the first time - alternative electron acceptors (1,4-benzoquinone, substituted quinones, 2,6-dichloroindophenol and ferricenium ion). As judged from the catalytic efficiencies k(cat)/K(m), some of these alternative electron acceptors are better substrates than oxygen, which might have implications for the proposed in vivo function of pyranose 2-oxidase. PMID:19501263

  9. Co(salophen)-Catalyzed Aerobic Oxidation of p-Hydroquinone: Mechanism and Implications for Aerobic Oxidation Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Anson, Colin W.; Ghosh, Soumya; Hammes-Schiffer, Sharon; Stahl, Shannon S.

    2016-03-30

    Macrocyclic metal complexes and p-benzoquinones are commonly used as co-catalytic redox mediators in aerobic oxidation reactions. In an effort to gain insight into the mechanism and energetic efficiency of these reactions, we investigated Co(salophen)-catalyzed aerobic oxidation of p-hydroquinone. Kinetic and spectroscopic data suggest that the catalyst resting-state consists of an equilibrium between a CoII(salophen) complex, a CoIII-superoxide adduct, and a hydrogen-bonded adduct between the hydroquinone and the CoIII–O2 species. The kinetic data, together with density functional theory data, suggest that the turnover-limiting step features proton-coupled electron transfer from a semi-hydroquinone species and a CoIII-hydroperoxide intermediate. Additional experimental and computational data suggest that a coordinated H2O2 intermediate oxidizes a second equivalent of hydroquinone. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. The NSF provided partial support for the EPR instrumentation (NSF CHE-0741901).

  10. New insights into the chemistry of Coenzyme Q-0: A voltammetric and spectroscopic study.

    Science.gov (United States)

    Gulaboski, Rubin; Bogeski, Ivan; Kokoskarova, Pavlinka; Haeri, Haleh H; Mitrev, Sasa; Stefova, Marina; Stanoeva, Jasmina Petreska; Markovski, Velo; Mirčeski, Valentin; Hoth, Markus; Kappl, Reinhard

    2016-10-01

    Coenzyme Q-0 (CoQ-0) is the only Coenzyme Q lacking an isoprenoid group on the quinoid ring, a feature important for its physico-chemical properties. Here, the redox behavior of CoQ-0 in buffered and non-buffered aqueous media was examined. In buffered aqueous media CoQ-0 redox chemistry can be described by a 2-electron-2-proton redox scheme, characteristic for all benzoquinones. In non-buffered media the number of electrons involved in the electrode reaction of CoQ-0 is still 2; however, the number of protons involved varies between 0 and 2. This results in two additional voltammetric signals, attributed to 2-electrons-1H(+) and 2-electrons-0H(+) redox processes, in which mono- and di-anionic compounds of CoQ-0 are formed. In addition, CoQ-0 exhibits a complex chemistry in strong alkaline environment. The reaction of CoQ-0 and OH(-) anions generates several hydroxyl derivatives as products. Their structures were identified with HPLC/MS. The prevailing radical reaction mechanism was analyzed by electron paramagnetic resonance spectroscopy. The hydroxyl derivatives of CoQ-0 have a strong antioxidative potential and form stable complexes with Ca(2+) ions. In summary, our results allow mechanistic insights into the redox properties of CoQ-0 and its hydroxylated derivatives and provide hints on possible applications. PMID:27268099

  11. Promoting solution phase discharge in Li-O2 batteries containing weakly solvating electrolyte solutions

    Science.gov (United States)

    Gao, Xiangwen; Chen, Yuhui; Johnson, Lee; Bruce, Peter G.

    2016-08-01

    On discharge, the Li-O2 battery can form a Li2O2 film on the cathode surface, leading to low capacities, low rates and early cell death, or it can form Li2O2 particles in solution, leading to high capacities at relatively high rates and avoiding early cell death. Achieving discharge in solution is important and may be encouraged by the use of high donor or acceptor number solvents or salts that dissolve the LiO2 intermediate involved in the formation of Li2O2. However, the characteristics that make high donor or acceptor number solvents good (for example, high polarity) result in them being unstable towards LiO2 or Li2O2. Here we demonstrate that introduction of the additive 2,5-di-tert-butyl-1,4-benzoquinone (DBBQ) promotes solution phase formation of Li2O2 in low-polarity and weakly solvating electrolyte solutions. Importantly, it does so while simultaneously suppressing direct reduction to Li2O2 on the cathode surface, which would otherwise lead to Li2O2 film growth and premature cell death. It also halves the overpotential during discharge, increases the capacity 80- to 100-fold and enables rates >1 mA cmareal-2 for cathodes with capacities of >4 mAh cmareal-2. The DBBQ additive operates by a new mechanism that avoids the reactive LiO2 intermediate in solution.

  12. Redetermined structure, inter-molecular inter-actions and absolute configuration of royleanone.

    Science.gov (United States)

    Fun, Hoong-Kun; Chantrapromma, Suchada; Salae, Abdul Wahab; Razak, Ibrahim Abdul; Karalai, Chatchanok

    2011-05-01

    The structure of the title diterpenoid, C(20)H(28)O(3), {systematic name: (4bS,8aS)-3-hy-droxy-2-isopropyl-4b,8,8-trimethyl-4b,5,6,7,8,8a,9,10-octa-hydro-phenanthrene-1,4-dione} is confirmed [Eugster et al. (1993 ▶). Private communication (refcode HACGUN). CCDC, Union Road, Cambridge] and its packing is now described. Its absolute structure was established by refinement against data collected with Cu radiation: the two stereogenic centres both have S configurations. One cyclo-hexane ring adopts a chair conformation whereas the other cyclo-hexane ring is in a half-chair conformation and the benzoquinone ring is slightly twisted. An intra-molecular O-H⋯O hydrogen bond generates an S(5) ring motif. In the crystal, mol-ecules are linked into chains along [010] by O-H⋯O hydrogen bonds and weak C-H⋯O inter-actions. The packing also features C⋯O [3.131 (3) Å] short contacts. PMID:21754362

  13. Synthesis, Half-Wave Potentials and Antiproliferative Activity of 1-Aryl-substituted Aminoisoquinolinequinones

    Directory of Open Access Journals (Sweden)

    Juana Andrea Ibacache

    2014-01-01

    Full Text Available The synthesis of a variety of 1-aryl-7-phenylaminoisoquinolinequinones from 1,4-benzoquinone and arylaldehydes via the respective 1-arylisoquinolinequinones is reported. The cyclic voltammograms of the new compounds exhibit two one-electron reduction waves to the corresponding radical-anion and dianion and two quasi-reversible oxidation peaks. The half-wave potential values (EI½ of the members of the series have proven sensitive to the electron-donor effect of the aryl group (phenyl, 2-thienyl, 2-furyl at the 1-position as well as to the phenylamino groups (anilino, p-anisidino at the 7-position. The antiproliferative activity of the new compounds was evaluated in vitro using the MTT colorimetric method against one normal cell line (MRC-5 lung fibroblasts and two human cancer cell lines: AGS human gastric adenocarcinoma and HL-60 human promyelocytic leukemia cells in 72-h drug exposure assays. Among the series, compounds 5a, 5b, 5g, 5h, 6a and 6d exhibited interesting antiproliferative activities against human gastric adenocarcinoma. The 1-arylisoquinolinequinone 6a was found to be the most promising active compound against the tested cancer cell lines in terms of IC50 values (1.19; 1.24 µM and selectivity index (IS: 3.08; 2.96, respect to the anti-cancer agent etoposide used as reference (IS: 0.57; 0.14.

  14. Ultrasensitive electrochemical immunoassay for DNA methyltransferase activity and inhibitor screening based on methyl binding domain protein of MeCP2 and enzymatic signal amplification.

    Science.gov (United States)

    Yin, Huanshun; Zhou, Yunlei; Xu, Zhenning; Wang, Mo; Ai, Shiyun

    2013-11-15

    In this work, we fabricated a novel electrochemical immunosensor for detection of DNA methylation, analysis of DNA MTase activity and screening of MTase inhibitor. The immunosensor was on the basis of methyl binding domain protein of MeCP2 as DNA CpG methylation recognization unit, anti-His tag antibody as "immuno-bridge" and horseradish peroxidase labeled immuneglobulin G functionalized gold nanoparticles (AuNPs-IgG-HRP) as signal amplification unit. In the presence of M. SssI MTase, the symmetrical sequence of 5'-CCGG-3' was methylated and then recognized by MeCP2 protein. By the immunoreactions, anti-His tag antibody and AuNPs-IgG-HRP was captured on the electrode surface successively. Under the catalysis effect of HRP towards hydroquinone oxidized by H2O2, the electrochemical reduction signal of benzoquinone was used to analyze M. SssI MTase activity. The electrochemical reduction signal demonstrated a wide linear relationship with M. SssI concentration ranging from 0.05 unit/mL to 90 unit/mL, achieving a detection limit of 0.017 unit/mL (S/N=3). The most important advantages of this method were its high sensitivity and good selectivity, which enabled the detection of even one-base mismatched sequence. In addition, we also verified that the developed method could be applied for screening the inhibitors of DNA MTase and for developing new anticancer drugs.

  15. Spectrophotometric method for the determination, validation, spectroscopic and thermal analysis of diphenhydramine in pharmaceutical preparation

    Science.gov (United States)

    Ulu, Sevgi Tatar; Elmali, Fikriye Tuncel

    2010-09-01

    A sensitive, simple and rapid spectrophotometric method was developed for the determination of diphenhydramine in pharmaceutical preparation. The method was based on the charge-transfer complex of the drug, as n-electron donor, with 2,3-dichloro-5,6-dicyano- p-benzoquinone (DDQ), as π-acceptor. The formation of this complex was also confirmed by UV-vis, FTIR and 1H NMR spectra techniques and thermal analysis. The proposed method was validated according to the ICH guidelines with respect to linearity, limit of detection, limit of quantification, accuracy, precision, recovery and robustness. The linearity range for concentrations of diphenhydramine was found to be 12.5-150 μg/mL with acceptable correlation coefficients. The detection and quantification limits were found to be 2.09 and 6.27 μg/mL, respectively. The proposed and references methods were applied to the determination of drug in syrup. This preparation were also analyzed with an reference method and statistical comparison by t- and F-tests revealed that there was no significant difference between the results of the two methods with respect to mean values and standard deviations at the 95% confidence level.

  16. Fennel and raspberry leaf as possible inhibitors of acetaminophen oxidation.

    Science.gov (United States)

    Langhammer, Astrid Jordet; Nilsen, Odd Georg

    2014-10-01

    In addition to CYP2E1, several CYP isoenzymes, notably CYP1A2, 2D6, and 3A4, are suggested to contribute in acetaminophen oxidation and formation of the hepatotoxic metabolite N-acetyl-p-benzoquinone imine (NAPQI). The in vitro CYP2E1 inhibitory potentials of fennel and raspberry leaf, herbs previously found to inhibit CYP1A2, 2D6, and 3A4 activities in vitro, were investigated. Extracts from commercially available herbal products were incubated with recombinant cDNA-expressed human CYP2E1. A validated LC/MS/MS methodology was applied for determination of 6-hydroxychlorzoxazone formation with disulfiram used as a positive inhibitory control. CYP2E1 IC50 inhibition constants were found to be 23 ± 4 and 27 ± 5 µg/ml for fennel and raspberry leaf, respectively, constants significantly lower than those presented in the literature for other herbal extracts. Together with previous findings, the presented in vitro data for CYP2E1 inhibition suggest that fennel and raspberry leaf have a significant potential of inhibiting all the major metabolic pathways for acetaminophen oxidation and NAPQI formation. Both herbs should be further investigated for their in vivo ability of inhibiting acetaminophen oxidation and NAPQI formation.

  17. Simultaneous removal of phenol, Cu and Cd from water with corn cob silica-alginate beads.

    Science.gov (United States)

    Shim, Jaehong; Lim, Jeong-Muk; Shea, Patrick J; Oh, Byung-Taek

    2014-05-15

    Phenol and heavy metals in petroleum waste are environmental and human health concerns, but physicochemical removal is often cost-prohibitive and can produce toxic secondary products and treatment residues. An environmentally benign alternative combines corn cob silica with alginate and immobilized bacteria into beads for treating contaminated water. The concentration of phenol was decreased >92% by Pseudomonas putida YNS1 on aliginate-silica beads (2%, w/v) after equilibrating for 96h with water containing 214mg phenol/L. GC-MS analysis indicated formation of benzoquinone and other polar products. Beads containing corn cob silica decreased Cu concentrations by 84-88% and Cd by 83-87% within 24h. In a mixture of 114mg phenol, 43mg Cu and 51mg Cd/L, phenol removal (93% within 96h) only occurred with beads containing the silica and bacterial strain. Beads containing corn cob silica removed >97% of the Cu and >99% of the Cd, critical for reducing toxicity to the bacteria. Beads with the immobilized strain removed phenol when zeolite was used instead of corn cob silica, but beads with silica were more effective for Cu and Cd removal. Results show the potential of corn cob silica combined with alginate and immobilized bacteria for removing phenol and heavy metals from contaminated water. PMID:24685529

  18. Determination of Eicosapentaenoic, Docosahexaenoic, and Arachidonic Acids in Human Plasma by High-Performance Liquid Chromatography with Electrochemical Detection.

    Science.gov (United States)

    Kotani, Akira; Watanabe, Mizuki; Yamamoto, Kazuhiro; Kusu, Fumiyo; Hakamata, Hideki

    2016-01-01

    A high-performance liquid chromatography with electrochemical detection (HPLC-ECD) system was developed for the simultaneous determination of eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), and arachidonic acid (AA) in human plasma. In the present HPLC-ECD system, EPA, DHA, and AA were separated using a reverse-phase C30 column and detected based on the voltammetric reduction of 3,5-di-tert-butyl-1,2-benzoquinone (DBBQ). Chromatographic peak areas were proportional to the concentration of EPA, DHA, and AA from 0.75 μM to 0.1 mM (r > 0.998). The concentrations of EPA, DHA, and AA in plasma from healthy human subjects after overnight fasting were determined, and the ratio of EPA to AA was obtained by the present HPLC-ECD method, which required 40 μL of human plasma and a simple procedure of sample preparation using diethyl ether extraction. Moreover, changes in EPA, DHA, and AA concentrations in a human subject were monitored before and after fish oil supplement administration by the present HPLC-ECD system. PMID:27682409

  19. 新型羟基和醌碳自由基产生的分子机理%A Novel Mechanism for Metal-Independent Production of Hydroxyl Radicals and Carbon-Centered Quinone Ketoxy Radicals

    Institute of Scientific and Technical Information of China (English)

    朱本占; 覃浩; 黄春华

    2011-01-01

    The hydroxyl radical (·OH) has been considered to be one of the most reactive oxygen species produced in biological systems. It has been shown that ·OH can cause oxidative damage to DNA and other macromolecules. One of the most widely accepted mechanisms for ·OH production is through the transition metal-catalyzed Fenton reaction. Pentachlorophenol (PCP) has been widely used as a wood preservative. Using e-lectron spin resonance (ESR) secondary spin-trapping methods, we found that ·OH can be produced by H2O2 and tetrachloro-1,4-benzoquinone (TCBQ) (one of the major carcinogenic metabolites of PCP) independent of transition metal ions. Further studies showed that TCBQ, but not its corresponding semiquinone radical, the tetrachlorosemi-quinone radical, is essential for ·OH production. Based on these data, we propose that ·OH production by H2O2 and TCBQ is through the following novel mechanism: a nucle-ophilic attack of H2O2 to TCBQ, forming a trichloro-hydroperoxyl-1,4-benzoquinone intermediate, which decomposes homolytically to produce ·OH. Through complementary application of ESR spin-trapping and other methods, we also detected and identified, for the first time, a novel carbon-centered quinone ketoxy radical.%羟基自由基((’)OH)被公认是生物系统中最具活性的活性氧物种,能导致生物体内DNA等生物大分子氧化损伤.目前,最被广泛接受的(')OH的产生机理是过渡金属离子催化的Fenton反应.五氯酚(PCP)是一种重要的生物杀灭剂,主要用作木材保护.采用电子自旋共振二级自旋捕获等分析手段,发现H2O2和五氯酚的代谢产物之一四氯苯醌(TCBQ)能通过不依赖于金属离子的途径产生(')OH;进一步的研究发现是TCBQ,而非其相应的半醌自由基对(')OH的产生极其重要.基于这些数据和分析,提出以下新型(')OH产生分子机理:H2O2对TCBQ进行亲核攻击形成不稳定的三氯氢过氧基苯醌中间产物,其可均裂产生(')OH.综合采

  20. Utilisation des sécrétions de myriapodes chez les lémurs et les sapajous : fonction curative ou signalisation sociale ? Fur-rubbing with millipedes in lemurs and capuchin monkeys: social function or zoopharmacognosy?

    Directory of Open Access Journals (Sweden)

    Bruno Simmen

    2011-10-01

    Full Text Available L’utilisation des myriapodes en friction sur le pelage et d’autres zones corporelles est documentée chez les primates en conditions naturelles, notamment à partir des observations récurrentes menées chez le genre Cebus. La typologie de ces comportements suggère différentes hypothèses, fonctionnelles (zoopharmacognosie, alimentaire, sociale ou non (sensorielle, auto-stimulation. Nous présentons des observations qualitatives comparées de l’utilisation non alimentaire de myriapodes diplopodes chez une forme hybride du genre Eulemur au Sud de Madagascar (occurrences en janvier 2005 et chez le sapajou Cebus apella en Guyane Française (occurrences en mars-avril 1996. L’application des sécrétions à benzoquinones sur une large partie du pelage chez Cebus contraste avec la friction exclusive de la zone périgénitale faisant suite au flairage du diplopode chez Eulemur qui manifeste en outre une réponse stéréotypée analogue au flehmen. Dans notre étude, l’imprégnation de fluides à forte intensité olfactive potentialiserait la signalisation de l’identité individuelle chez Eulemur alors que le "fur-rubbing" chez Cebus est compatible avec l’hypothèse commune d’une forme d’appropriation des défenses antiparasitaires de ces invertébrés. La sécrétion de ces défenses chimiques n’est pas automatiquement déclenchée par la manipulation des diplopodes. Le stress induit par les morsures légères (Eulemur et Cebus et l’arrachage des pattes sur plusieurs segments (Cebus augmente la probabilité de sécrétion, ce qui témoignerait d’un apprentissage d’autant plus efficace des conditions d’émission de ces fluides que l’usage est spécifique et très opportuniste.Body-rubbing with millipedes is repeatedly documented in primates living under natural conditions, mainly in capuchin monkeys (Cebus spp.. Various functional (zoopharmacognosy, ingestion, social and non-functional hypotheses (sensory, auto

  1. Synthesis, structure, spectra and reactivity of iron(III) complexes of imidazole and pyrazole containing ligands as functional models for catechol dioxygenases.

    Science.gov (United States)

    Dhanalakshmi, Thirumanasekaran; Suresh, Eringathodi; Palaniandavar, Mallayan

    2009-10-21

    them. In contrast to the iron(iii) complexes of imidazole-based ligands, those of the tripodal pyrazole-based ligands yield major amounts of the oxidized product benzoquinone and small amounts of both intra- and extradiol products. One of the pyrazole arms coordinated in the equatorial plane of these sterically constrained complexes is substituted by a solvent molecule upon adduct formation with DBC(2-), which encourages molecular oxygen to attack this site leading to benzoquinone formation. The DBSQ/DBC(2-) redox potentials of both the imidazole- and pyrazole-based complexes fall in the narrow range of -0.186 to -0.214 V supporting this proposal. PMID:19789784

  2. Progress in Chemical Constituents and Pharmaceutical Activities of Porana Genus Plants%飞蛾藤属植物化学成分和药理作用研究进展

    Institute of Scientific and Technical Information of China (English)

    李斌; 陈钰妍; 李顺祥

    2013-01-01

    通过检索国内外相关文献,重点阐述和归纳飞蛾藤属植物化学成分和药理活性方面的研究进展.结果表明,目前从飞蛾藤属植物中共分离得到33个化合物,包括甾体及其苷类、香豆素及其苷类、黄酮及其苷类、木脂素类、苯醌类、萜类、酰胺类、酚类等.药理活性主要为强心、抗凝血、防治高尿酸血症、抗炎镇痛、抗肿瘤、抑菌、杀螨虫等.深入开展飞蛾藤属植物化学成分和药理作用的研究对发现新的药用活性成分及药用资源的开发、利用和保护有重要意义.%To summarize the research progress of porana genus plants in chemical constituents and pharmaceutical activities by retrieved literatures home and abroad. It shows that 33 chemical constituents have been extracted from porana genus plants, including steroids and their glycosides, coumarins and their glycosides, flavonoids and their glycosides, lignans, benzoquinones, terpenes, amides, and phenols. Modern pharmacological research shows that compounds of porana genus plants have a variety of pharmacological activities, such as cardiac effect, anticoagulant, prevention of hyperuricemia, anti-inflammatory, antitumor, antibacterial, acaricidal activity, etc. To carry out the studies related to porana plants has the great significance for discovering and developing new medicines and new medicinal resources.

  3. Radiolytic reductions and oxidations in dimethyl sulfoxide solutions. Solvent effects on reactivity of halogen atom complexes

    International Nuclear Information System (INIS)

    Radiolysis of dimethyl sulfoxide (DMSO) solutions containing various additives was used to achieve clean one-electron reduction or oxidation of solutes. Pulse radiolysis of benzoquinone in DMSO solutions containing acetone and triethylamine permitted conversion of all primary radicals into reducing species. The total yield of reduction in the γ-radiolysis of methyl viologen solutions was found to be 0.37 μmol/J. In the pulse radiolysis of TMPD and triphenylamine in aerated DMSO containing LiCl and/or CCl4, all the primary radicals were converted into oxidizing species and gave a maximum yield of 0.39 μmol/J. In the latter systems, oxidation, was partly by halogen atom complexes. The reactivity of complexes of DMSO (DMSO-Cl DMSO-Br) and of halide ions (Br2sm-bullet-, I2sm-bullet-) was examined for several organic compounds. DMSO-Cl oxidizes chlorpromazine triphenylamine, and zinc porphyrin with rate constants of the order of 107-108 M-1s-1, and the rates increase upon addition of CH2Cl2 as well as upon addition of water and formamide. DMSO-Cl also reacts with olefins by addition of Cl to the double bond; the rate constants increase upon increasing the electron-donating properties of the substituents on the double bond. The rate constants for oxidation of chlorpromazine by Br2sm-bullet- and I2sm-bullet- increase by more than 2 orders of magnitude upon changing the solvent from DMSO gradually to water. The change was less with acetonitrile/water mixtures, and the difference is probably due to differences in ion solvation. 28 refs., 3 figs., 4 tabs

  4. Electrochemical degradation of 4-chlorophenol using a novel Pd/C gas-diffusion electrode

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hui; Wang, Jianlong [Laboratory of Environmental Technology, Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China)

    2007-11-30

    Pd/C catalyst was prepared by hydrogen reduction method and used for the Pd/C gas-diffusion electrode. It was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV) techniques. The electrochemical degradation of 4-chlorophenol was investigated in a diaphragm electrolysis device, by two different feeding gas modes, using the Pd/C gas-diffusion electrode and the carbon/polytetrafluoroethylene (C/PTFE) gas-diffusion electrode as a cathode, respectively. The results indicated that Pd particles with an average size of 4.0 nm were highly dispersed in the activated carbon with an amorphous structure; Pd content on the surface of the Pd/C catalyst reached 1.3 at.%. Furthermore, feeding with hydrogen gas firstly and then with air was in favor of improving 4-chlorophenol removal efficiency. The Pd/C gas-diffusion cathode can not only reductively dechlorinate 4-chlorophenols by feeding hydrogen gas, but also accelerate the two-electron reduction of O{sub 2} to hydrogen peroxide (H{sub 2}O{sub 2}) by feeding air. Therefore, the removal efficiency of 4-chlorophenol by using the Pd/C gas-diffusion cathode was better than that of the C/PTFE gas-diffusion cathode. And both the removal efficiency and the dechlorination degree of 4-chlorophenol reached about 100% after 60 min, and the average removal efficiency of 4-chlorophenol in terms of chemical oxygen demand (COD) exceeded 70% after 120 min. The analysis of high-performance liquid chromatography (HPLC) identified that phenol was the dechlorination product, and hydroquinone, benzoquinone, maleic, fumaric, crylic, malonic, oxalic, acetic and formic acids were the main oxidation intermediates. A reaction pathway involving all these intermediates was proposed. (author)

  5. A Liquid Junction Photoelectrochemical Solar Cell Based on p-Type MeNH3PbI3 Perovskite with 1.05 V Open-Circuit Photovoltage.

    Science.gov (United States)

    Hsu, Hsien-Yi; Ji, Li; Ahn, Hyun S; Zhao, Ji; Yu, Edward T; Bard, Allen J

    2015-11-25

    A liquid junction photoelectrochemical (PEC) solar cell based on p-type methylammonium lead iodide (p-MeNH3PbI3) perovskite with a large open-circuit voltage is developed. MeNH3PbI3 perovskite is readily soluble or decomposed in many common solvents. However, the solvent dichloromethane (CH2Cl2) can be employed to form stable liquid junctions. These were characterized with photoelectrochemical cells with several redox couples, including I3(-)/I(-), Fc/Fc(+), DMFc/DMFc(+), and BQ/BQ(•-) (where Fc is ferrocene, DMFc is decamethylferrocene, BQ is benzoquinone) in CH2Cl2. The solution-processed MeNH3PbI3 shows cathodic photocurrents and hence p-type behavior. The difference between the photocurrent onset potential and the standard potential for BQ/BQ(•-) is 1.25 V, which is especially large for a semiconductor with a band gap of 1.55 eV. A PEC photovoltaic cell, with a configuration of p-MeNH3PbI3/CH2Cl2, BQ (2 mM), BQ(•-) (2 mM)/carbon, shows an open-circuit photovoltage of 1.05 V and a short-circuit current density of 7.8 mA/cm(2) under 100 mW/cm(2) irradiation. The overall optical-to-electrical energy conversion efficiency is 6.1%. The PEC solar cell shows good stability for 5 h under irradiation.

  6. Development and Validation of Stability Indicating HPTLC Method for Estimation of Embelin in Embelia tsjeriam cottam

    Directory of Open Access Journals (Sweden)

    S. V. Kulkarni

    2015-05-01

    Full Text Available Embelin, a naturally occurring benzoquinone, is obtained from fruits of Embelia tsjeriam cottam, which plays a vital role in the Ayurvedic system of medicine. An approach for the stress degradation was successfully applied for the development of stability indicating HPTLC method for the determination of Embelin. It was spotted on the plates precoated with silica gel 60 F254 and developed using toluene: ethyl acetate: formic acid, (6:3.5:0.5 v/v/v as mobile phase. Densitometry analysis was carried out at 291 nm. The method showed high sensitivity with good linearity over the concentration range of 200-1000ng/spot with correlation coefficient value 0.997. The accuracy of the method was established based on the recovery studies. The LOD and LOQ were 6.09ng/band and 18.48ng/band respectively. The system showed a peak for Embelin at Rf of 0.68 ± 0.02.The aim of our study was to observe the effect of various stress conditions on this potential drug candidate. Stress testing of Embelin was carried out according to the International Conference of Harmonization (ICH guideline Q1A (R2. Embelin was subjected to stress conditions of acid, alkaline hydrolysis, oxidation, photolysis and thermal degradation. A significant degradation was found to occur by acid and oxidation hydrolysis and to a lesser extent under thermal stress and alkaline hydrolysis; and much lesser with photolytic stress. Stress degradation studies on embelin provide an insight into its stability.

  7. Halogen-substituted (C-β-D-glucopyranosyl)-hydroquinone regioisomers: synthesis, enzymatic evaluation and their binding to glycogen phosphorylase.

    Science.gov (United States)

    Alexacou, Kyra-Melinda; Zhang, Yun Zhi; Praly, Jean-Pierre; Zographos, Spyros E; Chrysina, Evangelia D; Oikonomakos, Nikos G; Leonidas, Demetres D

    2011-09-01

    Electrophilic halogenation of C-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl) 1,4-dimethoxybenzene (1) afforded regioselectively products halogenated at the para position to the D-glucosyl moiety (8, 9) that were deacetylated to 3 (chloride) and 16 (bromide). For preparing meta regioisomers, 1 was efficiently oxidized with CAN to afford C-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl) 1,4-benzoquinone 2 which, in either MeOH or H(2)O-THF containing few equivalents of AcCl, added hydrochloric acid to produce predominantly meta (with respect to the sugar moiety) chlorinated hydroquinone derivatives 5 and 18, this latter being deacetylated to 4. The deacetylated meta (4, 5) or para (3, 16) halohydroquinones were evaluated as inhibitors of glycogen phosphorylase (GP, a molecular target for inhibition of hepatic glycogenolysis under high glucose concentrations) by kinetics and X-ray crystallography. These compounds are competitive inhibitors of GPb with respect to α-D-glucose-1-phosphate. The measured IC(50) values (μM) [169.9±10.0 (3), 95 (4), 39.8±0.3 (5) 136.4±4.9 (16)] showed that the meta halogenated inhibitors (4, 5) are more potent than their para analogs (3, 16). The crystal structures of GPb in complex with these compounds at high resolution (1.97-2.05 Å) revealed that the inhibitors are accommodated at the catalytic site and stabilize the T conformation of the enzyme. The differences in their inhibitory potency can be interpreted in terms of variations in the interactions with protein residues of the different substituents on the aromatic part of the inhibitors. PMID:21821421

  8. 32P analysis of DNA adducts in tissues of benzene-treated rats

    International Nuclear Information System (INIS)

    Solid tumors have been reported in the Zymbal gland, oral and nasal cavities, liver, and mammary gland of Sprague-Dawley rats following chronic, high-dose administration of benzene. The carcinogenic activity of benzene is thought to be caused by activation to toxic metabolites that can interact with DNA, forming covalent adducts. A nuclease P1-enhanced 32P-postlabeling assay, having a sensitivity limit of 1 adduct in 10(9-10) DNA nucleotides, was found suitable for measuring aromatic DNA adducts derived in vitro from catechol, benzenetriol (BT), phenol, hydroquinone (HQ), and benzoquinone (BQ), potential metabolites of benzene. When DNA specimens isolated from tissues of female Sprague-Dawley rats at 24 hr after an oral gavage dose of 200 to 500 mg/kg, 5 days/week, in olive oil (3 mL/kg) for 1 day, 1 week, 5 weeks, and 10 weeks were analyzed by the 32P-postlabeling procedure, no aromatic adducts were detected unequivocally with DNA samples of liver, kidney, bone marrow, and mammary gland. With Zymbal gland DNA, three weak spots at levels totaling four lesions per 10(9) DNA nucleotides were seen only after 10 weeks of treatment, and these adducts did not correspond chromatographically to major adducts in vitro from the above specified compounds. Consequently, this finding requires confirmatory experiments. This distinct adduct pattern may relate to tumor induction in this organ following benzene administration. Our results also indicate that DNA adducts derived from catechol, BT, phenol, HQ, and BQ are either not formed in vivo with benzene or formed at levels below the detection limit of 1 adduct per 10(9-10) DNA nucleotides

  9. Electrochemical degradation of clofibric acid in water by anodic oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Sires, Ignasi [Laboratori de Ciencia i Tecnologia Electroquimica de Materials, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Cabot, Pere Lluis [Laboratori de Ciencia i Tecnologia Electroquimica de Materials, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Centellas, Francesc [Laboratori de Ciencia i Tecnologia Electroquimica de Materials, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Garrido, Jose Antonio [Laboratori de Ciencia i Tecnologia Electroquimica de Materials, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Rodriguez, Rosa Maria [Laboratori de Ciencia i Tecnologia Electroquimica de Materials, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Arias, Conchita [Laboratori de Ciencia i Tecnologia Electroquimica de Materials, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Brillas, Enric [Laboratori de Ciencia i Tecnologia Electroquimica de Materials, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain)]. E-mail: brillas@ub.edu

    2006-10-05

    Aqueous solutions containing the metabolite clofibric acid (2-(4-chlorophenoxy)-2-methylpropionic acid) up to close to saturation in the pH range 2.0-12.0 have been degraded by anodic oxidation with Pt and boron-doped diamond (BDD) as anodes. The use of BDD leads to total mineralization in all media due to the efficient production of oxidant hydroxyl radical ({center_dot}OH). This procedure is then viable for the treatment of wastewaters containing this compound. The effect of pH, apparent current density, temperature and metabolite concentration on the degradation rate, consumed specific charge and mineralization current efficiency has been investigated. Comparative treatment with Pt yields poor decontamination with complete release of stable chloride ion. When BDD is used, this ion is oxidized to Cl{sub 2}. Clofibric acid is more rapidly destroyed on Pt than on BDD, indicating that it is more strongly adsorbed on the Pt surface enhancing its reaction with {center_dot}OH. Its decay kinetics always follows a pseudo-first-order reaction and the rate constant for each anode increases with increasing apparent current density, being practically independent of pH and metabolite concentration. Aromatic products such as 4-chlorophenol, 4-chlorocatechol, 4-chlororesorcinol, hydroquinone, p-benzoquinone and 1,2,4-benzenetriol are detected by gas chromatography-mass spectrometry (GC-MS) and reversed-phase chromatography. Tartronic, maleic, fumaric, formic, 2-hydroxyisobutyric, pyruvic and oxalic acids are identified as generated carboxylic acids by ion-exclusion chromatography. These acids remain stable in solution using Pt, but they are completely converted into CO{sub 2} with BDD. A reaction pathway for clofibric acid degradation involving all these intermediates is proposed.

  10. Structures of the PutA peripheral membrane flavoenzyme reveal a dynamic substrate-channeling tunnel and the quinone-binding site.

    Science.gov (United States)

    Singh, Harkewal; Arentson, Benjamin W; Becker, Donald F; Tanner, John J

    2014-03-01

    Proline utilization A (PutA) proteins are bifunctional peripheral membrane flavoenzymes that catalyze the oxidation of L-proline to L-glutamate by the sequential activities of proline dehydrogenase and aldehyde dehydrogenase domains. Located at the inner membrane of Gram-negative bacteria, PutAs play a major role in energy metabolism by coupling the oxidation of proline imported from the environment to the reduction of membrane-associated quinones. Here, we report seven crystal structures of the 1,004-residue PutA from Geobacter sulfurreducens, along with determination of the protein oligomeric state by small-angle X-ray scattering and kinetic characterization of substrate channeling and quinone reduction. The structures reveal an elaborate and dynamic tunnel system featuring a 75-Å-long tunnel that links the two active sites and six smaller tunnels that connect the main tunnel to the bulk medium. The locations of these tunnels and their responses to ligand binding and flavin reduction suggest hypotheses about how proline, water, and quinones enter the tunnel system and where L-glutamate exits. Kinetic measurements show that glutamate production from proline occurs without a lag phase, consistent with substrate channeling and implying that the observed tunnel is functionally relevant. Furthermore, the structure of reduced PutA complexed with menadione bisulfite reveals the elusive quinone-binding site. The benzoquinone binds within 4.0 Å of the flavin si face, consistent with direct electron transfer. The location of the quinone site implies that the concave surface of the PutA dimer approaches the membrane. Altogether, these results provide insight into how PutAs couple proline oxidation to quinone reduction. PMID:24550478

  11. Cytochromes P450 in benzene metabolism and involvement of their metabolites and reactive oxygen species in toxicity.

    Science.gov (United States)

    Gut, I; Nedelcheva, V; Soucek, P; Stopka, P; Tichavská, B

    1996-12-01

    Cytochrome P450 (CYP) 2E1 was the most efficient CYP enzyme that oxidized benzene to soluble and covalently bound metabolites in rat and human liver microsomes. The covalent binding was due mostly to the formation of benzoquinone (BQ), the oxidation product of hydroquinone (HQ), and was inversely related to the formation of soluble metabolites. In rats, inhalation of benzene (4 mg/liter of air) caused a rapid destruction of CYP2B1 previously induced by phenobarbital. The ability of benzene metabolites to destroy liver microsomal CYP in vitro decreased in the order BQ > HQ > catechol > phenol. The destruction was reversed by ascorbate and diminished by alpha-tocopherol, suggesting that HQ was not toxic, whereas BQ and semiquinone radical (SQ) caused the effect. In the presence of nicotinamide adenine dinucleotide phosphate, reduced (NADPH) the microsomes did not oxidize HQ to BQ, while the formation of superoxide anion radical from both HQ and BQ was markedly quenched. Destruction of CYP in vitro caused by HQ or BQ was not mediated by hydroxyl radical formation or by lipid peroxidation. On the contrary, HQ and BQ inhibited NADPH-mediated lipid peroxidation. Ascorbate induced high levels of hydroxyl radical formation and lipid peroxidation, which were differentially affected by quinones, indicating different mechanisms. Despite reducing the toxicity of HQ and BQ, ascorbate appeared to induce its own toxicity, reflected in high levels of lipid peroxidation. Iron redox cycling played a significant role in the NADPH-induced hydroxyl radical formation but not in that caused by ascorbate; however, lipid peroxidation induced by NADPH or ascorbate was suppressed by ethylenediaminetraacetate, indicating a crucial role of iron. Thus, the data indicate that the quinones destroyed CYP directly and not via oxygen activation or lipid peroxidation.

  12. Multiresidue method for the triphenylmethane dyes in fish: Malachite green, crystal (gentian) violet, and brilliant green

    International Nuclear Information System (INIS)

    Liquid chromatographic methods are presented for the quantitative and confirmatory determination of crystal violet (CV; also known as gentian violet), leucocrystal violet (LCV), brilliant green (BG), and leucobrilliant green (LBG) in catfish. LCV and LBG were oxidized to the chromic CV and BG by reaction with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, and residues were measured as the combined CV ± LCV and BG ± LBG. These methods are extensions of published methods for malachite green (MG) analysis to allow simultaneous determination of MG, CV, and BG. Residues were extracted from muscle with ammonium acetate buffer and acetonitrile, and extracts cleaned up using dichloromethane partitioning and solid-phase extraction. Extracts were analyzed by liquid chromatography with visible detection (LC-VIS). The method was validated for catfish fortified with LCV over the range 0.25-10 ng g-1 and CV at 2 ng g-1. Average recoveries were 90.6% (±8.1% R.S.D., n = 45) for LCV and 84.4% (±4.2% R.S.D., n = 6) for CV. The average recovery for samples fortified with BG or LBG over the range 0.5-10 ng g-1 was 67.2% (±14.8% R.S.D., n = 31). CV and BG were confirmed in fish extracts by ion trap LC-mass spectrometry (LC-MSn) with no discharge-atmospheric pressure chemical ionization. Average LC-MSn recoveries were 96.5, 96.6, and 70.2% for samples fortified with CV, LCV, and BG or LBG. The limits of detection for CV, BG, and MG were in the range of 0.07-0.24 ng g-1 (ppb) for the two different instrumental methods. This methodology was applied to the analysis of catfish treated with CV and BG

  13. The cooperative electrochemical oxidation of chlorophenols in anode-cathode compartments

    Energy Technology Data Exchange (ETDEWEB)

    Wang Hui [Laboratory of Environmental Technology, INET, Tsinghua University, Beijing 100084 (China); Wang Jianlong [Laboratory of Environmental Technology, INET, Tsinghua University, Beijing 100084 (China)], E-mail: wangjl@tsinghua.edu.cn

    2008-06-15

    By using a self-made carbon/polytetrafluoroethylene (C/PTFE) O{sub 2}-fed as the cathode and Ti/IrO{sub 2}/RuO{sub 2} as the anode, the degradation of three organic compounds (phenol, 4-chlorophenol, and 2,4-dichlorophenol) was investigated in the diaphragm (with terylene as diaphragm material) electrolysis device by electrochemical oxidation process. The result indicated that the concentration of hydrogen peroxide (H{sub 2}O{sub 2}) was 8.3 mg/L, and hydroxyl radical (HO{center_dot}) was determined in the cathodic compartment by electron spin resonance spectrum (ESR). The removal efficiency for organic compounds reached about 90% after 120 min, conforming to the sequence of phenol, 4-chlorophenol, and 2,4-dichlorophenol. And the dechlorination degree of 4-chlorophenol exceeded 90% after 80 min. For H{sub 2}O{sub 2}, HO{center_dot} existed in the catholyte and reduction dechlorination at the cathode, the mineralization of organics in the cathodic compartment was better than that in the anodic compartment. The degradation of organics was supposed to be cooperative oxidation by direct or indirect electrochemical oxidation at the anode and H{sub 2}O{sub 2}, HO{center_dot} produced by oxygen reduction at the cathode. High-performance liquid chromatography (HPLC) allowed identifying phenol as the dechlorination product of 4-chlorophenol in the cathodic compartment, and hydroquinone, 4-chlorocatechol, benzoquinone, maleic, fumaric, oxalic, and formic acids as the main oxidation intermediates in the cathodic and anodic compartments. A reaction scheme involving all these intermediates was proposed.

  14. Potential of Wood-Rotting Fungi to Attack Polystyrene Sulfonate and Its Depolymerisation by Gloeophyllum trabeum via Hydroquinone-Driven Fenton Chemistry.

    Directory of Open Access Journals (Sweden)

    Martin C Krueger

    Full Text Available Synthetic polymers often pose environmental hazards due to low biodegradation rates and resulting accumulation. In this study, a selection of wood-rotting fungi representing different lignocellulose decay types was screened for oxidative biodegradation of the polymer polystyrene sulfonate (PSS. Brown-rot basidiomycetes showed PSS depolymerisation of up to 50 % reduction in number-average molecular mass (Mn within 20 days. In-depth investigations with the most efficient depolymeriser, a Gloeophyllum trabeum strain, pointed at extracellular hydroquinone-driven Fenton chemistry responsible for depolymerisation. Detection of hydroxyl radicals present in the culture supernatants showed good compliance with depolymerisation over the time course of PSS degradation. 2,5-Dimethoxy-1,4-hydroquinone (2,5-DMHQ, which was detected in supernatants of active cultures via liquid chromatography and mass spectrometry, was demonstrated to drive the Fenton processes in G. trabeum cultures. Up to 80% reduction in Mn of PSS where observed when fungal cultures were additionally supplemented with 2,5-dimethoxy benzoquinone, the oxidized from of 2,5-DMHQ. Furthermore, 2,5-DMHQ could initiate the Fenton's reagent-mediated PSS depolymerisation in cell-free systems. In contrast, white-rot fungi were unable to cause substantial depolymerising effects despite the expression of lignin-modifying exo-enzymes. Detailed investigations with laccase from Trametes versicolor revealed that only in presence of certain redox mediators limited PSS depolymerisation occurred. Our results indicate that brown-rot fungi might be suitable organisms for the biodegradation of recalcitrant synthetic polymeric pollutants.

  15. Tomato fruit chromoplasts behave as respiratory bioenergetic organelles during ripening.

    Science.gov (United States)

    Renato, Marta; Pateraki, Irini; Boronat, Albert; Azcón-Bieto, Joaquín

    2014-10-01

    During tomato (Solanum lycopersicum) fruit ripening, chloroplasts differentiate into photosynthetically inactive chromoplasts. It was recently reported that tomato chromoplasts can synthesize ATP through a respiratory process called chromorespiration. Here we show that chromoplast oxygen consumption is stimulated by the electron donors NADH and NADPH and is sensitive to octyl gallate (Ogal), a plastidial terminal oxidase inhibitor. The ATP synthesis rate of isolated chromoplasts was dependent on the supply of NAD(P)H and was fully inhibited by Ogal. It was also inhibited by the proton uncoupler carbonylcyanide m-chlorophenylhydrazone, suggesting the involvement of a chemiosmotic gradient. In addition, ATP synthesis was sensitive to 2,5-dibromo-3-methyl-6-isopropyl-p-benzoquinone, a cytochrome b6f complex inhibitor. The possible participation of this complex in chromorespiration was supported by the detection of one of its components (cytochrome f) in chromoplasts using immunoblot and immunocytochemical techniques. The observed increased expression of cytochrome c6 during ripening suggests that it could act as electron acceptor of the cytochrome b6f complex in chromorespiration. The effects of Ogal on respiration and ATP levels were also studied in tissue samples. Oxygen uptake of mature green fruit and leaf tissues was not affected by Ogal, but was inhibited increasingly in fruit pericarp throughout ripening (up to 26% in red fruit). Similarly, Ogal caused a significant decrease in ATP content of red fruit pericarp. The number of energized mitochondria, as determined by confocal microscopy, strongly decreased in fruit tissue during ripening. Therefore, the contribution of chromoplasts to total fruit respiration appears to increase in late ripening stages.

  16. [Mechanism and kinetics of phenol degradation by TiO2 photocatalytic combined technologies].

    Science.gov (United States)

    Zhang, Yi; Huang, Ruo-Nan; Wang, Xiao-Min; Wang, Qi; Cong, Yan-Qing

    2013-02-01

    The combination H2O2, or electrical catalytic (EC) system with TiO2 photbcatalytic system for phenol degradation was investigated. The catalytic systems of TiO2/UV, H2O2/UV, TiO2/UV/H2O2 and TiO2/UV/EC were compared to investigate the phenol degradation mechanism and kinetic model. The degradation of phenol in TiO2/UV/H2O2 and TiO2/UV/EC system is more effective than that in TiO2/UV system. With the solution pH of 6, TiO, concentration of 0.2 g.L-1, UV illumination of 2 h, the photocatalysis removal efficiency of phenol reaches to 86%, if the current density of 12 mA.cm-2 is added, the removal efficiency of phenol could reach to 100%. The energy utilization in different catalytic systems was also compared. When phenol is degraded in 15 min, in TiO2/UV/EC system the energy utilization is the highest of 0.0306 g.(kW. h)-1 with the energy consumption of 0.0640 kW.h-1. It indicates that much more energy is used in TiO2/UV/EC system for phenol degradation. During the analysis of intermediate products in different catalysis systems, the first-order kinetic model of phenol degradation and intermediate products such as hydroquinone, catechol and benzoquinone formation were established. The kinetic model is validated the phenol degradation pathway in different catalysis systems, and also indicates the TiO2/UV/EC system could enhance phenol and intermediate products degradation.

  17. Quinone-induced protein handling changes: Implications for major protein handling systems in quinone-mediated toxicity

    Energy Technology Data Exchange (ETDEWEB)

    Xiong, Rui; Siegel, David; Ross, David, E-mail: david.ross@ucdenver.edu

    2014-10-15

    Para-quinones such as 1,4-Benzoquinone (BQ) and menadione (MD) and ortho-quinones including the oxidation products of catecholamines, are derived from xenobiotics as well as endogenous molecules. The effects of quinones on major protein handling systems in cells; the 20/26S proteasome, the ER stress response, autophagy, chaperone proteins and aggresome formation, have not been investigated in a systematic manner. Both BQ and aminochrome (AC) inhibited proteasomal activity and activated the ER stress response and autophagy in rat dopaminergic N27 cells. AC also induced aggresome formation while MD had little effect on any protein handling systems in N27 cells. The effect of NQO1 on quinone induced protein handling changes and toxicity was examined using N27 cells stably transfected with NQO1 to generate an isogenic NQO1-overexpressing line. NQO1 protected against BQ–induced apoptosis but led to a potentiation of AC- and MD-induced apoptosis. Modulation of quinone-induced apoptosis in N27 and NQO1-overexpressing cells correlated only with changes in the ER stress response and not with changes in other protein handling systems. These data suggested that NQO1 modulated the ER stress response to potentiate toxicity of AC and MD, but protected against BQ toxicity. We further demonstrated that NQO1 mediated reduction to unstable hydroquinones and subsequent redox cycling was important for the activation of the ER stress response and toxicity for both AC and MD. In summary, our data demonstrate that quinone-specific changes in protein handling are evident in N27 cells and the induction of the ER stress response is associated with quinone-mediated toxicity. - Highlights: • Unstable hydroquinones contributed to quinone-induced ER stress and toxicity.

  18. Comparative Study of 17-AAG and NVP-AUY922 in Pancreatic and Colorectal Cancer Cells: Are There Common Determinants of Sensitivity?

    Directory of Open Access Journals (Sweden)

    Leticia Mayor-López

    2014-10-01

    Full Text Available The use of heat shock protein 90 (Hsp90 inhibitors is an attractive antineoplastic therapy. We wanted to compare the effects of the benzoquinone 17-allylamino-17-demethoxygeldanamycin (17-AAG, tanespimycin and the novel isoxazole resorcinol–based Hsp90 inhibitor NVP-AUY922 in a panel of pancreatic and colorectal carcinoma cell lines and in colorectal primary cultures derived from tumors excised to patients. PANC-1, CFPAC-1, and Caco-2 cells were intrinsically resistant to 17-AAG but sensitive to NVP-AUY922. Other cellular models were sensitive to both inhibitors. Human epidermal growth factor receptor receptors and their downstream signaling pathways were downregulated in susceptible cellular models, and concurrently, Hsp70 was induced. Intrinsic resistance to 17-AAG did not correlate with expression of ATP-binding cassette transporters involved in multidrug resistance. Some 17-AAG-resistant, NVP-AUY922–sensitive cell lines lacked NAD(PH:quinone oxidoreductase 1 (NQO1 enzyme and activity. However, colorectal LoVo cells still responded to both drugs in spite of having undetectable levels and activity of NQO1. Pharmacological and biologic inhibition of NQO1 did not confer resistance to 17-AAG in sensitive cell lines. Therefore, even though 17-AAG sensitivity is related to NQO1 protein levels and enzymatic activity, the absence of NQO1 does not necessarily convey resistance to 17-AAG in these cellular models. Moreover, NVP-AUY922 does not require NQO1 for its action and is a more potent inhibitor than 17-AAG in these cells. More importantly, we show in this report that NVP-AUY922 potentiates the inhibitory effects of chemotherapeutic agents, such as gemcitabine or oxaliplatin, and other drugs that are currently being evaluated in clinical trials as antitumor agents.

  19. Synthesis and characterization of Ag3PO4 immobilized with graphene oxide (GO) for enhanced photocatalytic activity and stability over 2,4-dichlorophenol under visible light irradiation

    International Nuclear Information System (INIS)

    Highlights: • A series of Ag3PO4–GO photocatalysts with different GO content were prepared. • Photocatalytic activity of Ag3PO4–GO to 2,4-DCP increased with GO content increasing. • GO played significant role in the enhanced photocatalytic activity and stability. • Degradation pathway of 2,4-DCP and photocatalytic mechanism of Ag3PO4–GO were proposed. - Abstract: A series of visible-light responsive photocatalysts prepared using Ag3PO4 immobilized with graphene oxide (GO) with varying GO content were obtained by an electrostatically driven method, and 2,4-dichlorophenol (2,4-DCP) was used to evaluate the performance of the photocatalysts. The composites exhibited superior photocatalytic activity and stability compared with pure Ag3PO4. When the content of GO was 5%, the degradation efficiency of 2,4-DCP could reach 98.95%, and 55.91% of the total organic (TOC) content was removed within 60 min irradiation. Meanwhile, the efficiency of 91.77% was achieved for 2,4-DCP degradation even after four times of recycling in the photocatalysis/Ag3PO4–GO (5%) system. Reactive species of O2·−, OH· and h+ were considered as the main participants for oxidizing 2,4-DCP, as confirmed by the free radical capture experiments. And some organic intermediates including 4-chlorophenol (4-CP), hydroquinone (HQ), benzoquinone (BZQ), 2-chlorohydroquinone and hydroxyhydroquinone (HHQ) were detected by comparison with the standard retention times from the high performance liquid chromatography (HPLC). In short, the enhanced photocatalytic property of Ag3PO4–GO was closely related to the strong absorption ability of GO relative to 2,4-DCP, the effective separation of photogenerated electron–hole pairs, and the excellent electron capture capability of GO

  20. Quantification and human health risk assessment of by-products of photo catalytic oxidation of ethylbenzene, xylene and toluene in indoor air of analytical laboratories.

    Science.gov (United States)

    Dhada, Indramani; Sharma, Mukesh; Nagar, Pavan Kumar

    2016-10-01

    The by-products of TiO2-based photocatalytic oxidation (PCO) of ethylbenze, p,m-xylene, o-xylene and toluene (EXT) in vapour phase and those adsorbed on the catalyst surface (solid phase) were identified and quantified on GC/GC-MS. A factor was developed in terms of μg of by-product produced per mg of EXT removed per sq-meter surface area of catalyst for estimating the mass of by-products produced. The by-products quantified were: acetone, hexane, cyclohexane, benzene, crotonaldehyde, toulene, 1,4-benzoquinone, benzaldehyde, phenol, benzylalcohol, cresol, hydroquinone and benzoic acid. The by-products accounted for 2.3-4.2% of the total mass of EXT treated. For treating concentrations of 220μg/m(3) (ethylbenzene), 260μg/m(3) (p,m-xylene), 260μg/m(3) (o-xylene) and 320μg/m(3) (toluene), at a flow rate of 7L/min for 12h in a laboratory of volume 195m(3), the estimated cancer risks of by-products to the occupants were 1.51×10(-6), 1.06×10(-6), 4.69×10(-7), and 1.58×10(-9) respectively. The overall hazard index (HI) of the by-products for EXT was of the order 10(-4); which is much less than desired level of 1.0. The estimated risks were within the acceptable level. This study has also suggested the photocatalytic degradation pathways for EX which are through formation of toluene. PMID:27208611

  1. Reaction of pyranose dehydrogenase from Agaricus meleagris with its carbohydrate substrates.

    Science.gov (United States)

    Graf, Michael M H; Sucharitakul, Jeerus; Bren, Urban; Chu, Dinh Binh; Koellensperger, Gunda; Hann, Stephan; Furtmüller, Paul G; Obinger, Christian; Peterbauer, Clemens K; Oostenbrink, Chris; Chaiyen, Pimchai; Haltrich, Dietmar

    2015-11-01

    Monomeric Agaricus meleagris pyranose dehydrogenase (AmPDH) belongs to the glucose-methanol-choline family of oxidoreductases. An FAD cofactor is covalently tethered to His103 of the enzyme. AmPDH can double oxidize various mono- and oligosaccharides at different positions (C1 to C4). To study the structure/function relationship of selected active-site residues of AmPDH pertaining to substrate (carbohydrate) turnover in more detail, several active-site variants were generated, heterologously expressed in Pichia pastoris, and characterized by biochemical, biophysical and computational means. The crystal structure of AmPDH shows two active-site histidines, both of which could take on the role as the catalytic base in the reductive half-reaction. Steady-state kinetics revealed that His512 is the only catalytic base because H512A showed a reduction in (kcat /KM )glucose by a factor of 10(5) , whereas this catalytic efficiency was reduced by two or three orders of magnitude for His556 variants (H556A, H556N). This was further corroborated by transient-state kinetics, where a comparable decrease in the reductive rate constant was observed for H556A, whereas the rate constant for the oxidative half-reaction (using benzoquinone as substrate) was increased for H556A compared to recombinant wild-type AmPDH. Steady-state kinetics furthermore indicated that Gln392, Tyr510, Val511 and His556 are important for the catalytic efficiency of PDH. Molecular dynamics (MD) simulations and free energy calculations were used to predict d-glucose oxidation sites, which were validated by GC-MS measurements. These simulations also suggest that van der Waals interactions are the main driving force for substrate recognition and binding. PMID:26284701

  2. Photocatalytic activity of porous multiwalled carbon nanotube-TiO2 composite layers for pollutant degradation.

    Science.gov (United States)

    Zouzelka, Radek; Kusumawati, Yuly; Remzova, Monika; Rathousky, Jiri; Pauporté, Thierry

    2016-11-01

    TiO2 nanoparticles are suitable building blocks nanostructures for the synthesis of porous functional thin films. Here we report the preparation of films using brookite, P25 titania and anatase pristine nanoparticles and of nanocomposite layers combining anatase nanoparticles and multi-walled carbon nanotube (MWCNT) at various concentrations. The structure and phase composition of the layers were characterized by X-ray diffraction and Raman spectroscopy. Their morphology and texture properties were determined by scanning electron microscopy and krypton adsorption experiments, respectively. Additionally to a strong absorption in the UV range, the composites exhibited light absorption in the visible range as well. The photocatalytic performance of the layers was tested in the degradation of aqueous solutions of 4-chlorophenol serving as a model of an eco-persistent pollutant. Besides the determination of the decrease in the concentration of 4-chlorophenol, also the formation of intermediate degradation products, namely hydroquinone and benzoquinone, was followed. The presence of MWCNTs had a beneficial effect on the photocatalytic performance, a marked increase in the photocatalytic degradation rate constant being observed even at very low concentrations of MWCNTs. Compared to a P25 reference layer, the first order rate reaction constant increased by about 100% for the composite films containing MWCNTs at concentrations above 0.6 wt%. The key parameters for the enhancement of the photocatalytic performance are discussed. The presence of carbon nanotubes influences beneficially the degradation of 4-chlorophenol by an attack of the primarily photoproduced hydroxyl radicals onto the 4-chlorophenol molecules. The degradation due to the direct charge transfer is practically not influenced at all. PMID:27262272

  3. [Toxicity of 4-Chlorophenol Solution Under Electrochemical Reduction-oxidation Process].

    Science.gov (United States)

    Wang, Yan; Shi, Qin; Wang, Hui; Bian, Zhao-yong

    2016-04-15

    The Pd-Fe/graphene multi-functional catalytic cathode was prepared by UV-assisted photocatalytic reduction. The catalytic cathode and a Ti/IrO₂/RuO₂ anode consisting of both three-electrode system (two cathodes) and two-electrode system (one cathode) were designed for the degradation of 4-chlorophenol in aid of olectrochemical reducing and oxidizing processes. The concentrations of the intermediates and products were monitored by high performance liquid chromatography (HPLC), total organic carbon (TOC), and ion chromatography (IC). The theoretical toxicity was calculated according to the formula. The actual toxicity of the solution during the degradation process was detected using the luminescent bacteria. The comparison of the actual toxicity and theoretical toxicity was performed to analyze the trend of the two systems. The results showed that the toxicity of the solution in anode compartment first increased and then decreased, but the toxicity in cathode compartment decreased during the whole degradation for both systems. This trend could be attributed to the intermediate formed, benzoquinone. Through the analysis of correlation, the correlation coefficient was 1 of the theoretical toxicity and actual toxicity at the level of P = 0.01, which indicated the result of toxicity was reliable. The toxicity of three-electrode system was lower than that of two-electrode system after 120 mm. The three-electrode system was considered to be better than the two-electrode system. Therefore, the detection of actual toxicity in electrochemical reducing and oxidizing process for the degradation of chlorophenols in the actual industry has wide application prospect. PMID:27548966

  4. Wuzhi tablet (Schisandra Sphenanthera extract) protects against acetaminophen-induced hepatotoxicity by inhibition of CYP-mediated bioactivation and regulation of NRF2-ARE and p53/p21 pathways.

    Science.gov (United States)

    Fan, Xiaomei; Jiang, Yiming; Wang, Ying; Tan, Huasen; Zeng, Hang; Wang, Yongtao; Chen, Pan; Qu, Aijuan; Gonzalez, Frank J; Huang, Min; Bi, Huichang

    2014-12-01

    Schisandra sphenanthera is widely used as a tonic and restorative in many countries to enhance the function of liver and other organs. Wuzhi tablet (WZ) is a preparation of an ethanol extract of Schisandra sphenanthera. Our previous study demonstrated that WZ exerted a protective effect toward acetaminophen (APAP)-induced hepatotoxicity. However, the molecular mechanisms of this protection remain unclear. This study aimed to determine what molecular pathways contributed to the hepatoprotective effects of WZ against APAP toxicity. Administration of WZ 3 days before APAP treatment significantly attenuated APAP hepatotoxicity in a dose-dependent manner and reduced APAP-induced JNK activation. Treatment with WZ resulted in potent inhibition of CYP2E1, CYP3A11, and CYP1A2 activities and then caused significant inhibition of the formation of the oxidized APAP metabolite N-acetyl-p-benzoquinone imine-reduced glutathione. The expression of NRF2 was increased after APAP and/or WZ treatment, whereas KEAP1 levels were decreased. The protein expression of NRF2 target genes including Gclc, Gclm, Ho-1, and Nqo1 was significantly increased by WZ treatment. Furthermore, APAP increased the levels of p53 and its downstream gene p21 to trigger cell cycle arrest and apoptosis, whereas WZ pretreatment could inhibit p53/p21 signaling to induce cell proliferation-associated proteins including cyclin D1, CDK4, PCNA, and ALR to promote hepatocyte proliferation. This study demonstrated that WZ prevented APAP-induced liver injury by inhibition of cytochrome P450-mediated APAP bioactivation, activation of the NRF2-antioxidant response element pathway to induce detoxification and antioxidation, and regulation of the p53, p21, cyclin D1, CDK4, PCNA, and ALR to facilitate liver regeneration after APAP-induced liver injury.

  5. Hepato-protective effects of six schisandra lignans on acetaminophen-induced liver injury are partially associated with the inhibition of CYP-mediated bioactivation.

    Science.gov (United States)

    Jiang, Yiming; Fan, Xiaomei; Wang, Ying; Tan, Huasen; Chen, Pan; Zeng, Hang; Huang, Min; Bi, Huichang

    2015-04-25

    Acetaminophen (APAP) overdose is the most frequent cause of drug-induced acute liver failure. Schisandra fructus is widely-used traditional Chinese medicine which possesses hepato-protective potential. Schisandrin A (SinA), Schisandrin B (SinB), Schisandrin C (SinC), Schisandrol A (SolA), Schisandrol B (SolB), and Schisantherin A (SthA) are the major bioactive lignans. Most recently, we found SolB exerts significant hepato-protection against APAP-induced liver injury. In this study, the protective effects of the other five schisandra lignans against APAP-induced acute hepatotoxicity in mice were investigated and compared with that of SolB. The results of morphological and biochemical assessment clearly demonstrated significant protective effects of SinA, SinB, SinC, SolA, SolB, and SthA against APAP-induced liver injury. Among these schisandra lignans, SinC and SolB exerted the strongest hepato-protective effects against APAP-induced hepatotoxicity. Six lignans pretreatment before APAP dosing could prevent the depletions of total liver glutathione (GSH) and mitochondrial GSH caused by APAP. Additionally, the lignans treatment inhibited the enzymatic activities of three CYP450 isoforms (CYP2E1, CYP1A2, and CYP3A11) related to APAP bioactivation, and further decreased the formation of APAP toxic intermediate N-acetyl-p-benzoquinone imine (NAPQI) in mouse microsomal incubation system. This study demonstrated that SinA, SinB, SinC, SolA, SolB and SthA exhibited significant protective actions toward APAP-induced liver injury, which was partially associated with the inhibition of CYP-mediated APAP bioactivation.

  6. Total syntheses of the telomerase inhibitors dictyodendrin B, C, and E.

    Science.gov (United States)

    Fürstner, Alois; Domostoj, Mathias M; Scheiper, Bodo

    2006-06-21

    Concise and flexible total syntheses of the pyrrolo[2,3-c]carbazole alkaloids dictyodendrin B (2), C (3), and E (5) are described. These polycyclic telomerase inhibitors of marine origin derive from the common intermediate 18 which was prepared on a multigram scale by a sequence comprising a TosMIC cycloaddition with formation of the pyrrole A-ring, a titanium-induced reductive oxoamide coupling reaction to generate an adjacent indole nucleus, and a photochemical 6pi-electrocyclization/aromatization tandem to forge the pyrrolocarbazole core. Conversion of 18 into dictyodendrin C required selective manipulations of the lateral protecting groups and oxidation with peroxoimidic acid to form the vinylogous benzoquinone core of the target. Zinc-induced reductive cleavage of the trichloroethyl sulfate ester then completed the first total synthesis of 3. Its relatives 2 and 5 also originate from compound 18 by a selective bromination of the pyrrole entity followed by elaboration of the resulting bromide 27 via metal-halogen exchange or cross-coupling chemistry, respectively. Particularly noteworthy in this context is the generation of the very labile p-quinomethide motif of dictyodendrin E by a palladium-catalyzed benzyl cross-coupling reaction followed by vinylogous oxidation of the resulting product 41 with DDQ. The Suzuki step could only be achieved with the aid of the borate complex 40 formed in situ from p-methoxybenzylmagnesium chloride and 9-MeO-9-BBN, whereas alternative methods employing benzylic boronates, -trifluoroborates, or -stannanes met with failure. PMID:16771525

  7. Mechanistic insights into the oxidation of substituted phenols via hydrogen atom abstraction by a cupric-superoxo complex.

    Science.gov (United States)

    Lee, Jung Yoon; Peterson, Ryan L; Ohkubo, Kei; Garcia-Bosch, Isaac; Himes, Richard A; Woertink, Julia; Moore, Cathy D; Solomon, Edward I; Fukuzumi, Shunichi; Karlin, Kenneth D

    2014-07-16

    To obtain mechanistic insights into the inherent reactivity patterns for copper(I)-O2 adducts, a new cupric-superoxo complex [(DMM-tmpa)Cu(II)(O2(•-))](+) (2) [DMM-tmpa = tris((4-methoxy-3,5-dimethylpyridin-2-yl)methyl)amine] has been synthesized and studied in phenol oxidation-oxygenation reactions. Compound 2 is characterized by UV-vis, resonance Raman, and EPR spectroscopies. Its reactions with a series of para-substituted 2,6-di-tert-butylphenols (p-X-DTBPs) afford 2,6-di-tert-butyl-1,4-benzoquinone (DTBQ) in up to 50% yields. Significant deuterium kinetic isotope effects and a positive correlation of second-order rate constants (k2) compared to rate constants for p-X-DTBPs plus cumylperoxyl radical reactions indicate a mechanism that involves rate-limiting hydrogen atom transfer (HAT). A weak correlation of (k(B)T/e) ln k2 versus E(ox) of p-X-DTBP indicates that the HAT reactions proceed via a partial transfer of charge rather than a complete transfer of charge in the electron transfer/proton transfer pathway. Product analyses, (18)O-labeling experiments, and separate reactivity employing the 2,4,6-tri-tert-butylphenoxyl radical provide further mechanistic insights. After initial HAT, a second molar equiv of 2 couples to the phenoxyl radical initially formed, giving a Cu(II)-OO-(ArO') intermediate, which proceeds in the case of p-OR-DTBP substrates via a two-electron oxidation reaction involving hydrolysis steps which liberate H2O2 and the corresponding alcohol. By contrast, four-electron oxygenation (O-O cleavage) mainly occurs for p-R-DTBP which gives (18)O-labeled DTBQ and elimination of the R group.

  8. Mechanistic Insights into the Oxidation of Substituted Phenols via Hydrogen Atom Abstraction by a Cupric–Superoxo Complex

    Science.gov (United States)

    2015-01-01

    To obtain mechanistic insights into the inherent reactivity patterns for copper(I)–O2 adducts, a new cupric–superoxo complex [(DMM-tmpa)CuII(O2•–)]+ (2) [DMM-tmpa = tris((4-methoxy-3,5-dimethylpyridin-2-yl)methyl)amine] has been synthesized and studied in phenol oxidation–oxygenation reactions. Compound 2 is characterized by UV–vis, resonance Raman, and EPR spectroscopies. Its reactions with a series of para-substituted 2,6-di-tert-butylphenols (p-X-DTBPs) afford 2,6-di-tert-butyl-1,4-benzoquinone (DTBQ) in up to 50% yields. Significant deuterium kinetic isotope effects and a positive correlation of second-order rate constants (k2) compared to rate constants for p-X-DTBPs plus cumylperoxyl radical reactions indicate a mechanism that involves rate-limiting hydrogen atom transfer (HAT). A weak correlation of (kBT/e) ln k2 versus Eox of p-X-DTBP indicates that the HAT reactions proceed via a partial transfer of charge rather than a complete transfer of charge in the electron transfer/proton transfer pathway. Product analyses, 18O-labeling experiments, and separate reactivity employing the 2,4,6-tri-tert-butylphenoxyl radical provide further mechanistic insights. After initial HAT, a second molar equiv of 2 couples to the phenoxyl radical initially formed, giving a CuII–OO–(ArO′) intermediate, which proceeds in the case of p-OR-DTBP substrates via a two-electron oxidation reaction involving hydrolysis steps which liberate H2O2 and the corresponding alcohol. By contrast, four-electron oxygenation (O–O cleavage) mainly occurs for p-R-DTBP which gives 18O-labeled DTBQ and elimination of the R group. PMID:24953129

  9. Photosynthetic Regulation of the Cyanobacterium Synechocystis sp. PCC 6803 Thioredoxin System and Functional Analysis of TrxB (Trx x) and TrxQ (Trx y) Thioredoxins

    Institute of Scientific and Technical Information of China (English)

    M. Esther Pérez-Pérez; Eugenio Martín-Figueroa; Francisco J. Florencio

    2009-01-01

    The expression of the genes encoding the ferredoxin-thioredoxin system including the ferredoxin-thiore-doxin reductase (FTR) genes ftrC and ftrV and the four different thioredoxin genes trxA (m-type; slr0623), trxB (x-type; slr1139), trxC (sll1057) and trxQ (y-type; slr0233) of the cyanobacterium Synechocystis sp. PCC 6803 has been studied according to changes in the photosynthetic conditions. Experiments of light-dark transition indicate that the expression of all these genes except trxQ decreases in the dark in the absence of glucose in the growth medium. The use of two electron transport inhibitors, 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU) and 2,5-dibromo-3-methyl-6-isopropyl-p-benzoquinone (DBMIB), reveals a differential effect on thioredoxin genes expression being trxC and trxQ almost unaf-fected, whereas trxA, trxB, and the ftr genes are down-regulated. In the presence of glucose, DCMU does not affect gene expression but DBMIB still does. Analysis of the single TrxB or TrxQ and the double TrxB TrxQ Synechocystis mutant strains reveal different functions for each of these thioredoxins under different growth conditions. Finally, a Synechocystis strain was generated containing a mutated version of TrxB (TrxBC34S), which was used to identify the potential in-vivo targets of this thioredoxin by a proteomic analysis.

  10. Localization of proteins in paint cross-sections by scanning electrochemical microscopy as an alternative immunochemical detection technique

    Energy Technology Data Exchange (ETDEWEB)

    Sciutto, Giorgia; Prati, Silvia [Microchemistry and Microscopy Art Diagnostic Laboratory, University of Bologna, Via Guaccimanni 42, Ravenna 48121 (Italy); Department of Chemistry “G. Ciamician”, University of Bologna, Via Selmi, Bologna 2 40126 (Italy); Mazzeo, Rocco, E-mail: rocco.mazzeo@unibo.it [Microchemistry and Microscopy Art Diagnostic Laboratory, University of Bologna, Via Guaccimanni 42, Ravenna 48121 (Italy); Department of Chemistry “G. Ciamician”, University of Bologna, Via Selmi, Bologna 2 40126 (Italy); Zangheri, Martina; Roda, Aldo; Bardini, Luca; Valenti, Giovanni; Rapino, Stefania [Department of Chemistry “G. Ciamician”, University of Bologna, Via Selmi, Bologna 2 40126 (Italy); Marcaccio, Massimo, E-mail: massimo.marcaccio@unibo.it [Department of Chemistry “G. Ciamician”, University of Bologna, Via Selmi, Bologna 2 40126 (Italy)

    2014-06-01

    Highlights: • Advanced immuno-electrochemical detection of proteins in paint samples by SECM. • Analysis performed directly on cross-section with high spatial resolution. • Identification of HRP catalytic activity for a selective location of analyte. • Satisfactory results were obtained for aged real samples. • The way forward for an extensive application of SECM in conservation science is shown. - Abstract: The qualitative identification of proteinaceous substances, as well as their location within a complex paint stratigraphy, is one of the most challenging issues in the characterization of painting materials. Nevertheless, information on paint components represent a crucial task for studies concerning both the ancient painting techniques adopted and the state of conservation, being fundamental investigations for the selection of appropriate conservation actions. The present research was aimed at developing a new detection approach for the immunochemical localization of ovalbumin in paint cross-sections based on the use of scanning electrochemical microscopy (SECM). The immunochemical analyses were performed using an anti-ovalbumin primary antibody and a secondary antibody labelled with horseradish peroxidase (HRP). SECM measurements were performed in feedback mode using benzoquinone (BQ)/hydroquinone (H{sub 2}Q) redox couple. In presence of hydrogen peroxide (H{sub 2}O{sub 2}), HRP catalyzes the re-oxidation of H{sub 2}Q to BQ and the increment of BQ concentration in correspondence of the target protein was detected by SECM through the electrochemical reduction of the regenerated BQ at the microelectrode. Indeed, the localization of ovalbumin was possible thanks to a clear discrimination of SECM currents, achieved by the comparison of the measurements recorded before and after H{sub 2}O{sub 2} administration, based on the HRP on/off approach. The method was evaluated both on samples from standard mocks-up and on a historical sample, collected from a

  11. Enzyme-assisted total synthesis of the optical antipodes D-myo-inositol 3,4,5-trisphosphate and D-myo-inositol 1,5, 6-trisphosphate: aspects of their structure-activity relationship to biologically active inositol phosphates.

    Science.gov (United States)

    Adelt, S; Plettenburg, O; Stricker, R; Reiser, G; Altenbach, H J; Vogel, G

    1999-04-01

    Unambiguous total syntheses of both optical antipodes of the enantiomeric pair D-myo-inositol 3,4,5-trisphosphate (Ins(3,4,5)P3) and D-myo-inositol 1,5,6-trisphosphate (Ins(1,5,6)P3) are described. The ring system characteristic of myo-inositol was constructed de novo from p-benzoquinone. X-ray data for the enzymatically resolved (1S,2R,3R,4S)-1,4-diacetoxy-2,3-dibromocyclohex-5-ene enabled the unequivocal assignment of the absolute configuration. Subsequent transformations under stereocontrolled conditions led to enantiopure C2-symmetrical 1,4-(di-O-benzyldiphospho)conduritol B derivatives. Their synthetic potential was exploited to prepare Ins(3,4,5,6)P4 and Ins(1,4,5,6)P4 in three steps. With a recently identified and partially purified InsP5/InsP4 phosphohydrolase from Dictyostelium discoideum, these enantiomers could be converted to the target compounds, Ins(3,4,5)P3 and Ins(1,5,6)P3, on a preparative scale. An HPLC system employed for both purification of the inositol phosphates and analytical runs ensured that the products were isomerically homogeneous. The sensitivity of detection achieved by a complexometric postcolumn derivatization method indicates that the complexation properties of Ins(3,4,5)P3/Ins(1,5,6)P3 resemble those of Ins(1,2,3)P3, a compound with antioxidant potential. The set of inositol phosphates synthesized was used to clarify structural motifs important for molecular recognition by p42(IP4), a high-affinity Ins(1,3,4,5)P4/PtdIns(3,4,5)P3-specific binding protein from pig cerebellum. PMID:10197969

  12. Identification of the para-nitrophenol catabolic pathway, and characterization of three enzymes involved in the hydroquinone pathway, in pseudomonas sp. 1-7

    Directory of Open Access Journals (Sweden)

    Zhang Shuangyu

    2012-03-01

    Full Text Available Abstract Background para-Nitrophenol (PNP, a priority environmental pollutant, is hazardous to humans and animals. However, the information relating to the PNP degradation pathways and their enzymes remain limited. Results Pseudomonas sp.1-7 was isolated from methyl parathion (MP-polluted activated sludge and was shown to degrade PNP. Two different intermediates, hydroquinone (HQ and 4-nitrocatechol (4-NC were detected in the catabolism of PNP. This indicated that Pseudomonas sp.1-7 degraded PNP by two different pathways, namely the HQ pathway, and the hydroxyquinol (BT pathway (also referred to as the 4-NC pathway. A gene cluster (pdcEDGFCBA was identified in a 10.6 kb DNA fragment of a fosmid library, which cluster encoded the following enzymes involved in PNP degradation: PNP 4-monooxygenase (PdcA, p-benzoquinone (BQ reductase (PdcB, hydroxyquinol (BT 1,2-dioxygenase (PdcC, maleylacetate (MA reductase (PdcF, 4-hydroxymuconic semialdehyde (4-HS dehydrogenase (PdcG, and hydroquinone (HQ 1,2-dioxygenase (PdcDE. Four genes (pdcDEFG were expressed in E. coli and the purified pdcDE, pdcG and pdcF gene products were shown to convert HQ to 4-HS, 4-HS to MA and MA to β-ketoadipate respectively by in vitro activity assays. Conclusions The cloning, sequencing, and characterization of these genes along with the functional PNP degradation studies identified 4-NC, HQ, 4-HS, and MA as intermediates in the degradation pathway of PNP by Pseudomonas sp.1-7. This is the first conclusive report for both 4-NC and HQ- mediated degradation of PNP by one microorganism.

  13. Nonmicrobial Nitrophenol Degradation via Peroxygenase Activity of Dehaloperoxidase-Hemoglobin from Amphitrite ornata.

    Science.gov (United States)

    McCombs, Nikolette L; D'Antonio, Jennifer; Barrios, David A; Carey, Leiah M; Ghiladi, Reza A

    2016-05-01

    The marine hemoglobin dehaloperoxidase (DHP) from Amphitrite ornata was found to catalyze the H2O2-dependent oxidation of nitrophenols, an unprecedented nonmicrobial degradation pathway for nitrophenols by a hemoglobin. Using 4-nitrophenol (4-NP) as a representative substrate, the major monooxygenated product was 4-nitrocatechol (4-NC). Isotope labeling studies confirmed that the O atom incorporated was derived exclusively from H2O2, indicative of a peroxygenase mechanism for 4-NP oxidation. Accordingly, X-ray crystal structures of 4-NP (1.87 Å) and 4-NC (1.98 Å) bound to DHP revealed a binding site in close proximity to the heme cofactor. Peroxygenase activity could be initiated from either the ferric or oxyferrous states with equivalent substrate conversion and product distribution. The 4-NC product was itself a peroxidase substrate for DHP, leading to the secondary products 5-nitrobenzene-triol and hydroxy-5-nitro-1,2-benzoquinone. DHP was able to react with 2,4-dinitrophenol (2,4-DNP) but was unreactive against 2,4,6-trinitrophenol (2,4,6-TNP). pH dependence studies demonstrated increased reactivity at lower pH for both 4-NP and 2,4-DNP, suggestive of a pH effect that precludes the reaction with 2,4,6-TNP at or near physiological conditions. Stopped-flow UV-visible spectroscopic studies strongly implicate a role for Compound I in the mechanism of 4-NP oxidation. The results demonstrate that there may be a much larger number of nonmicrobial enzymes that are underrepresented when it comes to understanding the degradation of persistent organic pollutants such as nitrophenols in the environment.

  14. Cell-specific activation and detoxification of benzene metabolites in mouse and human bone marrow: Identification of target cells and a potential role for modulation of apoptosis in benzene toxicity

    Energy Technology Data Exchange (ETDEWEB)

    Ross, D.; Siegel, D.; Schattenberg, D.G. [Univ. of Colorado Health Sciences Center, Denver, CO (United States)] [and others

    1996-12-01

    The role of cell-specific metabolism in benzene toxicity was examined in both murine and human bone marrow. Hemopoietic progenitor cells and stromal cells are important control points for regulation of hemopoiesis. We show that the selective toxicity of hydroquinone at the level of the macrophage in murine bone marrow stroma may be explained by a high peroxidase/nicotanimicle adenine dinucleotide phosphate, reduced [NAD(P)H]:quinone oxidoreductase (NQO1) ratio. Peroxidases metabolize hydroquinone to the reactive 1,4-benzoquinone, whereas NQO1 reduces the quinones formed, resulting in detoxification. Peroxidase and NQO1 activity in human stromal cultures vary as a function of time in culture, with peroxidase activity decreasing and NQO1 activity increasing with time. Peroxidase activity and, more specifically, myeloperoxidase, which had previously been considered to be expressed at the promyelocyte level, was detected in murine lineage-negative and human CD34{sup +} progenitor cells. This provides a metabolic mechanism whereby phenolic metabolites of benzene can be bioactivated in progenitor cells, which are considered initial target cells for the development of leukemias. Consequences of a high peroxidase/NQO1 ratio in HL-60 cells were shown to include hydroquinone-induced apoptosis. Hydroquinone can also inhibit proteases known to play a role in induction of apoptosis, suggesting that it may be able to inhibit apoptosis induced by other stimuli. Modulation of apoptosis may lead to aberrant hemopoiesis and neoplastic progression. This enzyme-directed approach has identified target cells of the phenolic metabolites of benzene in bone marrow and provided a metabolic basis for benzene-induced toxicity at the level of the progenitor cell in both murine and human bone marrow. 60 refs., 8 figs.

  15. Measurement of enzyme activity in single cells by voltammetry using a microcell with a positionable dual electrode.

    Science.gov (United States)

    Gao, Ning; Zhao, Minghui; Zhang, Xiaoli; Jin, Wenrui

    2006-01-01

    The electrochemical single-cell analysis for enzyme activity was developed using microcells on a microcell array coupled with a positionable dual microelectrode. The microcell array with the nanoliter-scale microcells was constructed using simple chemical etching without photolithographic techniques. The positionable dual microelectrodes consisted of the nanometer-to-micrometer-radius Au disk working electrode and a approximately 80-microm-radius Ag/AgCl reference electrode. Peroxidase was chosen as the model enzyme. Factors that concern electrochemical single-cell analysis in microcells such as solution evaporation, interference of soluble oxygen, electrode size, solution volume, and electrode fouling were investigated and discussed. The 20 or 100 nL of detection volume was found to be suitable for peroxidase determination in single neutrophils or single acute promyelocytic leukemia cells without interference from intracellular macromolecules and electrode fouling, when the dual electrode with a 10-microm-radius Au disk working electrode was used. Cells were perforated with digitonin before transferring them into the microcells, to lyse cells easily. The perforated cells were transferred into the microcells by pushing a microscope slide on a drop of the cell suspension on the microcell array. After a single cell in the microcell was lysed using a freeze-thawing technique and allowed to dry, physiological buffer saline containing 2.0 x 10(-3) mol/L hydroquinone and 2.0 x 10(-3) mol/L H2O2 as the substrates of the enzyme-catalyzed reaction was added. The microcell array was positioned in a constant-humidity chamber to prevent evaporation. Then the dual electrode was inserted into the microcell by means of a scanning electrochemical microscope and the product benzoquinone of the enzyme-catalyzed reaction was voltammetrically detected. Peroxidase activity could be quantified using the steady-state current on the voltammogram after subtracting the blank and using the

  16. Quantitative determination of enzyme activity in single cells by scanning microelectrode coupled with a nitrocellulose film-covered microreactor by means of a scanning electrochemical microscope.

    Science.gov (United States)

    Zhang, Xiaoli; Sun, Fuchan; Peng, Xuewei; Jin, Wenrui

    2007-02-01

    An electrochemical method for quantitative determination of enzyme activity in single cells was developed by scanning a microelectrode (ME) over a nitrocellulose film-covered microreactor with micropores by means of a scanning electrochemical microscope (SECM). Peroxidase (PO) in neutrophils was chosen as the model system. The microreactor consisted of a microwell with a solution and a nitrocellulose film with micropores. A single cell perforated by digitonin was injected into the microwell. After the perforated cell was lysed and allowed to dry, physiological buffer saline (PBS) containing hydroquinone (H2Q) and H2O2 as substrates of the enzyme-catalyzed reaction was added in the microwell. The microwell containing the extract of the lysed cell and the enzyme substrates was covered with Parafilm to prevent evaporation. The solution in the microwell was incubated for 20 min. In this case, the released PO from the cell converted H2Q into benzoquinone (BQ). Then, the Parafilm was replaced by a nitrocellulose film with micropores to fabricate the microreactor. The microreactor was placed in an electrochemical cell containing PBS, H2Q, and H2O2. After a 10-microm-radius Au ME was inserted into the electrochemical cell and approached down to the microreactor, the ME was scanned along the central line across the microreactor by means of a SECM. The scan curve with a peak was obtained by detecting BQ that diffused out from the microreactor through the micropores on the nitrocellulose film. PO activity could be quantified on the basis of the peak current on the scan curve using a calibration curve. This method had two obvious advantages: no electrode fouling and no oxygen interference. PMID:17263362

  17. Overexpression of Heat Shock Factor Gene HsfA3 Increases Galactinol Levels and Oxidative Stress Tolerance in Arabidopsis.

    Science.gov (United States)

    Song, Chieun; Chung, Woo Sik; Lim, Chae Oh

    2016-06-30

    Heat shock factors (Hsfs) are central regulators of abiotic stress responses, especially heat stress responses, in plants. In the current study, we characterized the activity of the Hsf gene HsfA3 in Arabidopsis under oxidative stress conditions. HsfA3 transcription in seedlings was induced by reactive oxygen species (ROS), exogenous hydrogen peroxide (H2O2), and an endogenous H2O2 propagator, 2,5-dibromo-3-methyl-6-isopropyl-p-benzoquinone (DBMIB). HsfA3-overexpressing transgenic plants exhibited increased oxidative stress tolerance compared to untransformed wild-type plants (WT), as revealed by changes in fresh weight, chlorophyll fluorescence, and ion leakage under light conditions. The expression of several genes encoding galactinol synthase (GolS), a key enzyme in the biosynthesis of raffinose family oligosaccharides (RFOs), which function as antioxidants in plant cells, was induced in HsfA3 overexpressors. In addition, galactinol levels were higher in HsfA3 overexpressors than in WT under unstressed conditions. In transient transactivation assays using Arabidopsis leaf protoplasts, HsfA3 activated the transcription of a reporter gene driven by the GolS1 or GolS2 promoter. Electrophoretic mobility shift assays showed that GolS1 and GolS2 are directly regulated by HsfA3. Taken together, these findings provide evidence that GolS1 and GolS2 are directly regulated by HsfA3 and that GolS enzymes play an important role in improving oxidative stress tolerance by increasing galactinol biosynthesis in Arabidopsis. PMID:27109422

  18. Spectroscopic and thermal investigations on the charge transfer interaction between risperidone as a schizophrenia drug with some traditional π-acceptors: Part 2

    Science.gov (United States)

    El-Habeeb, Abeer A.; Al-Saif, Foziah A.; Refat, Moamen S.

    2013-03-01

    The focus of present investigation was to assess the utility of non-expensive techniques in the evaluation of risperidone (Ris) in solid and solution states with different traditional π-acceptors and subsequent incorporation of the analytical determination into pharmaceutical formulation for a faster release of risperidone. Charge-transfer complexes (CTC) of risperidone with picric acid (PA), 2,3-dichloro-5,6-dicyano-p-benzoquinon (DDQ), tetracyanoquinodimethane (TCNQ), tetracyano ethylene (TCNE), tetrabromo-p-quinon (BL) and tetrachloro-p-quinon (CL) have been studied spectrophotometrically in absolute methanol at room temperature. The stoichiometries of the complexes were found to be 1:1 ratio by the photometric molar ratio between risperidone and the π-acceptors. The equilibrium constants, molar extinction coefficient (ɛCT) and spectroscopic-physical parameters (standard free energy (ΔGo), oscillator strength (f), transition dipole moment (μ), resonance energy (RN) and ionization potential (ID)) of the complexes were determined upon the modified Benesi-Hildebrand equation. Risperidone in pure form was applied in this study. The results indicate that the formation constants for the complexes depend on the nature of electron acceptors and donor, and also the spectral studies of the complexes were determined by (infrared, Raman, and 1H NMR) spectra and X-ray powder diffraction (XRD). The most stable mono-protonated form of Ris is characterized by the formation of +Nsbnd H (pyrimidine ring) intramolecular hydrogen bonded. In the high-wavenumber spectral region ˜3400 cm-1, the bands of the +Nsbnd H stretching vibrations and of the pyrimidine nitrogen atom could be potentially useful to discriminate the investigated forms of Ris. The infrared spectra of both Ris complexes are confirming the participation of +Nsbnd H pyrimidine ring in the donor-acceptor interaction.

  19. Jacaranone induces apoptosis in melanoma cells via ROS-mediated downregulation of Akt and p38 MAPK activation and displays antitumor activity in vivo.

    Directory of Open Access Journals (Sweden)

    Mariana H Massaoka

    Full Text Available BACKGROUND: Malignant melanoma is a deadly type of metastatic skin cancer with increased incidence over the past 30 years. Despite the advanced knowledge on the biology, immunobiology and molecular genetics of melanoma, the alternatives of treatment are limited with poor prognosis. On clinical trials, natural products and among them redox-active quinones have been tested in the attempt to control the growth of cancer cells. Recently, we isolated jacaranone from Pentacalia desiderabilis, a benzoquinone derivative that showed a broad antitumor activity and protective anti-melanoma effect in a syngeneic model. The purified substance is active at micromolar concentrations, is not hemolytic, and is not toxic in naïve mice. METHODOLOGY/PRINCIPAL FINDINGS: The jacaranone antitumor activity was shown against several human cancer cell lines in vitro. Moreover, the induction of apoptosis in murine melanoma cells and jacaranone antitumor activity in vivo, in a melanoma experimental model, were also shown. Jacaranone renders antiproliferative and proapoptotic responses in tumor cells, by acting on Akt and p38 MAPK signaling pathways through generation of reactive oxygen species (ROS. The free radical scavenger N-acetyl-cysteine (NAC was able to completely suppress cell death induced by jacaranone as it blocked Akt downregulation, p38 MAPK activation as well as upregulation of proapoptotic Bax. Notably, treatment of melanoma growing subcutaneously in mice with jacaranone significantly extended the mean survival times in a dose-dependent manner. CONCLUSIONS/SIGNIFICANCE: The results provide evidence for the mechanisms of action of jacaranone and emphasize the potential use of this quinone for the treatment of melanoma.

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

    Science.gov (United States)

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

    2009-11-01

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

  1. Odoriferous Defensive stink gland transcriptome to identify novel genes necessary for quinone synthesis in the red flour beetle, Tribolium castaneum.

    Directory of Open Access Journals (Sweden)

    Jianwei Li

    Full Text Available Chemical defense is one of the most important traits, which endow insects the ability to conquer a most diverse set of ecological environments. Chemical secretions are used for defense against anything from vertebrate or invertebrate predators to prokaryotic or eukaryotic parasites or food competitors. Tenebrionid beetles are especially prolific in this category, producing several varieties of substituted benzoquinone compounds. In order to get a better understanding of the genetic and molecular basis of defensive secretions, we performed RNA sequencing in a newly emerging insect model, the red flour beetle Tribolium castaneum (Coleoptera: Tenebrionidae. To detect genes that are highly and specifically expressed in the odoriferous gland tissues that secret defensive chemical compounds, we compared them to a control tissue, the anterior abdomen. 511 genes were identified in different subtraction groups. Of these, 77 genes were functionally analyzed by RNA interference (RNAi to recognize induced gland alterations morphologically or changes in gland volatiles by gas chromatography-mass spectrometry. 29 genes (38% presented strong visible phenotypes, while 67 genes (87% showed alterations of at least one gland content. Three of these genes showing quinone-less (ql phenotypes - Tcas-ql VTGl; Tcas-ql ARSB; Tcas-ql MRP - were isolated, molecularly characterized, their expression identified in both types of the secretory glandular cells, and their function determined by quantification of all main components after RNAi. In addition, microbe inhibition assays revealed that a quinone-free status is unable to impede bacterial or fungal growth. Phylogenetic analyses of these three genes indicate that they have evolved independently and specifically for chemical defense in beetles.

  2. Stability of solutions of antineoplastic agents during preparation and storage for in vitro assays. General considerations, the nitrosoureas and alkylating agents.

    Science.gov (United States)

    Bosanquet, A G

    1985-01-01

    In vitro drug sensitivity of tumour biopsies is currently being determined using a variety of methods. For these chemosensitivity assays many drugs are required at short notice, and this in turn means that the drugs must generally be stored in solution. There are, however, a number of potential problems associated with dissolving and storing drugs for in vitro use, which include (a) drug adsorption; (b) effects of freezing; (c) drug stability under the normal conditions of dilution and setting up of an in vitro assay; and (d) insolubility of drugs in normal saline (NS) or phosphate-buffered saline (PBS). These problems are considered in general, and some recommendations for use of solutions of drugs in in vitro assays are suggested. The nitrosoureas and alkylating agents are also investigated in greater detail in this respect. The nitrosoureas are found to be very labile in PBS at pH 7, with 5% degradation (t0.95) occurring in 10-50 min at room temperature. These values are increased about 10-fold on refrigeration and about 5- to 10-fold on reduction of the pH of the medium to pH 4-5. At pH 7 and room temperature, t0.95 is observed in under 1 h with the alkylating agents nitrogen mustard, chlorambucil, melphalan, 2,5-diaziridinyl-3,6-bis(2-hydroxyethylamino)-1,4-benzoquinone (BZQ), dibromodulcitol, dibromomannitol, treosulphan, and procarbazine. Of the other alkylating agents, 4-hydroperoxycylophosphamide (sometimes used in vitro in place of cyclophosphamide), busulphan, dianhydrogalactitol, aziridinylbenzoquinone (AZQ), and dacarbazine have a t0.95 of between 2 and 24 h, while ifosfamide and pentamethylmelamine are both stable in aqueous solution for greater than 7 days. About half the drugs studied in detail have been stored frozen in solution for in vitro use, although very little is known about their stability under these conditions.

  3. Assessing the chemotaxis behavior of Physarum polycephalum to a range of simple volatile organic chemicals.

    Science.gov (United States)

    de Lacy Costello, Ben P J; Adamatzky, Andrew I

    2013-09-01

    The chemotaxis behavior of the plasmodial stage of the true slime mold Physarum Polycephalum was assessed when given a binary choice between two volatile organic chemicals (VOCs) placed in its environment. All possible binary combinations were tested between 19 separate VOCs selected due to their prevalence and biological activity in common plant and insect species. The slime mold exhibited positive chemotaxis toward a number of VOCs with the following order of preference:   Farnesene > β-myrcene > tridecane > limonene > p-cymene > 3-octanone > β-pinene > m-cresol > benzylacetate > cis-3-hexenylacetate. For the remaining compounds, no positive chemotaxis was observed in any of the experiments, and for most compounds there was an inhibitory effect on the growth of the slime mold. By assessing this lack of growth or failure to propagate, it was possible to produce a list of compounds ranked in terms of their inhibitory effect: nonanal > benzaldehyde > methylbenzoate > linalool > methyl-p-benzoquinone > eugenol > benzyl alcohol > geraniol > 2-phenylethanol. This analysis shows a distinct preference of the slime mold for non-oxygenated terpene and terpene-like compounds (farnesene, β-myrcene, limonene, p-cymene and β-pinene). In contrast, terpene-based alcohols such as geraniol and linalool were found to have a strong inhibitory effect on the slime mold. Both the aldehydes utilized in this study had the strongest inhibitory effect on the slime mold of all the 19 VOCs tested. Interestingly, 3-octanone, which has a strong association with a "fungal odor," was the only compound with an oxygenated functionality where Physarum Polycephalum exhibits distinct positive chemotaxis. PMID:24265848

  4. Electro-Fenton degradation of antimicrobials triclosan and triclocarban

    International Nuclear Information System (INIS)

    The antimicrobials triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether) and triclocarban (N-(4-chlorophenyl)-N'-(3,4-dichlorophenyl)urea) have been degraded by four electro-Fenton systems using undivided electrolytic cells with a Pt or boron-doped diamond (BDD) anode and a carbon felt or O2 diffusion cathode. The main oxidant is hydroxyl radical (·OH) produced both on the anode surface from water oxidation and in the medium by Fenton's reaction, which takes place between electrogenerated H2O2 and Fe2+ coming from cathodic reduction of O2 and Fe3+, respectively. Triclosan from saturated aqueous solutions of pH 3.0 is completely removed in all cells, decreasing its decay rate in the order: Pt/carbon felt > BDD/carbon felt > Pt/O2 diffusion > BDD/O2 diffusion, in agreement with their ·OH generation ability from Fenton's reaction. Glyoxylic, maleic and oxalic acids are identified as aliphatic intermediates. Complexes between oxalic acid and iron ions persist largely in solution, although Fe2+-oxalato complexes are mineralized by ·OH in the medium and Fe3+-oxalato complexes are destroyed by ·OH on BDD. Analogous treatments of more concentrated triclosan solutions using a 20:80 (v/v) acetonitrile/water mixture as solvent evidence the role of hydroxyl radicals along the degradation. In this hydroorganic medium hydroxylated derivatives such as 2,4-dichlorophenol, 4-chlorocatechol, chlorohydroquinone and chloro-p-benzoquinone, and carboxylic acids such as maleic, oxalic, formic and acetic acids are detected as products. Complete destruction of iron-oxalato complexes and released Cl- ion involves some oxidizing species coming from parallel acetonitrile oxidation. The same electro-Fenton systems also yield the overall removal of triclocarban in acetonitrile/water mixtures, giving rise to urea, hydroquinone, chlorohydroquinone, 1-chloro-4-nitrobenzene and 1,2-dichloro-4-nitrobenzene as primary intermediates

  5. The Oxygen quantum yield in diverse algae and cyanobacteria is controlled by partitioning of flux between linear and cyclic electron flow within photosystem II.

    Science.gov (United States)

    Ananyev, Gennady; Gates, Colin; Dismukes, G Charles

    2016-09-01

    We have measured flash-induced oxygen quantum yields (O2-QYs) and primary charge separation (Chl variable fluorescence yield, Fv/Fm) in vivo among phylogenetically diverse microalgae and cyanobacteria. Higher O2-QYs can be attained in cells by releasing constraints on charge transfer at the Photosystem II (PSII) acceptor side by adding membrane-permeable benzoquinone (BQ) derivatives that oxidize plastosemiquinone QB(-) and QBH2. This method allows uncoupling PSII turnover from its natural regulation in living cells, without artifacts of isolating PSII complexes. This approach reveals different extents of regulation across species, controlled at the QB(-) acceptor site. Arthrospira maxima is confirmed as the most efficient PSII-WOC (water oxidizing complex) and exhibits the least regulation of flux. Thermosynechococcus elongatus exhibits an O2-QY of 30%, suggesting strong downregulation. WOC cycle simulations with the most accurate model (VZAD) show that a light-driven backward transition (net addition of an electron to the WOC, distinct from recombination) occurs in up to 25% of native PSIIs in the S2 and S3 states, while adding BQ prevents backward transitions and increases the lifetime of S2 and S3 by 10-fold. Backward transitions occur in PSIIs that have plastosemiquinone radicals in the QB site and are postulated to be physiologically regulated pathways for storing light energy as proton gradient through direct PSII-cyclic electron flow (PSII-CEF). PSII-CEF is independent of classical PSI/cyt-b6f-CEF and provides an alternative proton translocation pathway for energy conversion. PSII-CEF enables variable fluxes between linear and cyclic electron pathways, thus accommodating species-dependent needs for redox and ion-gradient energy sources powered by a single photosystem. PMID:27117512

  6. Benzene-derived N2-(4-hydroxyphenyl)-deoxyguanosine adduct: UvrABC incision and its conformation in DNA

    Energy Technology Data Exchange (ETDEWEB)

    Hang, Bo; Rodriguez, Ben; Yang, Yanu; Guliaev, Anton B.; Chenna, Ahmed

    2010-06-14

    Benzene, a ubiquitous human carcinogen, forms DNA adducts through its metabolites such as p-benzoquinone (p-BQ) and hydroquinone (HQ). N(2)-(4-Hydroxyphenyl)-2'-deoxyguanosine (N(2)-4-HOPh-dG) is the principal adduct identified in vivo by (32)P-postlabeling in cells or animals treated with p-BQ or HQ. To study its effect on repair specificity and replication fidelity, we recently synthesized defined oligonucleotides containing a site-specific adduct using phosphoramidite chemistry. We here report the repair of this adduct by Escherichia coli UvrABC complex, which performs the initial damage recognition and incision steps in the nucleotide excision repair (NER) pathway. We first showed that the p-BQ-treated plasmid was efficiently cleaved by the complex, indicating the formation of DNA lesions that are substrates for NER. Using a 40-mer substrate, we found that UvrABC incises the DNA strand containing N(2)-4-HOPh-dG in a dose- and time-dependent manner. The specificity of such repair was also compared with that of DNA glycosylases and damage-specific endonucleases of E. coli, both of which were found to have no detectable activity toward N(2)-4-HOPh-dG. To understand why this adduct is specifically recognized and processed by UvrABC, molecular modeling studies were performed. Analysis of molecular dynamics trajectories showed that stable G:C-like hydrogen bonding patterns of all three Watson-Crick hydrogen bonds are present within the N(2)-4-HOPh-G:C base pair, with the hydroxyphenyl ring at an almost planar position. In addition, N(2)-4-HOPh-dG has a tendency to form more stable stacking interactions than a normal G in B-type DNA. These conformational properties may be critical in differential recognition of this adduct by specific repair enzymes.

  7. Oxidation of lignin and cellulose, humification and coalification

    Energy Technology Data Exchange (ETDEWEB)

    Volborth, A.

    1976-06-09

    Oxygen plays an important role in the first stages of the decomposition of organic substances derived from plant material. The decomposition and reformation of such organic matter as cellulose and lignin leads, through-humification and a sequence of metamorphic processes, to the formation of coal. Initially, oxidation reactions cause the formation of dark-colored humic acids, later under more anaerobic conditions, pressure and higher temperatures, polymerization occurs as the sediment becomes buried. Under these conditions phenolic compounds are more stable, also during the processes of decomposition phenolic substances are more resistant to microorganisms, and thus seem to accumulate. The humification process may be considered as the first step in coalification. It starts by rapid decomposition of the cellulose and by enzymatic degradation of the lignin of the rotting plant substance to form C/sub 6/-C/sub 3/ or C/sub 6/-C/sub 1/ compounds. These lose methoxyl groups and carboxyl groups and can form hydroquinones which may polymerize and combine, forming humic acids. Degradation may proceed also to aliphatic compounds. Most of the reactions seem to lead to benzoquinones which dimerize and polymerize further, causing an increase in aromatization with age, and under more anaerobic conditions later during coalification. When conditions become anaerobic, melanoidin and glucosamin compounds form and nitrogen fixation occurs. This explains the presence of about 1 to 3.5 percent nitrogen in humic acid concentrates, lignin, lignite, subbituminous and bituminous coal. The fixation of nitrogen also results in further reduction of carbon in humic substance during the later stages of humification. Further coalification of buried humified strata of decomposed organic material causes reduction as the methoxyl and oxygen group content decreases, and CO and CO/sub 2/ gases and H/sub 2/O evolve and gradual dehydration occurs.

  8. In situ energy transfer quenching of quantum dot electrochemiluminescence for sensitive detection of cancer biomarkers.

    Science.gov (United States)

    Yang, Mengli; Chen, Ying; Xiang, Yun; Yuan, Ruo; Chai, Yaqin

    2013-12-15

    In this work, we develop a sensitive and selective method for the detection of a cancer biomarker (carcinoembryonic antigen, CEA) based on a new electrochemiluminescence (ECL) energy transfer mechanism, in which the energy transfer occurs from the excited quantum dots (QDs) to the in situ electro-generated quenchers. A CdTe QD-containing composite film is first deposited on the electrode followed by the conjugation of the primary antibody (Ab1) on the film. Subsequent incubation of the modified sensing electrode with CEA and the secondary antibody-alkaline phosphatase-gold nanoparticle labels (Ab2-ALP-AuNP) leads to the formation of the Ab1/CEA/Ab2-ALP-AuNPs immunocomplexes on the electrode surface. The captured ALP catalyzes the p-nitrophenyl phosphate disodium salt (p-NPP) substrate in the ECL detection buffer to p-nitrophenol (p-NP). The potential sweep on the electrode results in the oxidation of p-NP to p-benzoquinone (p-BQ) and the generation of excited QDs. The ECL emission of the excited QDs is therefore quenched through direct energy transfer from the excited QDs to p-BQ. This ECL quenching effect is significantly amplified because of the numerous ALP enzymes involved in each antibody-antigen recognition event. This proposed method of amplified quenching of QD ECL emission offers a low detection limit of 1.67 pg mL(-1) for CEA. In addition, this method exhibits high reproducibility and selectivity and can also be applied to serum samples. Given these advantages, this new ECL energy transfer approach holds great promise for the detection of other biological targets and has potential applications in clinical diagnoses. PMID:23891869

  9. Vinpocetine reduces carrageenan-induced inflammatory hyperalgesia in mice by inhibiting oxidative stress, cytokine production and NF-κB activation in the paw and spinal cord.

    Directory of Open Access Journals (Sweden)

    Kenji W Ruiz-Miyazawa

    Full Text Available Vinpocetine is a safe nootropic agent used for neurological and cerebrovascular diseases. The anti-inflammatory activity of vinpocetine has been shown in cell based assays and animal models, leading to suggestions as to its utility in analgesia. However, the mechanisms regarding its efficacy in inflammatory pain treatment are still not completely understood. Herein, the analgesic effect of vinpocetine and its anti-inflammatory and antioxidant mechanisms were addressed in murine inflammatory pain models. Firstly, we investigated the protective effects of vinpocetine in overt pain-like behavior induced by acetic acid, phenyl-p-benzoquinone (PBQ and formalin. The intraplantar injection of carrageenan was then used to induce inflammatory hyperalgesia. Mechanical and thermal hyperalgesia were evaluated using the electronic von Frey and the hot plate tests, respectively, with neutrophil recruitment to the paw assessed by a myeloperoxidase activity assay. A number of factors were assessed, both peripherally and in the spinal cord, including: antioxidant capacity, reduced glutathione (GSH levels, superoxide anion, tumor necrosis factor alpha (TNF-α and interleukin 1 beta (IL-1β levels, as well as nuclear factor kappa B (NF-κB activation. Vinpocetine inhibited the overt pain-like behavior induced by acetic acid, PBQ and formalin (at both phases, as well as the carrageenan-induced mechanical and thermal hyperalgesia and associated neutrophil recruitment. Both peripherally and in the spinal cord, vinpocetine also inhibited: antioxidant capacity and GSH depletion; increased superoxide anion; IL-1β and TNF-α levels; and NF-κB activation. As such, vinpocetine significantly reduces inflammatory pain by targeting oxidative stress, cytokine production and NF-κB activation at both peripheral and spinal cord levels.

  10. Hydrogen bonded NHO chains formed by chloranilic acid (CLA) with 4,4′-di-t-butyl-2,2′-bipyridyl (dtBBP) in the solid state

    International Nuclear Information System (INIS)

    Graphical abstract: The molecular complex dtBBP·CLA, its crystal structure at 100 K, infrared, the DFT calculations, a phase transition at ca. 414 K, DSC, dielectric response analysis, proton dynamics, antiferroelectric properties. Highlights: ► We synthesized a novel molecular complex, dtBBP·CLA. ► We determined the crystal structure of dtBBP·CLA at 100 K. ► We detected a phase transition at 414 K in the complex and postulated its mechanism. ► We interpreted the infrared spectra of dtBBP·CLA. ► We used DFT to calculate the molecular structure of dtBBP·CLA in solid state. - Abstract: In crystalline state 2,5-dichloro-3,6-dihydroxy-p-benzoquinone (chloranilic acid, CLA) forms with 4,4′-di-t-butyl-2,2′-bipyridyl (dtBBP) the hydrogen bonded chains along the b-axis. From one side of the CLA molecule the proton transfer takes place and the hydrogen bond length is very short (2.615 Å). A continuous infrared absorption is observed for dtBBP·CLA in the wavenumber range between 3100 and 800 cm−1 also indicating the strong hydrogen bonds. The DSC measurements show a weak, close to continuous, phase transition at 414 K. The complex dielectric permittivity for a single crystal sample was measured in the temperature range 100–440 K and at frequencies between 200 Hz and 2 MHz. The dielectric response is a combination of semiconducting properties and a relaxation process most probably connected with the proton dynamics in the hydrogen bonds. The mechanism of the structural phase transition is discussed.

  11. Rifampicin-activated human pregnane X receptor and CYP3A4 induction enhance acetaminophen-induced toxicity.

    Science.gov (United States)

    Cheng, Jie; Ma, Xiaochao; Krausz, Kristopher W; Idle, Jeffrey R; Gonzalez, Frank J

    2009-08-01

    Acetaminophen (APAP) is safe at therapeutic levels but causes hepatotoxicity via N-acetyl-p-benzoquinone imine-induced oxidative stress upon overdose. To determine the effect of human (h) pregnane X receptor (PXR) activation and CYP3A4 induction on APAP-induced hepatotoxicity, mice humanized for PXR and CYP3A4 (TgCYP3A4/hPXR) were treated with APAP and rifampicin. Human PXR activation and CYP3A4 induction enhanced APAP-induced hepatotoxicity as revealed by hepatic alanine aminotransferase (ALT) and aspartate aminotransferase (AST) activities elevated in serum, and hepatic necrosis after coadministration of rifampicin and APAP, compared with APAP administration alone. In contrast, hPXR mice, wild-type mice, and Pxr-null mice exhibited significantly lower ALT/AST levels compared with TgCYP3A4/hPXR mice after APAP administration. Toxicity was coincident with depletion of hepatic glutathione and increased production of hydrogen peroxide, suggesting increased oxidative stress upon hPXR activation. Moreover, mRNA analysis demonstrated that CYP3A4 and other PXR target genes were significantly induced by rifampicin treatment. Urinary metabolomic analysis indicated that cysteine-APAP and its metabolite S-(5-acetylamino-2-hydroxyphenyl)mercaptopyruvic acid were the major contributors to the toxic phenotype. Quantification of plasma APAP metabolites indicated that the APAP dimer formed coincident with increased oxidative stress. In addition, serum metabolomics revealed reduction of lysophosphatidylcholine in the APAP-treated groups. These findings demonstrated that human PXR is involved in regulation of APAP-induced toxicity through CYP3A4-mediated hepatic metabolism of APAP in the presence of PXR ligands.

  12. Investigation of acetaminophen toxicity in HepG2/C3a microscale cultures using a system biology model of glutathione depletion.

    Science.gov (United States)

    Leclerc, Eric; Hamon, Jeremy; Claude, Isabelle; Jellali, Rachid; Naudot, Marie; Bois, Frederic

    2015-06-01

    We have integrated in vitro and in silico information to investigate acetaminophen (APAP) and its metabolite N-acetyl-p-benzoquinone imine (NAPQI) toxicity in liver biochip. In previous works, we observed higher cytotoxicity of HepG2/C3a cultivated in biochips when exposed to 1 mM of APAP for 72 h as compared to Petri cultures. We complete our investigation with the present in silico approach to extend the mechanistic interpretation of the intracellular kinetics of the toxicity process. For that purpose, we propose a mathematical model based on the coupling of a drug pharmacokinetic model (PK) with a systemic biology model (SB) describing the reactive oxygen species (ROS) production by NAPQI and the subsequent glutathione (GSH) depletion. The SB model was parameterized using (i) transcriptomic data, (ii) qualitative results of time lapses ROS fluorescent curves for both control and 1-mM APAP-treated experiments, and (iii) additional GSH literature data. The PK model was parameterized (i) using the in vitro kinetic data (at 160 μM, 1 mM, 10 mM), (ii) using the parameters resulting from a physiologically based pharmacokinetic (PBPK) literature model for APAP, and (iii) by literature data describing NAPQI formation. The PK-SB model predicted a ROS increase and GSH depletion due to the NAPQI formation. The transition from a detoxification phase and NAPQI and ROS accumulation was predicted for a NAPQI concentration ranging between 0.025 and 0.25 μM in the cytosol. In parallel, we performed a dose response analysis in biochips that shows a reduction of the final hepatic cell number appeared in agreement with the time and doses associated with the switch of the NAPQI detoxification/accumulation. As a result, we were able to correlate in vitro extracellular APAP exposures with an intracellular in silico ROS accumulation using an integration of a coupled mathematical and experimental liver on chip approach.

  13. Acylcarnitine Profiles in Acetaminophen Toxicity in the Mouse: Comparison to Toxicity, Metabolism and Hepatocyte Regeneration

    Directory of Open Access Journals (Sweden)

    Jack Hinson

    2013-08-01

    Full Text Available High doses of acetaminophen (APAP result in hepatotoxicity that involves metabolic activation of the parent compound, covalent binding of the reactive intermediate N-acetyl-p-benzoquinone imine (NAPQI to liver proteins, and depletion of hepatic glutathione. Impaired fatty acid β-oxidation has been implicated in previous studies of APAP-induced hepatotoxicity. To better understand relationships between toxicity and fatty acid β-oxidation in the liver in APAP toxicity, metabolomic assays for long chain acylcarnitines were examined in relationship to established markers of liver toxicity, oxidative metabolism, and liver regeneration in a time course study in mice. Male B6C3F1 mice were treated with APAP (200 mg/kg IP or saline and sacrificed at 1, 2, 4, 8, 24 or 48 h after APAP. At 1 h, hepatic glutathione was depleted and APAP protein adducts were markedly increased. Alanine aminotransferase (ALT levels were elevated at 4 and 8 h, while proliferating cell nuclear antigen (PCNA expression, indicative of hepatocyte regeneration, was apparent at 24 h and 48 h. Elevations of palmitoyl, oleoyl and myristoyl carnitine were apparent by 2–4 h, concurrent with the onset of Oil Red O staining in liver sections. By 8 h, acylcarnitine levels were below baseline levels and remained low at 24 and 48 h. A partial least squares (PLS model suggested a direct association of acylcarnitine accumulation in serum to APAP protein adduct and hepatic glutathione levels in mice. Overall, the kinetics of serum acylcarnitines in APAP toxicity in mice followed a biphasic pattern involving early elevation after the metabolism phases of toxicity and later depletion of acylcarnitines.

  14. Metabolic pathway involved in 2-methyl-6-ethylaniline degradation by Sphingobium sp. strain MEA3-1 and cloning of the novel flavin-dependent monooxygenase system meaBA.

    Science.gov (United States)

    Dong, Weiliang; Chen, Qiongzhen; Hou, Ying; Li, Shuhuan; Zhuang, Kai; Huang, Fei; Zhou, Jie; Li, Zhoukun; Wang, Jue; Fu, Lei; Zhang, Zhengguang; Huang, Yan; Wang, Fei; Cui, Zhongli

    2015-12-01

    2-Methyl-6-ethylaniline (MEA) is the main microbial degradation intermediate of the chloroacetanilide herbicides acetochlor and metolachlor. Sphingobium sp. strain MEA3-1 can utilize MEA and various alkyl-substituted aniline and phenol compounds as sole carbon and energy sources for growth. We isolated the mutant strain MEA3-1Mut, which converts MEA only to 2-methyl-6-ethyl-hydroquinone (MEHQ) and 2-methyl-6-ethyl-benzoquinone (MEBQ). MEA may be oxidized by the P450 monooxygenase system to 4-hydroxy-2-methyl-6-ethylaniline (4-OH-MEA), which can be hydrolytically spontaneously deaminated to MEBQ or MEHQ. The MEA microbial metabolic pathway was reconstituted based on the substrate spectra and identification of the intermediate metabolites in both the wild-type and mutant strains. Plasmidome sequencing indicated that both strains harbored 7 plasmids with sizes ranging from 6,108 bp to 287,745 bp. Among the 7 plasmids, 6 were identical, and pMEA02' in strain MEA3-1Mut lost a 37,000-bp fragment compared to pMEA02 in strain MEA3-1. Two-dimensional electrophoresis (2-DE) and protein mass fingerprinting (PMF) showed that MEA3-1Mut lost the two-component flavin-dependent monooxygenase (TC-FDM) MeaBA, which was encoded by a gene in the lost fragment of pMEA02. MeaA shared 22% to 25% amino acid sequence identity with oxygenase components of some TC-FDMs, whereas MeaB showed no sequence identity with the reductase components of those TC-FDMs. Complementation with meaBA in MEA3-1Mut and heterologous expression in Pseudomonas putida strain KT2440 resulted in the production of an active MEHQ monooxygenase.

  15. 2-Hetaryl-1,3-tropolones based on five-membered nitrogen heterocycles: synthesis, structure and properties

    Directory of Open Access Journals (Sweden)

    Yury A. Sayapin

    2015-11-01

    Full Text Available A series of derivatives of 2-hetaryl-1,3-tropolone (β-tropolone was prepared by the acid-catalyzed reaction of 2-methylbenzoxazoles, 2-methylbenzothiazoles and 2,3,3-trimethylindoline with 3,4,5,6-tetrachloro-1,2-benzoquinone. The molecular structures of the three representative compounds were determined by X-ray crystallography. In crystal and (as shown by the DFT PBE0/6-311+G** calculations in solution, 2-hetaryl-4,5,6,7-tetrachloro- and 2-hetaryl-5,6,7-trichloro-1,3-tropolones exist in the NH-tautomeric form with a strong resonance-assisted intramolecular N–H···O hydrogen bond. The mechanism of the formation of 1,3-tropolones in the reaction of methylene-active five-membered heterocycles with o-chloranil in acetic acid solution has been studied using density functional theory (DFT methods. The reaction of 2-(2-benzoxa(thiazolyl-5,6,7-trichloro(4,5,6,7-tetrachloro-1,3-tropolones with alcohols leads to the contraction of the seven-membered tropone ring with the formation of 2-(2-benzoxa(thiazolyl-6-alkoxycarbonylphenols. The molecular structure of 2-(2-ethoxycarbonyl-6-hydroxy-3,4,5-trichlorophenylbenzoxazole has been determined by X-ray diffraction. 2-(2-Benzoxa(thiazolyl-6-alkoxycarbonylphenols display intense green fluorescence with anomalous Stokes shifts caused by the excited state intramolecular proton transfer (ESIPT effects.

  16. 2-Hetaryl-1,3-tropolones based on five-membered nitrogen heterocycles: synthesis, structure and properties

    Science.gov (United States)

    Sayapin, Yury A; Tupaeva, Inna O; Kolodina, Alexandra A; Gusakov, Eugeny A; Komissarov, Vitaly N; Makarova, Nadezhda I; Metelitsa, Anatoly V; Tkachev, Valery V; Aldoshin, Sergey M; Minkin, Vladimir I

    2015-01-01

    Summary A series of derivatives of 2-hetaryl-1,3-tropolone (β-tropolone) was prepared by the acid-catalyzed reaction of 2-methylbenzoxazoles, 2-methylbenzothiazoles and 2,3,3-trimethylindoline with 3,4,5,6-tetrachloro-1,2-benzoquinone. The molecular structures of the three representative compounds were determined by X-ray crystallography. In crystal and (as shown by the DFT PBE0/6-311+G** calculations) in solution, 2-hetaryl-4,5,6,7-tetrachloro- and 2-hetaryl-5,6,7-trichloro-1,3-tropolones exist in the NH-tautomeric form with a strong resonance-assisted intramolecular N–H···O hydrogen bond. The mechanism of the formation of 1,3-tropolones in the reaction of methylene-active five-membered heterocycles with o-chloranil in acetic acid solution has been studied using density functional theory (DFT) methods. The reaction of 2-(2-benzoxa(thia)zolyl)-5,6,7-trichloro(4,5,6,7-tetrachloro)-1,3-tropolones with alcohols leads to the contraction of the seven-membered tropone ring with the formation of 2-(2-benzoxa(thia)zolyl)-6-alkoxycarbonylphenols. The molecular structure of 2-(2-ethoxycarbonyl-6-hydroxy-3,4,5-trichlorophenyl)benzoxazole has been determined by X-ray diffraction. 2-(2-Benzoxa(thia)zolyl)-6-alkoxycarbonylphenols display intense green fluorescence with anomalous Stokes shifts caused by the excited state intramolecular proton transfer (ESIPT) effects. PMID:26664640

  17. Versatile chemical transformations of benzoxazole based ligands on complexation with 3d-metal ions.

    Science.gov (United States)

    Iasco, Olga; Novitchi, Ghenadie; Jeanneau, Erwann; Tommasino, Jean Bernard; Roques, Nans; Luneau, Dominique

    2012-02-20

    Two benzoxazoles derivative ligands were synthesized from the condensation of 3,5-di-tert-butyl-o-benzoquinone (DTBBQ) with ethanolamine or 1,3-diamino-2-hydroxypropane in methanol. Condensation of DTBBQ with ethanolamine gives the expected 5,7-di-tert-butyl-2-methylenhydroxylbenzoxazole (HL1) while with 1,3-diamino-2-hydroxypropane it gives (2-hydroxyethyl-2-{2,4-bis(1,1-dimethylethyl)-1-phenol-6 amino}-2{5,7-di-tert-butyl-benzoxazole}) (H(2)L2) with only one benzoxazole ring instead of the symmetric bis-benzoxazole derivative. The structure of HL1 and H(2)L2 were confirmed by NMR-spectroscopy and X-ray diffraction on a single crystal for HL1. The reaction of HL1 with CuCl(2) gives a mononuclear [Cu(II)(HL1)(2)Cl(2)] (1) complex for which the crystal structure shows that HL1 is preserved. In contrast, upon reaction with nickel(II), cobalt(II), and manganese(II) H(2)L2 is further oxidized and transformed in new ligands HL3 in mononuclear complexes [M(II)(L3)(2)] (M = Ni(II) (2); M = Co(II) (3)) and H(2)L4 in tetranuclear complex [Mn(II)(4)(HL4)(4)Cl(4)] (4) as found from the crystal structures of complexes 2-4. Electrochemical studies for complexes 2 and 3 evidence complicated redox properties. [Mn(II)(4)(HL4)(4)Cl(4)] (4) has a cubane-like structure with a "4 + 2" fashion The magnetic susceptibility of 4 is well fitted considering one Mn---Mn interaction J(a)(Mn(II)-Mn(II)) = -0.50(1) cm(-1) with g = 2.00(7).

  18. Biotic nitrosation of diclofenac in a soil aquifer system (Katari watershed, Bolivia).

    Science.gov (United States)

    Chiron, Serge; Duwig, Céline

    2016-09-15

    Up till now, the diclofenac (DCF) transformation into its nitrogen-derivatives, N-nitroso-DCF (NO-DCF) and 5-nitro-DCF (NO2-DCF), has been mainly investigated in wastewater treatment plant under nitrification or denitrification processes. This work reports, for the first time, an additional DCF microbial mediated nitrosation pathway of DCF in soil under strictly anoxic conditions probably involving codenitrification processes and fungal activities. This transformation pathway was investigated by using field observations data at a soil aquifer system (Katari watershed, Bolivia) and by carrying out soil slurry batch experiments. It was also observed for diphenylamine (DPA). Field measurements revealed the occurrence of NO-DCF, NO2-DCF and NO-DPA in groundwater samples at concentration levels in the 6-68s/L range. These concentration levels are more significant than those previously reported in wastewater treatment plant effluents taking into account dilution processes in soil. Interestingly, the p-benzoquinone imine of 5-OH-DCF was also found to be rather stable in surface water. In laboratory batch experiments under strictly anoxic conditions, the transformation of DCF and DPA into their corresponding N-nitroso derivatives was well correlated to denitrification processes. It was also observed that NO-DCF evolved into NO2-DCF while NO-DPA was stable. In vitro experiments showed that the Fisher-Hepp rearrangement could not account for NO2-DCF formation. One possible mechanism might be that NO-DCF underwent spontaneous NO loss to give the resulting intermediates diphenylaminyl radical or nitrenium cation which might evolve into NO2-DCF in presence of NO2 radical or nitrite ion, respectively. PMID:27183461

  19. Probing fundamental film parameters of immobilized enzymes--towards enhanced biosensor performance. Part II-Electroanalytical estimation of immobilized enzyme performance.

    Science.gov (United States)

    Fogel, R; Limson, J L

    2011-07-10

    The method of immobilization of a protein has a great influence on the overall conformation, and hence, functioning of the protein. Thus, a greater understanding of the events undergone by the protein during immobilization is key to manipulating the immobilization method to produce a strategy that influences the advantages of immobilization while minimizing their disadvantages in biosensor design. In this, the second paper of a two-part series, we have assessed the kinetic parameters of thin-film laccase monolayers, covalently attached to SAMs differing in spacer-arm length and lateral density of spacer arms. This was achieved using chronoamperometry and an electroactive product (p-benzoquinone), which was modeled in a non-linear regressional fashion to extract the relevant parameters. Finally, comparisons between the kinetic parameters presented in this paper and the rheological parameters of laccase monolayers immobilized in the same manner (Part I of this two paper series) were performed. Improvements in the maximal enzyme-catalysed current, i(max), the apparent Michaelis-Menten constant, K(m) and the apparent biosensor sensitivity were noted for most of the surfaces with increasing linker length. Decreasing the lateral density of the spacer-arms brought about a general improvement in these parameters, which is attributed to the decrease in multiple points of immobilization undergone by functional proteins. Finally, comparisons between rheological data and kinetics data showed that the degree of viscosity exhibited by protein films has a negative influence on attached protein layers, while enhanced protein hydration levels (assessed piezoelectrically from data obtained in Paper 1) has a positive effect on those surfaces comprising rigidly bound protein layers.

  20. Electric response in the antiferroelectric crystal of 4,4′-di-t-butyl-2,2′-bipyridyl with chloranilic acid

    Energy Technology Data Exchange (ETDEWEB)

    Rok, M., E-mail: magdalena.rok@chem.uni.wroc.pl; Piecha-Bisiorek, A.; Szklarz, P.; Bator, G.; Sobczyk, L.

    2015-05-01

    Highlights: • The semiconducting properties of the crystals were disclosed in the organic complex. • Dielectric relaxation and dc conductivity were investigated. • Activation energy for the thermally activated processes of the σ{sub dc} was estimated. • The effect of hydrogen bonds on the mechanism of the phase transition and the electric properties of the crystal was discussed. - Abstract: The electric response was analyzed in the vicinity of the structural phase transition at 412 K in the single crystals of 2,5-dichloro-3,6-dihydroxy-p-benzoquinone (chloranilic acid, CLA) with 4,4′-di-t-butyl-2,2′-bipyridyl (dtBBP). The dielectric permittivity of the complex measured along the b direction between 300 and 440 K and at frequencies ranging from 500 Hz to 2 MHz indicates two phenomena. At low frequencies, dielectric losses are ascribed to the electric conductivity of the crystal, while at high frequencies, to the dielectric relaxation described by means of the Cole–Cole relationship. The parameters of the dielectric response: the relaxation time, τ, the dielectric increment, ε{sub ο} − ε{sub ∞}, and the distribution parameter of the relaxation time, α, were estimated and analyzed. The low-temperature structure of the crystals indicates the antiferroelectric arrangement of the supramolecular hydrogen bonds. The dielectric results also presented for the deuterated crystals of dtBBP·CLA proved that the dynamics of protons in the hydrogen bonds are responsible for the mechanism of phase transition.

  1. Water oxidation chemistry of a synthetic dinuclear ruthenium complex containing redox-active quinone ligands.

    Science.gov (United States)

    Isobe, Hiroshi; Tanaka, Koji; Shen, Jian-Ren; Yamaguchi, Kizashi

    2014-04-21

    We investigated theoretically the catalytic mechanism of electrochemical water oxidation in aqueous solution by a dinuclear ruthenium complex containing redox-active quinone ligands, [Ru2(X)(Y)(3,6-tBu2Q)2(btpyan)](m+) [X, Y = H2O, OH, O, O2; 3,6-tBu2Q = 3,6-di-tert-butyl-1,2-benzoquinone; btpyan =1,8-bis(2,2':6',2″-terpyrid-4'-yl)anthracene] (m = 2, 3, 4) (1). The reaction involves a series of electron and proton transfers to achieve redox leveling, with intervening chemical transformations in a mesh scheme, and the entire molecular structure and motion of the catalyst 1 work together to drive the catalytic cycle for water oxidation. Two substrate water molecules can bind to 1 with simultaneous loss of one or two proton(s), which allows pH-dependent variability in the proportion of substrate-bound structures and following pathways for oxidative activation of the aqua/hydroxo ligands at low thermodynamic and kinetic costs. The resulting bis-oxo intermediates then undergo endothermic O-O radical coupling between two Ru(III)-O(•) units in an anti-coplanar conformation leading to bridged μ-peroxo or μ-superoxo intermediates. The μ-superoxo species can liberate oxygen with the necessity for the preceding binding of a water molecule, which is possible only after four-electron oxidation is completed. The magnitude of catalytic current would be limited by the inherent sluggishness of the hinge-like bending motion of the bridged μ-superoxo complex that opens up the compact, hydrophobic active site of the catalyst and thereby allows water entry under dynamic conditions. On the basis of a newly proposed mechanism, we rationalize the experimentally observed behavior of electrode kinetics with respect to potential and discuss what causes a high overpotential for water oxidation by 1.

  2. Single Plant Derived Nanotechnology for Synergistic Antibacterial Therapies

    Science.gov (United States)

    Kalluri, Jhansi R.; Gonzalez-Rodriguez, Roberto; Hartman, Phil S.; Loni, Armando; Canham, Leigh T.; Coffer, Jeffery L.

    2016-01-01

    present include stigmasterol and 2,6-dimethoxy-p-benzoquinone. PMID:27684478

  3. Pencil it in: pencil drawn electrochemical sensing platforms.

    Science.gov (United States)

    Foster, Christopher W; Brownson, Dale A C; Ruas de Souza, Ana P; Bernalte, Elena; Iniesta, Jesus; Bertotti, Mauro; Banks, Craig E

    2016-06-20

    Inspired by recent reports concerning the utilisation of hand drawn pencil macroelectrodes (PDEs), we report the fabrication, characterisation (physicochemical and electrochemical) and implementation (electrochemical sensing) of various PDEs drawn upon a flexible polyester substrate. Electrochemical characterisation reveals that there are no quantifiable electrochemical responses upon utilising these PDEs with an electroactive analyte that requires an electrochemical oxidation step first, therefore the PDEs have been examined towards the electroactive redox probes hexaammineruthenium(iii) chloride, potassium ferricyanide and ammonium iron(ii) sulfate. For the first time, characterisation of the number of drawn pencil layers and the grade of pencil are examined; these parameters are commonly overlooked when utilising PDEs. It is demonstrated that a PDE drawn ten times with a 6B pencil presented the most advantageous electrochemical platform, in terms of electrochemical reversibility and peak height/analytical signal. In consideration of the aforementioned limitation, analytes requiring an electrochemical reduction as the first process were solely analysed. We demonstrate the beneficial electroanalytical capabilities of these PDEs towards p-benzoquinone and the simultaneous detection of heavy metals, namely lead(ii) and cadmium(ii), all of which are explored for the first time utilising PDEs. Initially, the detection limits of this system were higher than desired for electroanalytical platforms, however upon implementation of the PDEs in a back-to-back configuration (in which two PDEs are placed back-to-back sharing a single connection to the potentiostat), the detection limits for lead(ii) and cadmium(ii) correspond to 10 μg L(-1) and 98 μg L(-1) respectively within model aqueous (0.1 M HCl) solutions.

  4. An Evaluation of Sensor Performance for Harmful Compounds by Using Photo-Induced Electron Transfer from Photosynthetic Membranes to Electrodes

    Science.gov (United States)

    Kasuno, Megumi; Kimura, Hiroki; Yasutomo, Hisataka; Torimura, Masaki; Murakami, Daisuke; Tsukatani, Yusuke; Hanada, Satoshi; Matsushita, Takayuki; Tao, Hiroaki

    2016-01-01

    Rapid, simple, and low-cost screening procedures are necessary for the detection of harmful compounds in the effluent that flows out of point sources such as industrial outfall. The present study investigated the effects on a novel sensor of harmful compounds such as KCN, phenol, and herbicides such as 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU), 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine (atrazine), and 2-N-tert-butyl-4-N-ethyl-6-methylsulfanyl-1,3,5-triazine-2,4-diamine (terbutryn). The sensor employed an electrode system that incorporated the photocurrent of intra-cytoplasmic membranes (so-called chromatophores) prepared from photosynthetic bacteria and linked using carbon paste electrodes. The amperometric curve (photocurrent-time curve) of photo-induced electron transfer from chromatophores of the purple photosynthetic bacterium Rhodobacter sphaeroides to the electrode via an exogenous electron acceptor was composed of two characteristic phases: an abrupt increase in current immediately after illumination (I0), and constant current over time (Ic). Compared with other redox compounds, 2,5-dichloro-1,4-benzoquinone (DCBQ) was the most useful exogenous electron acceptor in this system. Photo-reduction of DCBQ exhibited Michaelis-Menten-like kinetics, and reduction rates were dependent on the amount of DCBQ and the photon flux intensity. The Ic decreased in the presence of KCN at concentrations over 0.05 μM (=μmol·dm−3). The I0 decreased following the addition of phenol at concentrations over 20 μM. The Ic was affected by terbutryn at concentrations over 10 μM. In contrast, DCMU and atrazine had no effect on either I0 or Ic. The utility of this electrode system for the detection of harmful compounds is discussed. PMID:27023553

  5. Gas evolution in aluminum electrolytic capacitors

    Energy Technology Data Exchange (ETDEWEB)

    Gomez-Aleixandre, C.; Albella, J.M.; Martinez-Duart, J.M.

    1984-03-01

    Gas evolution in aluminum electrolytic capacitors constitutes one of their main drawbacks in comparison to other types of capacitors lacking a liquid electrolyte. In this respect, one of the most common causes of failure shown by liquid electrolyte capacitors is electrolyte leakage through the seal or even explosions produced by internal pressure buildup. In order to prevent these hazards, some substances, known as depolarizers, are usually added to the capacitor electrolyte with the purpose of absorbing the hydrogen evolved at the cathode (1, 2). Although the gas evolution problem in electrolytic capacitors has been known for a long time, there is a lack of literature on both direct measurements of the gas evolved and assessments of the amount of depolarizer active for the hydrogen absorption process. Aluminum electrolytic capacitors of 100..mu..F and 40V nominal voltage, miniature type (diam 8 mm, height 18.5 mm), were manufactured under standard specifications. The capacitors were filled with about 0.5 ml of an electrolyte consisting essentially of a solution of boric, adipic, and phosphoric acids in ethylene glycol. Picric acid and p-benzoquinone in molar concentrations of 0.01M and 0.05M, respectively, were added as depolarizers, yielding an electrolyte with a resistivity of about 80 ..cap omega..-cm and a pH of 5.1. The pressure inside the capacitors was monitored by a conventional Ushaped manometer made from a capillary glass tube filled with distilled water. The number of mols of gas generated in the capacitor (/eta/ /SUB g/ ) was calculated from the measured pressure (sensitivity 0.1 mm Hg) and the value of the internal volume of the manometercapacitor system.

  6. Solar photoelectro-Fenton degradation of the herbicide 4-chloro-2-methylphenoxyacetic acid optimized by response surface methodology

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Segura, Sergi [Laboratori d' Electroquimica dels Materials i del Medi Ambient, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Almeida, Lucio Cesar; Bocchi, Nerilso [Laboratorio de Pesquisas em Eletroquimica, Departamento de Quimica, Universidade Federal de Sao Carlos, C.P. 676, 13560-970 Sao Carlos - SP (Brazil); Brillas, Enric, E-mail: brillas@ub.edu [Laboratori d' Electroquimica dels Materials i del Medi Ambient, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain)

    2011-10-30

    Highlights: {yields} The herbicide MCPA is quickly mineralized by solar photoelectro-Fenton. {yields} A CCRD allowed the optimization of current, Fe{sup 2+} content and solution pH. {yields} TOC, MCE and energy consumption are described by response surface methodology. {yields} Generated hydroxyl radical destroys MCPA and its aromatic oxidation by-products. {yields} UV light of solar irradiation photolyzes the Fe(III)-carboxylate complexes produced. - Abstract: A central composite rotatable design and response surface methodology (RSM) were used to optimize the experimental variables of the solar photoelectro-Fenton (SPEF) treatment of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA). The experiments were made with a flow plant containing a Pt/air-diffusion reactor coupled to a solar compound parabolic collector (CPC) under recirculation of 10 L of 186 mg L{sup -1} MCPA solutions in 0.05 M Na{sub 2}SO{sub 4} at a liquid flow rate of 180 L h{sup -1} with an average UV irradiation intensity of about 32 W m{sup -2}. The optimum variables found for the SPEF process were 5.0 A, 1.0 mM Fe{sup 2+} and pH 3.0 after 120 min of electrolysis. Under these conditions, 75% of mineralization with 71% of current efficiency and 87.7 kWh kg{sup -1} TOC of energy consumption were obtained. MCPA decayed under the attack of generated hydroxyl radicals following a pseudo-first-order kinetics. Hydroxyl radicals also destroyed 4-chloro-2-methylphenol, methylhydroquinone and methyl-p-benzoquinone detected as aromatic by-products. Glycolic, maleic, fumaric, malic, succinic, tartronic, oxalic and formic acids were identified as generated carboxylic acids, which form Fe(III) complexes that are quickly photodecarboxylated by the UV irradiation of sunlight at the CPC photoreactor. A reaction sequence for the SPEF degradation of MCPA was proposed.

  7. Use of response surface methodology for development of new microwell-based spectrophotometric method for determination of atrovastatin calcium in tablets

    Directory of Open Access Journals (Sweden)

    Wani Tanveer A

    2012-11-01

    Full Text Available Abstract Background Response surface methodology by Box–Behnken design employing the multivariate approach enables substantial improvement in the method development using fewer experiments, without wastage of large volumes of organic solvents, which leads to high analysis cost. This methodology has not been employed for development of a method for analysis of atorvastatin calcium (ATR-Ca. Results The present research study describes the use of in optimization and validation of a new microwell-based UV-Visible spectrophotometric method of for determination of ATR-Ca in its tablets. By the use of quadratic regression analysis, equations were developed to describe the behavior of the response as simultaneous functions of the selected independent variables. Accordingly, the optimum conditions were determined which included concentration of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, time of reaction and temperature. The absorbance of the colored-CT complex was measured at 460 nm by microwell-plate absorbance reader. The method was validated, in accordance with ICH guidelines for accuracy, precision, selectivity and linearity (r² = 0.9993 over the concentration range of 20–200 μg/ml. The assay was successfully applied to the analysis of ATR-Ca in its pharmaceutical dosage forms with good accuracy and precision. Conclusion The assay described herein has great practical value in the routine analysis of ATR-Ca in quality control laboratories, as it has high throughput property, consumes minimum volume of organic solvent thus it offers the reduction in the exposures of the analysts to the toxic effects of organic solvents, environmentally friendly "Green" approach and reduction in the analysis cost by 50-fold.

  8. Oligomeric complexes of some heteroaromatic ligands and aromatic diamines with rhodium and molybdenum tetracarboxylates: 13C and 15N CPMAS NMR and density functional theory studies.

    Science.gov (United States)

    Leniak, Arkadiusz; Kamieński, Bohdan; Jaźwiński, Jarosław

    2015-05-01

    Seven new oligomeric complexes of 4,4'-bipyridine; 3,3'-bipyridine; benzene-1,4-diamine; benzene-1,3-diamine; benzene-1,2-diamine; and benzidine with rhodium tetraacetate, as well as 4,4'-bipyridine with molybdenum tetraacetate, have been obtained and investigated by elemental analysis and solid-state nuclear magnetic resonance spectroscopy, (13)C and (15)N CPMAS NMR. The known complexes of pyrazine with rhodium tetrabenzoate, benzoquinone with rhodium tetrapivalate, 4,4'-bipyridine with molybdenum tetrakistrifluoroacetate and the 1 : 1 complex of 2,2'-bipyridine with rhodium tetraacetate exhibiting axial-equatorial ligation mode have been obtained as well for comparison purposes. Elemental analysis revealed 1 : 1 complex stoichiometry of all complexes. The (15)N CPMAS NMR spectra of all new complexes consist of one narrow signal, indicating regular uniform structures. Benzidine forms a heterogeneous material, probably containing linear oligomers and products of further reactions. The complexes were characterized by the parameter complexation shift Δδ (Δδ = δcomplex  - δligand). This parameter ranged from around -40 to -90 ppm in the case of heteroaromatic ligands, from around -12 to -22 ppm for diamines and from -16 to -31 ppm for the complexes of molybdenum tetracarboxylates with 4,4'-bipyridine. The experimental results have been supported by a density functional theory computation of (15)N NMR chemical shifts and complexation shifts at the non-relativistic Becke, three-parameter, Perdew-Wang 91/[6-311++G(2d,p), Stuttgart] and GGA-PBE/QZ4P levels of theory and at the relativistic scalar and spin-orbit zeroth order regular approximation/GGA-PBE/QZ4P level of theory. Nucleus-independent chemical shifts have been calculated for the selected compounds. PMID:25614975

  9. Acute liver failure in a term neonate after repeated paracetamol administration

    Directory of Open Access Journals (Sweden)

    Fabio Bucaretchi

    2014-03-01

    Full Text Available Objective: Severe hepatotoxicity caused by paracetamol is rare in neonates. We report a case of paracetamol-induced acute liver failure in a term neonate. Case description: A 26-day-old boy was admitted with intestinal bleeding, shock signs, slight liver enlargement, coagulopathy, metabolic acidosis (pH=7.21; bicarbonate: 7.1mEq/L, hypoglycemia (18mg/dL, increased serum aminotransferase activity (AST=4,039IU/L; ALT=1,087IU/L and hyperbilirubinemia (total: 9.57mg/dL; direct: 6.18mg/dL after receiving oral paracetamol (10mg/kg/dose every 4 hours for three consecutive days (total dose around 180mg/kg; serum concentration 36-48 hours after the last dose of 77µg/ mL. Apart from supportive measures, the patient was successfully treated with intravenous N-acetylcysteine infusion during 11 consecutive days, and was discharged on day 34. The follow-up revealed full recovery of clinical and of laboratory findings of hepatic function. Comments: The paracetamol pharmacokinetics and pharmacodynamics in neonates and infants differ substantially from those in older children and adults. Despite the reduced rates of metabolism by the P-450 CYP2E1 enzyme system and the increased ability to synthesize glutathione - which provides greater resistance after overdoses -, it is possible to produce hepatotoxic metabolites (N-acetyl-p-benzoquinone that cause hepatocellular damage, if glutathione sources are depleted. Paracetamol clearance is reduced and the half-life of elimination is prolonged. Therefore, a particular dosing regimen should be followed due to the toxicity risk of cumulative doses. This report highlights the risk for severe hepatotoxicity in neonates after paracetamol multiple doses for more than two to three days.

  10. Development of a novel 96-microwell assay with high throughput for determination of olmesartan medoxomil in its tablets

    Directory of Open Access Journals (Sweden)

    Darwish Ibrahim A

    2012-01-01

    Full Text Available Abstract A novel 96-microwell-based spectrophotometric assay has been developed and validated for determination of olmesartan medoxomil (OLM in tablets. The formation of a colored charge-transfer (CT complex between OLM as a n-electron donor and 2, 5-dichloro-3, 6-dihydroxy-1, 4-benzoquinone (p-chloranilic acid, pCA as a π-electron acceptor was investigated, for the first time, and employed as a basis in the development of the proposed assay. The proposed assay was carried out in 96-microwell plates. The absorbance of the colored-CT complex was measured at 490 nm by microwell-plate absorbance reader. The optimum conditions of the reaction and the analytical procedures of the assay were established. Under the optimum conditions, linear relationship with good correlation coefficient was found between the absorbance and the concentration of OLM in the range of 1-200 μg ml-1. The limits of detection and quantitation were 0.3 and 1 μg ml-1, respectively. No interference was observed from the additives that are present in the pharmaceutical formulation or from hydrochlorothiazide and amlodipine that are co-formulated with OLM in some formulations. The assay was successfully applied to the analysis of OLM in tablets with good accuracy and precision. The assay described herein has great practical value in the routine analysis of OLM in quality control laboratories, as it has high throughput property, consumes minimum volume of organic solvent thus it offers the reduction in the exposures of the analysts to the toxic effects of organic solvents, and reduction in the analysis cost by 50-fold. Although the proposed assay was validated for OLM, however, the same methodology could be used for any electron-donating analyte for which a CT reaction can be performed.

  11. High throughput microwell spectrophotometric assay for olmesartan medoxomil in tablets based on its charge-transfer reaction with DDQ

    Directory of Open Access Journals (Sweden)

    Darwish Ibrahim A.

    2014-03-01

    Full Text Available The study describes the development and validation of a new microwell-based spectrophotometric assay for determination of olmesartan medoxomil (OLM in tablets. The formation of a colored charge-transfer (CT complex between OLM as an n-electron donor and 2,3-dichloro- -5,6-dicyano-1,4-benzoquinone (DDQ as a p-electron acceptor was investigated, and employed as the basis for the development of the new assay. The proposed assay was conducted in 96-microwell plates. The absorbance of the colored-CT complex was measured at 460 nm with a microplate reader. Optimum conditions of the reaction and the analytical procedures of the assay were established. Under the optimum conditions, a linear relationship with a good correlation coefficient was found between the absorbance and the concentration of OLM in the range of 2-200 μg per well. The limits of detection and quantitation were 0.53 and 1.61 μg per well, respectively. No interference was observed from the excipients present in OLM tablets or from hydrochlorothiazide and amlodipine besylate that were co-formulated with OLM in some of its formulations. The assay was successfully applied to the analysis of OLM in tablets with good accuracy and precision. The assay described herein has a great practical value in the routine analysis of OLM in quality control laboratories, since it has a high throughput property and consumes low volumes of organic solvent. It thus offers a reduction in the exposure of analysts to the toxic effects of organic solvents, as well as a reduction in the cost of analysis.

  12. Mutation of Rv2887, a marR-like gene, confers Mycobacterium tuberculosis resistance to an imidazopyridine-based agent.

    Science.gov (United States)

    Winglee, Kathryn; Lun, Shichun; Pieroni, Marco; Kozikowski, Alan; Bishai, William

    2015-11-01

    Drug resistance is a major problem in Mycobacterium tuberculosis control, and it is critical to identify novel drug targets and new antimycobacterial compounds. We have previously identified an imidazo[1,2-a]pyridine-4-carbonitrile-based agent, MP-III-71, with strong activity against M. tuberculosis. In this study, we evaluated mechanisms of resistance to MP-III-71. We derived three independent M. tuberculosis mutants resistant to MP-III-71 and conducted whole-genome sequencing of these mutants. Loss-of-function mutations in Rv2887 were common to all three MP-III-71-resistant mutants, and we confirmed the role of Rv2887 as a gene required for MP-III-71 susceptibility using complementation. The Rv2887 protein was previously unannotated, but domain and homology analyses suggested it to be a transcriptional regulator in the MarR (multiple antibiotic resistance repressor) family, a group of proteins first identified in Escherichia coli to negatively regulate efflux pumps and other mechanisms of multidrug resistance. We found that two efflux pump inhibitors, verapamil and chlorpromazine, potentiate the action of MP-III-71 and that mutation of Rv2887 abrogates their activity. We also used transcriptome sequencing (RNA-seq) to identify genes which are differentially expressed in the presence and absence of a functional Rv2887 protein. We found that genes involved in benzoquinone and menaquinone biosynthesis were repressed by functional Rv2887. Thus, inactivating mutations of Rv2887, encoding a putative MarR-like transcriptional regulator, confer resistance to MP-III-71, an effective antimycobacterial compound that shows no cross-resistance to existing antituberculosis drugs. The mechanism of resistance of M. tuberculosis Rv2887 mutants may involve efflux pump upregulation and also drug methylation. PMID:26303802

  13. Organic anodes and sulfur/selenium cathodes for advanced Li and Na batteries

    Science.gov (United States)

    Luo, Chao

    To address energy crisis and environmental pollution induced by fossil fuels, there is an urgent demand to develop sustainable, renewable, environmental benign, low cost and high capacity energy storage devices to power electric vehicles and enhance clean energy approaches such as solar energy, wind energy and hydroenergy. However, the commercial Li-ion batteries cannot satisfy the critical requirements for next generation rechargeable batteries. The commercial electrode materials (graphite anode and LiCoO 2 cathode) are unsustainable, unrenewable and environmental harmful. Organic materials derived from biomasses are promising candidates for next generation rechargeable battery anodes due to their sustainability, renewability, environmental benignity and low cost. Driven by the high potential of organic materials for next generation batteries, I initiated a new research direction on exploring advanced organic compounds for Li-ion and Na-ion battery anodes. In my work, I employed croconic acid disodium salt and 2,5-Dihydroxy-1,4-benzoquinone disodium salt as models to investigate the effects of size and carbon coating on electrochemical performance for Li-ion and Na-ion batteries. The results demonstrate that the minimization of organic particle size into nano-scale and wrapping organic materials with graphene oxide can remarkably enhance the rate capability and cycling stability of organic anodes in both Li-ion and Na-ion batteries. To match with organic anodes, high capacity sulfur and selenium cathodes were also investigated. However, sulfur and selenium cathodes suffer from low electrical conductivity and shuttle reaction, which result in capacity fading and poor lifetime. To circumvent the drawbacks of sulfur and selenium, carbon matrixes such as mesoporous carbon, carbonized polyacrylonitrile and carbonized perylene-3, 4, 9, 10-tetracarboxylic dianhydride are employed to encapsulate sulfur, selenium and selenium sulfide. The resulting composites exhibit

  14. Integrated electrokinetic magnetic bead-based electrochemical immunoassay on microfluidic chips for reliable control of permitted levels of zearalenone in infant foods.

    Science.gov (United States)

    Hervás, Mirian; López, Miguel A; Escarpa, Alberto

    2011-05-21

    Microfluidic technology has now become a novel sensing platform where different analytical steps, biological recognition materials and suitable transducers can be cleverly integrated yielding a new sensor generation. A novel "lab-on-a-chip" strategy integrating an electrokinetic magnetic bead-based electrochemical immunoassay on a microfluidic chip for reliable control of permitted levels of zearalenone in infant foods is proposed. The strategy implies the creative use of the simple channel layout of the double-T microchip to perform sequentially the immunointeraction and enzymatic reaction by applying a program of electric fields suitably connected to the reservoirs for driving the fluidics at different chambers in order to perform the different reactions. Both zones are used with the aid of a magnetic field to avoid in a very simple and elegant way the non-specific adsorption. Immunological reaction is performed under a competitive enzyme-linked immunosorbent assay (ELISA) where the mycotoxin ZEA and an enzyme-labelled derivative compete for the binding sites of the specific monoclonal antibody immobilised onto protein G modified magnetic beads. Horseradish peroxidase (HRP), in the presence of hydrogen peroxide, catalyses the oxidation of hydroquinone (HQ) to benzoquinone (BQN), whose back electrochemical reduction was detected at +0.1 V. Controlled-electrokinetic fluidic handling optimized conditions are addressed for all analytical steps cited above, and allows performing the complete immunoassay for the target ZEA analyte in less than 15 minutes with unique analytical merits: competitive immunoassay currents showed a very well-defined concentration dependence with a good precision as well as a suitable limit of detection of 0.4 µg L(-1), well below the legislative requirements, and an extremely low systematic error of 2% from the analysis of a maize certified reference material revealing additionally an excellent accuracy. Also, the reliability of the

  15. Metabolic Pathway Involved in 2-Methyl-6-Ethylaniline Degradation by Sphingobium sp. Strain MEA3-1 and Cloning of the Novel Flavin-Dependent Monooxygenase System meaBA

    Science.gov (United States)

    Dong, Weiliang; Chen, Qiongzhen; Hou, Ying; Li, Shuhuan; Zhuang, Kai; Huang, Fei; Zhou, Jie; Li, Zhoukun; Wang, Jue; Fu, Lei; Zhang, Zhengguang; Huang, Yan; Wang, Fei

    2015-01-01

    2-Methyl-6-ethylaniline (MEA) is the main microbial degradation intermediate of the chloroacetanilide herbicides acetochlor and metolachlor. Sphingobium sp. strain MEA3-1 can utilize MEA and various alkyl-substituted aniline and phenol compounds as sole carbon and energy sources for growth. We isolated the mutant strain MEA3-1Mut, which converts MEA only to 2-methyl-6-ethyl-hydroquinone (MEHQ) and 2-methyl-6-ethyl-benzoquinone (MEBQ). MEA may be oxidized by the P450 monooxygenase system to 4-hydroxy-2-methyl-6-ethylaniline (4-OH-MEA), which can be hydrolytically spontaneously deaminated to MEBQ or MEHQ. The MEA microbial metabolic pathway was reconstituted based on the substrate spectra and identification of the intermediate metabolites in both the wild-type and mutant strains. Plasmidome sequencing indicated that both strains harbored 7 plasmids with sizes ranging from 6,108 bp to 287,745 bp. Among the 7 plasmids, 6 were identical, and pMEA02′ in strain MEA3-1Mut lost a 37,000-bp fragment compared to pMEA02 in strain MEA3-1. Two-dimensional electrophoresis (2-DE) and protein mass fingerprinting (PMF) showed that MEA3-1Mut lost the two-component flavin-dependent monooxygenase (TC-FDM) MeaBA, which was encoded by a gene in the lost fragment of pMEA02. MeaA shared 22% to 25% amino acid sequence identity with oxygenase components of some TC-FDMs, whereas MeaB showed no sequence identity with the reductase components of those TC-FDMs. Complementation with meaBA in MEA3-1Mut and heterologous expression in Pseudomonas putida strain KT2440 resulted in the production of an active MEHQ monooxygenase. PMID:26386060

  16. The strontium inorganic mutant of the water oxidizing center (CaMn4O5) of PSII improves WOC efficiency but slows electron flux through the terminal acceptors.

    Science.gov (United States)

    Gates, Colin; Ananyev, Gennady; Dismukes, G Charles

    2016-09-01

    Herein we extend prior studies of biosynthetic strontium replacement of calcium in PSII-WOC core particles to characterize whole cells. Previous studies of Thermosynechococcus elongatus found a lower rate of light-saturated O2 from isolated PSII-WOC(Sr) cores and 5-8× slower rate of oxygen release. We find similar properties in whole cells, and show it is due to a 20% larger Arrhenius activation barrier for O2 evolution. Cellular adaptation to the sluggish PSII-WOC(Sr) cycle occurs in which flux through the QAQB acceptor gate becomes limiting for turnover rate in vivo. Benzoquinone derivatives that bind to QB site remove this kinetic chokepoint yielding 31% greater O2 quantum yield (QY) of PSII-WOC(Sr) vs. PSII-WOC(Ca). QY and efficiency of the WOC(Sr) catalytic cycle are greatly improved at low light flux, due to fewer misses and backward transitions and 3-fold longer lifetime of the unstable S3 state, attributed to greater thermodynamic stabilization of the WOC(Sr) relative to the photoactive tyrosine YZ. More linear and less cyclic electron flow through PSII occurs per PSII-WOC(Sr). The organismal response to the more active PSII centers in Sr-grown cells at 45°C is to lower the number of active PSII-WOC per Chl, producing comparable oxygen and energy per cell. We conclude that redox and protonic energy fluxes created by PSII are primary determinants for optimal growth rate of T. elongatus. We further conclude that the (Sr-favored) intermediate-spin S=5/2 form of the S2 state is the active form in the catalytic cycle relative to the low-spin S=1/2 form. PMID:27317268

  17. Flavodoxin:quinone reductase (FqrB): a redox partner of pyruvate:ferredoxin oxidoreductase that reversibly couples pyruvate oxidation to NADPH production in Helicobacter pylori and Campylobacter jejuni.

    Science.gov (United States)

    St Maurice, Martin; Cremades, Nunilo; Croxen, Matthew A; Sisson, Gary; Sancho, Javier; Hoffman, Paul S

    2007-07-01

    Pyruvate-dependent reduction of NADP has been demonstrated in cell extracts of the human gastric pathogen Helicobacter pylori. However, NADP is not a substrate of purified pyruvate:ferredoxin oxidoreductase (PFOR), suggesting that other redox active enzymes mediate this reaction. Here we show that fqrB (HP1164), which is essential and highly conserved among the epsilonproteobacteria, exhibits NADPH oxidoreductase activity. FqrB was purified by nickel interaction chromatography following overexpression in Escherichia coli. The protein contained flavin adenine dinucleotide and exhibited NADPH quinone reductase activity with menadione or benzoquinone and weak activity with cytochrome c, molecular oxygen, and 5,5'-dithio-bis-2-nitrobenzoic acid (DTNB). FqrB exhibited a ping-pong catalytic mechanism, a k(cat) of 122 s(-1), and an apparent K(m) of 14 muM for menadione and 26 muM for NADPH. FqrB also reduced flavodoxin (FldA), the electron carrier of PFOR. In coupled enzyme assays with purified PFOR and FldA, FqrB reduced NADP in a pyruvate- and reduced coenzyme A (CoA)-dependent manner. Moreover, in the presence of NADPH, CO(2), and acetyl-CoA, the PFOR:FldA:FqrB complex generated pyruvate via CO(2) fixation. PFOR was the rate-limiting enzyme in the complex, and nitazoxanide, a specific inhibitor of PFOR of H. pylori and Campylobacter jejuni, also inhibited NADP reduction in cell-free lysates. These capnophilic (CO(2)-requiring) organisms contain gaps in pathways of central metabolism that would benefit substantially from pyruvate formation via CO(2) fixation. Thus, FqrB provides a novel function in pyruvate metabolism and, together with production of superoxide anions via quinone reduction under high oxygen tensions, contributes to the unique microaerobic lifestyle that defines the epsilonproteobacterial group. PMID:17468253

  18. Strategies of development of antiviral agents directed against influenza virus replication.

    Science.gov (United States)

    Hsieh, Hsing-Pang; Hsu, John T-A

    2007-01-01

    In this review, we will discuss drug design based on proven and potential anti-influenza drug targets including viral hemagglutinin (HA), neuraminidase (NA), M2 ion channel, 3P polymerase complex, and host factors such as kinases. We have summarized influenza inhibitors based on their mode of actions. For instance, included are descriptions of (1) inhibitors of HA cleavage, such as nafamostat, camostat, gabexate, epsilon-aminocapronic acid and aprotinin, (2) inhibitors of fusion and entry, such as benzoquinones and hydroquinones, CL 385319, BMY-27709, stachyflin, and their analogues, (3) inhibitors of viral RNPs/polymerase/endonuclease, such as T-705, L-735,822, flutimide and their analogues, (4) inhibitors of MEK, such as PD 0325901, CI-1040 and ARRY-142886, and (5) inhibitors of NA such as DANA, FANA, zanamivir, and oseltamivir, etc. Although amantadine and rimantadine are not recommended for treating influenza virus infections because of drug resistance problem, these viral M2 ion channel blockers established a proof-of-concept that the endocytosis of virion into host cells can be a valid drug target because M2 protein is involved in the endocytosis process. The influenza polymerase complex not only catalyzes RNA polymerization but also encodes the "cap snatching" activity. After being exported from the nucleus to the cytoplasm, the newly synthesized vRNPs are assembled into virions at the plasma membrane. The progeny virions will then leave the host cells through the action of NA. The strategies for discovery of small molecule inhibitors of influenza virus replication based on each particular mechanism will be discussed. Finally, the lessons learned from the design of NA inhibitors (NAI) are also included. Many exciting opportunities await the cadre of virologists, medicinal chemists, and pharmacologists to design novel influenza drugs with favorable pharmacological and pharmacokinetic properties to combat this threatening infectious disease. PMID:18220789

  19. A double signal electrochemical human immunoglobulin G immunosensor based on gold nanoparticles-polydopamine functionalized reduced graphene oxide as a sensor platform and AgNPs/carbon nanocomposite as signal probe and catalytic substrate.

    Science.gov (United States)

    Zhang, Si; Huang, Na; Lu, Qiujun; Liu, Meiling; Li, Haitao; Zhang, Youyu; Yao, Shouzhuo

    2016-03-15

    In this paper, a double signal electrochemical Human immunoglobulin G (HIgG) immunosensor based on AgNPs/carbon nanocomposite (Ag/C NC) as the signal probe and catalytic substrate was developed for fast and sensitive detection of HIgG. The as-prepared AuNPs-PDA-rGO nanocomposite and Ag/C NC were confirmed by UV-vis, Fourier transform infrared spectroscopy, scanning electron microscopy and transmission electron microscopy. Electrochemical impedance spectroscopy, cyclic voltammetry and differential pulse voltammetry were used to investigate the electrochemical properties of the proposed immunosensor. The AuNPs-PDA-rGO nanocomposite can improve the electron transfer rate and capture more Ab1. In the sandwich-type immunoassay process, the Ag/C NC functionalized bioconjugates were captured on HIgG/Ab1/AuNPs-PDA-rGO surface and the electrochemical double-signal strategy was employed. These double electrochemical detection signals were directly monitored the oxidation current originated from Ag/C NC and indirectly detected the reduction current of benzoquinone which was produced from the reaction of H2O2 and HQ by catalysis of Ag/C NC in electrochemical detection of HIgG. Under the optimized conditions, the current responses were changed with the concentrations of HIgG for the proposed immunosensor with wide linear ranges of 0.1 to 100 ngmL(-1) and 0.01-100 ngmL(-1) with the lowest detection concentration of 0.001 ng mL(-1) in the absence and presence of H2O2 and HQ. The double-signal strategy is used for detection of HIgG, and the results came from the two signals were well consistent with each other. The proposed immunosensor was successfully applied in analysis of human IgG in real samples and this strategy may provide a relative simple and effective method for construction of other immunsensors in detection of other biomarkers in clinical medicine. PMID:26556185

  20. Enhanced photocatalytic activity of BaTiO{sub 3}@g-C{sub 3}N{sub 4} for the degradation of methyl orange under simulated sunlight irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Xian, T. [State Key Laboratory of Advanced Processing and Recycling of Non-ferrous Metals, Lanzhou University of Technology, Lanzhou 730050 (China); School of Science, Lanzhou University of Technology, Lanzhou 730050 (China); Yang, H., E-mail: hyang@lut.cn [State Key Laboratory of Advanced Processing and Recycling of Non-ferrous Metals, Lanzhou University of Technology, Lanzhou 730050 (China); School of Science, Lanzhou University of Technology, Lanzhou 730050 (China); Di, L.J. [School of Science, Lanzhou University of Technology, Lanzhou 730050 (China); Dai, J.F. [State Key Laboratory of Advanced Processing and Recycling of Non-ferrous Metals, Lanzhou University of Technology, Lanzhou 730050 (China); School of Science, Lanzhou University of Technology, Lanzhou 730050 (China)

    2015-02-15

    Highlights: • BaTiO{sub 3}@g-C{sub 3}N{sub 4} composites were prepared by a simple mixing-calcining method. • The composites exhibit enhanced photocatalytic activity compared to bare BaTiO{sub 3} and g-C{sub 3}N{sub 4}. • The effect of BQ, AO and ethanol on the photocatalytic efficiency was investigated. • {sup ·}O{sub 2} and h{sup +} are the main active species responsible for the dye degradation. • {sup ·}OH radicals play a relatively small role in the photocatalytic reaction. - Abstract: BaTiO{sub 3}@g-C{sub 3}N{sub 4} composites were prepared by a simple mixing-calcining method. SEM observation indicates that BaTiO{sub 3} nanoparticles are uniformly assembled onto the surface of g-C{sub 3}N{sub 4} platelets. The photocatalytic activity of as-prepared BaTiO{sub 3}@g-C{sub 3}N{sub 4} composites were evaluated by the degradation of methyl orange (MO) under simulated sunlight irradiation, revealing that the composites exhibit enhanced photocatalytic activity compared to bare BaTiO{sub 3} and g-C{sub 3}N{sub 4}. This can be explained by the efficient separation of the photogenerated electron-hole pairs due to the migration of the carriers between g-C{sub 3}N{sub 4} and BaTiO{sub 3}; as a result, electrons and holes are increasingly available for the photocatalytic reaction. Hydroxyl radicals were detected by the photoluminescence technique using terephthalic acid as a probe molecule and are found to be produced equally on the irradiated BaTiO{sub 3} particles and BaTiO{sub 3}@g-C{sub 3}N{sub 4} composites. The effect of benzoquinone, ammonium oxalate and ethanol on the photocatalytic efficiency was also investigated. According to the experimental results, superoxide radicals and photogenerated holes are suggested to be the main active species responsible for the dye degradation, while hydroxyl radicals play a relatively small role in the photocatalytic reaction.

  1. Synthesis and characterization of Ag{sub 3}PO{sub 4} immobilized with graphene oxide (GO) for enhanced photocatalytic activity and stability over 2,4-dichlorophenol under visible light irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Xiao-juan [Department of Environmental Science and Engineering, Xiangtan University, Xiangtan 411105 (China); Dai, You-zhi, E-mail: daiyzh@xtu.edu.cn [Department of Environmental Science and Engineering, Xiangtan University, Xiangtan 411105 (China); Wang, Xing-yan; Guo, Jing; Liu, Tan-hua [Department of Environmental Science and Engineering, Xiangtan University, Xiangtan 411105 (China); Li, Fen-fang [Department of Environmental Science and Engineering, Xiangtan University, Xiangtan 411105 (China); Department of Environmental Science, Changsha Environmental Protection Vocational College, Changsha410004 (China)

    2015-07-15

    Highlights: • A series of Ag{sub 3}PO{sub 4}–GO photocatalysts with different GO content were prepared. • Photocatalytic activity of Ag{sub 3}PO{sub 4}–GO to 2,4-DCP increased with GO content increasing. • GO played significant role in the enhanced photocatalytic activity and stability. • Degradation pathway of 2,4-DCP and photocatalytic mechanism of Ag{sub 3}PO{sub 4}–GO were proposed. - Abstract: A series of visible-light responsive photocatalysts prepared using Ag{sub 3}PO{sub 4} immobilized with graphene oxide (GO) with varying GO content were obtained by an electrostatically driven method, and 2,4-dichlorophenol (2,4-DCP) was used to evaluate the performance of the photocatalysts. The composites exhibited superior photocatalytic activity and stability compared with pure Ag{sub 3}PO{sub 4}. When the content of GO was 5%, the degradation efficiency of 2,4-DCP could reach 98.95%, and 55.91% of the total organic (TOC) content was removed within 60 min irradiation. Meanwhile, the efficiency of 91.77% was achieved for 2,4-DCP degradation even after four times of recycling in the photocatalysis/Ag{sub 3}PO{sub 4}–GO (5%) system. Reactive species of O{sub 2}{sup ·−}, OH· and h{sup +} were considered as the main participants for oxidizing 2,4-DCP, as confirmed by the free radical capture experiments. And some organic intermediates including 4-chlorophenol (4-CP), hydroquinone (HQ), benzoquinone (BZQ), 2-chlorohydroquinone and hydroxyhydroquinone (HHQ) were detected by comparison with the standard retention times from the high performance liquid chromatography (HPLC). In short, the enhanced photocatalytic property of Ag{sub 3}PO{sub 4}–GO was closely related to the strong absorption ability of GO relative to 2,4-DCP, the effective separation of photogenerated electron–hole pairs, and the excellent electron capture capability of GO.

  2. Electro-Fenton degradation of antimicrobials triclosan and triclocarban

    Energy Technology Data Exchange (ETDEWEB)

    Sires, Ignasi [Laboratori d' Electroquimica dels Materials i del Medi Ambient, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Oturan, Nihal [Universite de Marne la Vallee, Laboratoire des Geomateriaux et Geologie de l' Ingenieur, 5 Boulevard Descartes, Champs-sur-Marne, 77454 Marne-la-Vallee Cedex 2 (France); Oturan, Mehmet A. [Universite de Marne la Vallee, Laboratoire des Geomateriaux et Geologie de l' Ingenieur, 5 Boulevard Descartes, Champs-sur-Marne, 77454 Marne-la-Vallee Cedex 2 (France); Rodriguez, Rosa Maria [Laboratori d' Electroquimica dels Materials i del Medi Ambient, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Garrido, Jose Antonio [Laboratori d' Electroquimica dels Materials i del Medi Ambient, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Brillas, Enric [Laboratori d' Electroquimica dels Materials i del Medi Ambient, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain)]. E-mail: brillas@ub.edu

    2007-05-05

    The antimicrobials triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether) and triclocarban (N-(4-chlorophenyl)-N'-(3,4-dichlorophenyl)urea) have been degraded by four electro-Fenton systems using undivided electrolytic cells with a Pt or boron-doped diamond (BDD) anode and a carbon felt or O{sub 2} diffusion cathode. The main oxidant is hydroxyl radical ({center_dot}OH) produced both on the anode surface from water oxidation and in the medium by Fenton's reaction, which takes place between electrogenerated H{sub 2}O{sub 2} and Fe{sup 2+} coming from cathodic reduction of O{sub 2} and Fe{sup 3+}, respectively. Triclosan from saturated aqueous solutions of pH 3.0 is completely removed in all cells, decreasing its decay rate in the order: Pt/carbon felt > BDD/carbon felt > Pt/O{sub 2} diffusion > BDD/O{sub 2} diffusion, in agreement with their {center_dot}OH generation ability from Fenton's reaction. Glyoxylic, maleic and oxalic acids are identified as aliphatic intermediates. Complexes between oxalic acid and iron ions persist largely in solution, although Fe{sup 2+}-oxalato complexes are mineralized by {center_dot}OH in the medium and Fe{sup 3+}-oxalato complexes are destroyed by {center_dot}OH on BDD. Analogous treatments of more concentrated triclosan solutions using a 20:80 (v/v) acetonitrile/water mixture as solvent evidence the role of hydroxyl radicals along the degradation. In this hydroorganic medium hydroxylated derivatives such as 2,4-dichlorophenol, 4-chlorocatechol, chlorohydroquinone and chloro-p-benzoquinone, and carboxylic acids such as maleic, oxalic, formic and acetic acids are detected as products. Complete destruction of iron-oxalato complexes and released Cl{sup -} ion involves some oxidizing species coming from parallel acetonitrile oxidation. The same electro-Fenton systems also yield the overall removal of triclocarban in acetonitrile/water mixtures, giving rise to urea, hydroquinone, chlorohydroquinone, 1-chloro-4

  3. Geometry and quadratic nonlinearity of charge transfer complexes in solution using depolarized hyper-Rayleigh scattering.

    Science.gov (United States)

    Pandey, Ravindra; Ghosh, Sampa; Mukhopadhyay, S; Ramasesha, S; Das, Puspendu K

    2011-01-28

    We report large quadratic nonlinearity in a series of 1:1 molecular complexes between methyl substituted benzene donors and quinone acceptors in solution. The first hyperpolarizability, β(HRS), which is very small for the individual components, becomes large by intermolecular charge transfer (CT) interaction between the donor and the acceptor in the complex. In addition, we have investigated the geometry of these CT complexes in solution using polarization resolved hyper-Rayleigh scattering (HRS). Using linearly (electric field vector along X direction) and circularly polarized incident light, respectively, we have measured two macroscopic depolarization ratios D=I(2ω,X,X)/I(2ω,Z,X) and D(')=I(2ω,X,C)/I(2ω,Z,C) in the laboratory fixed XYZ frame by detecting the second harmonic scattered light in a polarization resolved fashion. The experimentally obtained first hyperpolarizability, β(HRS), and the value of macroscopic depolarization ratios, D and D('), are then matched with the theoretically deduced values from single and double configuration interaction calculations performed using the Zerner's intermediate neglect of differential overlap self-consistent reaction field technique. In solution, since several geometries are possible, we have carried out calculations by rotating the acceptor moiety around three different axes keeping the donor molecule fixed at an optimized geometry. These rotations give us the theoretical β(HRS), D and D(') values as a function of the geometry of the complex. The calculated β(HRS), D, and D(') values that closely match with the experimental values, give the dominant equilibrium geometry in solution. All the CT complexes between methyl benzenes and chloranil or 1,2-dichloro-4,5-dicyano-p-benzoquinone investigated here are found to have a slipped parallel stacking of the donors and the acceptors. Furthermore, the geometries are staggered and in some pairs, a twist angle as high as 30° is observed. Thus, we have demonstrated in

  4. Chlorin-based supramolecular assemblies for artificial photosynthesis

    Energy Technology Data Exchange (ETDEWEB)

    Wasielewski, Michael R.; Wiederrecht, Gary P.; Svec, Walter A.; Niemczyk, Mark P. [Chemistry Division, Argonne National Laboratory, Argonne (United States)

    1995-08-01

    Photosynthetic reaction center models consisting of zinc 9-desoxo-pyrochlorophyllide, ZC, that are bonded at their 3-position to the 5-position of a 2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrin, ZP, which is in turn bonded at its 15-position to 2-triptycenenaphthoquinone, 2-triptycenebenzoquinone, 1-triptycenebenzoquinone, or N-(4-phenyl), N`-(n-octyl)-1,4,5,8-naphthalenediimide, 1, 2, 3, and 4, respectively, were prepared. Steric hindrance between adjacent substituents positions the {pi} system of the chlorophyll perpendicular to that of the porphyrin. In turn, the {pi} system of the chlorophyll is held about 60 to that of the O-O axis of the quinones in 1 and 2, parallel to the quinone O-O axis in 3, and parallel to the N-N axis in the diimide acceptor in 4. The resulting structures place the ZC donors in 1, 2, 3 and 4 at fixed center-to-center distances of 20, 18, 14, and 21 A from the acceptors, respectively. Photoexcitation of 1-4 in 2-methyltetrahydrofuran glass at 77K results in a single observable electron transfer reaction: {sup 1}ZC-ZP-X>ZC{sup +}-ZP-X{sup -}, where X=benzoquinone (BQ), naphthoquinone (NQ) or naphthalenediimide (NI), that occurs with {tau}=4.5, 3.3, 2.0, and 2.0 ps for 1, 2, 3, and 4, respectively. The final ZC{sup +}-ZP-X{sup -} radical pairs live for 12.7, 8.4, 2.5, and 10 ms at 77K in 1, 2, 3, and 4, respectively, and exhibit spin-polarized EPR spectra characteristic of spin-correlated radical pairs. The EPR spectra of 1-4 can be simulated using the distances and orientations of the radicals relative to one another determined from the molecular structures of 1-4. These long-lived, spin-polarized radical ion pairs closely mimic the bacteriochlorophyll cation - quinone anion radical pair produced in photosynthetic reaction centers and provide a useful tool for studying the interaction of the surrounding medium with the charge separated radical ion pair

  5. Novel microwell-based spectrophotometric assay for determination of atorvastatin calcium in its pharmaceutical formulations

    Directory of Open Access Journals (Sweden)

    Abdel-Rahman Hamdy M

    2011-10-01

    Full Text Available Abstract The formation of a colored charge-transfer (CT complex between atorvastatin calcium (ATR-Ca as a n-electron donor and 2, 3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ as a π-electron acceptor was investigated, for the first time. The spectral characteristics of the CT complex have been described, and the reaction mechanism has been proved by computational molecular modeling. The reaction was employed in the development of a novel microwell-based spectrophotometric assay for determination of ATR-Ca in its pharmaceutical formulations. The proposed assay was carried out in 96-microwell plates. The absorbance of the colored-CT complex was measured at 460 nm by microwell-plate absorbance reader. The optimum conditions of the reaction and the analytical procedures of the assay were established. Under the optimum conditions, linear relationship with good correlation coefficient (0.9995 was found between the absorbance and the concentration of ATR-Ca in the range of 10-150 μg/well. The limits of detection and quantitation were 5.3 and 15.8 μg/well, respectively. No interference was observed from the additives that are present in the pharmaceutical formulation or from the drugs that are co-formulated with ATR-Ca in its combined formulations. The assay was successfully applied to the analysis of ATR-Ca in its pharmaceutical dosage forms with good accuracy and precision. The assay described herein has great practical value in the routine analysis of ATR-Ca in quality control laboratories, as it has high throughput property, consumes minimum volume of organic solvent thus it offers the reduction in the exposures of the analysts to the toxic effects of organic solvents, and reduction in the analysis cost by 50-fold. Although the proposed assay was validated for ATR-Ca, however, the same methodology could be used for any electron-donating analyte for which a CT reaction can be performed.

  6. Spectrophotometric determination of phenol in the presence of congeners by multivariated calibration

    Directory of Open Access Journals (Sweden)

    KELY VIVIANE DE SOUZA

    2001-12-01

    Full Text Available The generation of poly-hydroxilated transient species during the photochemical treatment of phenol usually impedes the spectrophotmetric monitoring of its degradation process. Frequently, the appearance of compounds such as pyrocatechol, hydroquinone and benzoquinone produces serious spectral interference, which hinder the use of the classical univariate calibration process. In this work, the use of multivariate calibration is proposed to permit the spectrophotometric determination of phenol in the presence of these intermediates. Using 20 synthetic mixtures containing phenol and the interferents, a calibration model was developed by using a partial least square regression process (PLSR and processing the absorbance signal between 180 and 300 nm. The model was validated by using 3 synthetic mixtures. In this operation, typical errors lower than 3% were observed. Close correlation between the results obtained by liquid chromatography and the proposed method was also observed.A geração de espécies transientes polihidroxiladas, durante o tratamento fotoquímico de fenol, geralmente impede a utilização de espectrofotometria UV-VIS no monitoramento do processo de degradação. Freqüentemente, o surgimento de espécies como pirocatecol, hidroquinona e benzoquinona produz sérios problemas de interferências espectral, os quais inviabilizam a utilização de processos clássico de calibração univariada. Neste trabalho esta se propondo a utilização de processos de calibração multivariada para viabilizar a determinação espectrofotométrica de fenol na presença destes intermediários. O modelo de calibração multivariada foi desenvolvido por regressão de mínimos quadrados parciais (PLSR, utilizando-se 20 misturas sintéticas contendo fenol e interferentes e processando-se o sinal de absorbância obtido entre 180 e 300 nm. O modelo foi validado utilizando-se um conjunto de 3 misturas sintéticas, o que levou à obtenção de erros de

  7. Reduction of Pu(V) and Np(V) by leonardite humic acids and their quinonoid-enriched derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Shcherbina, N.S.; Kalmykov, St.N.; Perminova, I.V.; Kovalenko, A.N. [Department of Chemistry, Lomonosov Moscow State University, 119992, Moscow (Russian Federation)

    2005-07-01

    Full text of publication follows: Humic substances (HS) are natural poly-electrolytes ubiquitous in aquatic environment responsible for complexation of metal ions. The presence of phenolic and quinonoid moieties in the structure of HS provide for their ability to take part in redox interactions. Capability of HS to reduce plutonium from higher oxidation states (Pu(V) and Pu(VI)) to tetravalent state was reported in several studies. However, the disparate results were reported for Np(V). The contradicting results on the redox behavior of HS could originate from the structural differences of the humic materials tested, in particular, from varying content of the redox-active quinonoid moieties. To test this hypothesis, the goal of this research was to evaluate reducing performance of leonardite humic acids and of their quinonoid-enriched derivatives with respect to Pu(V) and Np(V). The quinonoid-enriched humic derivatives were obtained using the reaction of formaldehyde co-poly-condensation between parent humic material - leonardite humic acid - and model dihydroxybenzenes - hydroquinone, catechol and 1,4-benzoquinone. The humic material: quinonoid monomer ration of 1 g per 250 mg was used. The reduction of Np(V) was studied at micro- and macro-concentration level: 10{sup -7} M and 10{sup -4} M, respectively. In case of Pu(V) the concentration was about 10{sup -10} M. The HS concentrations varied from 1 to 100 ppm, while ionic strength was zero. All experiments were conducted in anaerobic conditions and in the darkness. The kinetics of Pu(V) reduction was studied using solvent extraction (TTA in toluene); to monitor Np(V) reduction two independent techniques were used: solvent extraction and VIS-NIR spectrophotometry. The latter allows measuring absorbance of NpO{sub 2}{sup +} and Np-humate complexes at 981.3 and 987.4 nm, respectively. Fast reduction of Pu(V) by the parent humic material was observed and the reduction rate increased with a decrease in pH. In case of

  8. Ozagrel hydrochloride, a selective thromboxane A2 synthase inhibitor, alleviates liver injury induced by acetaminophen overdose in mice

    Directory of Open Access Journals (Sweden)

    Tomishima Yoshiro

    2013-01-01

    Full Text Available Abstract Background Overdosed acetaminophen (paracetamol, N-acetyl-p-aminophenol; APAP causes severe liver injury. We examined the effects of ozagrel, a selective thromboxane A2 (TXA2 synthase inhibitor, on liver injury induced by APAP overdose in mice. Methods Hepatotoxicity was induced to ICR male mice by an intraperitoneal injection with APAP (330 mg/kg. The effects of ozagrel (200 mg/kg treatment 30 min after the APAP injection were evaluated with mortality, serum alanine aminotransferase (ALT levels and hepatic changes, including histopathology, DNA fragmentation, mRNA expression and total glutathione contents. The impact of ozagrel (0.001-1 mg/mL on cytochrome P450 2E1 (CYP2E1 activity in mouse hepatic microsome was examined. RLC-16 cells, a rat hepatocytes cell line, were exposed to 0.25 mM N-acetyl-p-benzoquinone imine (NAPQI, a hepatotoxic metabolite of APAP. In this model, the cytoprotective effects of ozagrel (1–100 muM were evaluated by the WST-1 cell viability assay. Results Ozagel treatment significantly attenuated higher mortality, elevated serum alanine aminotransferase levels, excessive hepatic centrilobular necrosis, hemorrhaging and DNA fragmentation, as well as increase in plasma 2,3-dinor thromboxane B2 levels induced by APAP injection. Ozagrel also inhibited the hepatic expression of cell death-related mRNAs induced by APAP, such as jun oncogene, FBJ osteosarcoma oncogene (fos and C/EBP homologous protein (chop, but did not suppress B-cell lymphoma 2-like protein11 (bim expression and hepatic total glutathione depletion. These results show ozagrel can inhibit not all hepatic changes but can reduce the hepatic necrosis. Ozagrel had little impact on CYP2E1 activity involving the NAPQI production. In addition, ozagrel significantly attenuated cell injury induced by NAPQI in RLC-16. Conclusions We demonstrate that the TXA2 synthase inhibitor, ozagrel, dramatically alleviates liver injury induced by APAP in mice, and suggest

  9. In vivo Anti-Inflammatory and Antinociceptive Activities of the Extracts and Chemical Constituents of an Endemic Turkish Plant, Salsola grandis

    Directory of Open Access Journals (Sweden)

    Nurgün Küçükboyacı

    2015-10-01

    Full Text Available Salsola is one of the largest and most important genera in the family Chenopodiaceae. Salsola species are used for their anti-inflammatory, antinociceptive, anthelmintic and antipruritic effects and also as diuretic in traditional medicines worldwide. The aim of the present study is to assess the activity potential of the extracts, subextracts and isolated compounds from the aerial parts of and Salsola grandis, an endemic species in Turkey in a scientific platform. The effects of the extracts, subextracts and isolated compounds were investigated using in vivo experimental models of inflammation and pain in mice, and also total phenolic content of the plant was determined. For the evaluation of the anti-inflammatory activity, carrageenan-induced paw edema and for the assessment of antinociceptive activity, p-benzoquinone-induced nociception tests in mice were employed. The crude ethanol extract of the plant was sequentially fractionated into five subextracts, namely n-hexane, CHCl 3, EtOAc, n-BuOH and remaining water subextracts. Further studies were carried out on the bioactive n -BuOH subextract. Through bioassay-guided fractionation and isolation procedures from active fraction , ten flavonoids, i sorhamnetin-3-O-rutinoside(1, quercetin-3-O-rutinoside (2,quercetin-3-O-metylether (3,tiliroside (4, isorhamnetin-3-glucuronide (5, isorhamnetin-3-O-glucoside (6,quercetin-3-O-galactoside (7, quercetin-3-O-rhamnoside (8,quercetin (9 and manghaslin (10, and two oleanane-type saponins, momordin II b (11 andmomordin II c (12, and one amino acid derivative compound, N-acetyltryptophan (13 were isolated, and their structures were established on the basis of spectroscopic techniques. The anti-inflammatory and antinociceptive activities of 1 , 4, 6, 7 and 12 were investigated firstly in this study, and 4 and 7 were found to have the most potent inhibitory activity in used models. The present study demonstrates the anti-inflammatory and antinociceptive

  10. Evidence of superoxide radical contribution to demineralization of sulfamethoxazole by visible-light-driven Bi{sub 2}O{sub 3}/Bi{sub 2}O{sub 2}CO{sub 3}/Sr{sub 6}Bi{sub 2}O{sub 9} photocatalyst

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Shiyuan; Niu, Junfeng, E-mail: junfengn@bnu.edu.cn; Bao, Yueping; Hu, Lijuan

    2013-11-15

    Highlights: • Bi{sub 2}O{sub 3}/Bi{sub 2}O{sub 2}CO{sub 3}/Sr{sub 6}Bi{sub 2}O{sub 9} can degrade SMX efficiently using visible light. • 36% of TOC reduction was achieved after 120 min treatment. • The main mineralization products were confirmed. • Formation of O{sub 2}·{sup −} was evidenced by using ESR and a chemiluminescent probe. -- Abstract: Photocatalytic degradation of sulfamethoxazole (SMX) was investigated using Bi{sub 2}O{sub 3}/Bi{sub 2}O{sub 2}CO{sub 3}/Sr{sub 6}Bi{sub 2}O{sub 9} (BSO) photocatalyst under visible light (>420 nm) irradiation. The photochemical degradation of SMX followed pseudo-first-order kinetics. The reaction kinetics was determined as a function of initial SMX concentrations (5–20 mg L{sup −1}), initial pH (3–11) and BSO concentrations (6–600 mg L{sup −1}). Approximately, 90% of SMX (10 mg L{sup −1}) degradation and 36% of TOC reduction were achieved at pH 7.0 after 120 min irradiation. The main mineralization products, including NH{sub 4}{sup +}, NO{sub 3}{sup −}, SO{sub 4}{sup 2−} and CO{sub 2}, as well as intermediates 3-amino-5-methylisoxazole (AMI), p-benzoquinone (BZQ), and sulfanilic acid (SNA) were detected in aqueous solution. The formation of O{sub 2}·{sup −} radical was evidenced by using electron spin resonance and a chemiluminescent probe, luminal. A possible degradation mechanism involving excitation of BSO, followed by charge injection into the BSO conduction band and formation of reactive superoxide radical (O{sub 2}·{sup −}) was proposed for the mineralization of SMX. During the reaction, the O{sub 2}·{sup −} radical attacks the sulfone moiety and causes the cleavage of the S-N bond, which leads to the formation of two sub-structure analogs, AMI and SNA.

  11. Degradation of Acid Orange 7 Dye in Two Hybrid Plasma Discharge Reactors

    Science.gov (United States)

    Shen, Yongjun; Lei, Lecheng; Zhang, Xingwang; Ding, Jiandong

    2014-11-01

    To get an optimized pulsed electrical plasma discharge reactor and to increase the energy utilization efficiency in the removal of pollutants, two hybrid plasma discharge reactors were designed and optimized. The reactors were compared via the discharge characteristics, energy transfer efficiency, the yields of the active species and the energy utilization in dye wastewater degradation. The results showed that under the same AC input power, the characteristics of the discharge waveform of the point-to-plate reactor were better. Under the same AC input power, the two reactors both had almost the same peak voltage of 22 kV. The peak current of the point-to-plate reactor was 146 A, while that of the wire-to-cylinder reactor was only 48.8 A. The peak powers of the point-to-plate reactor and the wire-to-cylinder reactor were 1.38 MW and 1.01 MW, respectively. The energy per pulse of the point-to-plate reactor was 0.2221 J, which was about 29.4% higher than that of the wire-to-cylinder reactor (0.1716 J). To remove 50% Acid Orange 7 (AO7), the energy utilizations of the point-to-plate reactor and the wire-to-cylinder reactor were 1.02 × 10-9 mol/L and 0.61 × 10-9 mol/L, respectively. In the point-to-plate reactor, the concentration of hydrogen peroxide in pure water was 3.6 mmol/L after 40 min of discharge, which was higher than that of the wire-to-cylinder reactor (2.5 mmol/L). The concentration of liquid phase ozone in the point-to-plate reactor (5.7 × 10-2 mmol/L) was about 26.7% higher than that in the wire-to-cylinder reactor (4.5 × 10-2 mmol/L). The analysis results of the variance showed that the type of reactor and reaction time had significant impacts on the yields of the hydrogen peroxide and ozone. The main degradation intermediates of AO7 identified by gas chromatography and mass spectrometry (GCMS) were acetic acid, maleic anhydride, p-benzoquinone, phenol, benzoic acid, phthalic anhydride, coumarin and 2-naphthol. Proposed degradation pathways were

  12. Chemical evidence for the pH-dependent control of ion-pair geometry in cathepsin B. Benzofuroxan as a reactivity probe sensitive to differences in the mutual disposition of the thiolate and imidazolium components of cysteine proteinase catalytic sites.

    Science.gov (United States)

    Willenbrock, F; Brocklehurst, K

    1986-08-15

    Benzofuroxan reacts with the catalytic-site thiol group of cathepsin B (EC 3.4.22.1) to produce stoichiometric amount of the chromophoric reduction product, o-benzoquinone dioxime. In a study of the pH-dependence of the kinetics of this reaction, most data were collected for the bovine spleen enzyme, but the more limited data collected for the rat liver enzyme were closely similar both in the magnitude of the values of the second-order rate constants (k) and in the shape of the pH-k profile. In acidic and weakly alkaline media, the reaction is faster than the reactions of benzofuroxan with some other cysteine proteinases. For example, in the pH region around 5-6, the reaction of cathepsin B is about 10 times faster than that of papain, 15 times faster than that of stem bromelain and 6 times faster than that of ficin. The pH-dependence of k for the reaction of cathepsin B with benzofuroxan was determined in the pH range 2.7-8.3. In marked contrast with the analogous reactions of papain, ficin and stem bromelain [reported by Shipton & Brocklehurst (1977) Biochem. J. 167, 799-810], the pH-k profile for the cathepsin B reaction contains a sigmoidal component with pKa 5.2 in which k increases with decrease in pH. This modulation of the reactivity of the catalytic-site -S-/-ImH+ ion-pair state of cathepsin B (produced by protonic dissociation from -SH/-ImH+ with pKa approx. 3) towards a small, rigid, electrophilic reagent, in a reaction that appears to involve both components of the ion-pair for efficient reaction, suggests that the state of ionization of a group associated with a molecular pKa of approx. 5 may control ion-pair geometry. This might account for the remarkable finding [reported by Willenbrock & Brocklehurst (1984) Biochem. J. 222, 805-814] that, although the ion-pair appears to be generated in cathepsin B as the pH is increased across pKa 3.4, catalytic competence is not generated until the pH is increased across pKa 5-6.

  13. The role of nitrite and nitrate ions as photosensitizers in the phototransformation of phenolic compounds in seawater

    International Nuclear Information System (INIS)

    Nitrite and nitrate are known to be involved in photochemical processes occurring in natural waters. In this study we have investigated the role played by these photosensitizers towards the transformation of xenobiotic organic matter in marine water, with the goal of assessing the typical transformation routes induced in seawater by irradiated nitrite/nitrate. For this purpose, phenol was chosen as model molecule. Phenol transformation was investigated under simulated solar radiation in the presence of nitrite (in the range of 1 × 10−5–1 × 10−2 M) or nitrate ions, in pure water at pH 8, in artificial seawater (containing same dissolved salts as seawater but no organic matter), and in natural seawater. In all experiments, phenol degradation rate and formation of intermediates were assessed. As expected, phenol disappearance rate decreased with decreasing nitrite concentration and was slightly reduced by the presence of chloride. Other salts present in artificial seawater (e.g. HCO3−, CO32− and Br−) had a more marked effect on phenol transformation. Analysis of intermediates formed in the different matrices under study showed generation of hydroxyl-, nitro- and chloroderivatives of phenol, to a different extent depending on experimental conditions. 1,4-Benzoquinone prevailed in all cases, nitroderivatives were only formed with nitrite but were not detected in nitrate-spiked solutions. Competition was observed between halogenation and nitration of phenol, with variable outcome depending on nitrite concentration. The most likely reason is competition between nitrating and halogenating species for reaction with the phenoxyl radical. A kinetic model able to justify the occurrence of different intermediates under the adopted conditions is presented and discussed. -- Highlights: ► Nitrite and nitrate-mediated solar-driven transformations of pollutant in seawater were studied. ► Phenol degradation rate and formation of intermediates were assessed.

  14. Regulation of coenzyme Q biosynthesis in yeast: a new complex in the block.

    Science.gov (United States)

    González-Mariscal, Isabel; García-Testón, Elena; Padilla, Sergio; Martín-Montalvo, Alejandro; Pomares-Viciana, Teresa; Vazquez-Fonseca, Luis; Gandolfo-Domínguez, Pablo; Santos-Ocaña, Carlos

    2014-02-01

    Coenzyme Q (CoQ) is an isoprenylated benzoquinone found in mitochondria, which functions mainly as an electron carrier from complex I or II to complex III in the inner membrane. CoQ is also an antioxidant that specifically prevents the oxidation of lipoproteins and the plasma membrane. Most of the information about the synthesis of CoQ comes from studies performed in Saccharomyces cerevisiae. CoQ biosynthesis is a highly regulated process of sequential modifications of the benzene ring. There are three pieces of evidence supporting the involvement of a multienzymatic complex in yeast CoQ6 biosynthesis: (a) the accumulation of a unique early precursor in all null mutants of the COQ genes series, 4-hydroxy-3-hexaprenyl benzoate (HHB), (b) the lack of expression of several Coq proteins in COQ null mutants, and (c) the restoration of CoQ biosynthesis complex after COQ8 overexpression. The model we propose based on the formation of a multiprotein complex should facilitate a better understanding of CoQ biosynthesis. According to this model, the complex assembly requires the synthesis of a precursor such as HHB by Coq2p that must be recognized by the regulatory protein Coq4p to act as the core component of the complex. The phosphorylation of Coq3p and Coq5p by the kinase Coq8p facilitates the formation of an initial precomplex of 700 kDa that contains all Coq proteins with the exception of Coq7p. The precomplex is required for the synthesis of 5-demethoxy-Q6 , the substrate of Coq7p. When cells require de novo CoQ6 synthesis, Coq7p is dephosphorylated by Ptc7p, a mitochondrial phosphatase that activates the synthesis of CoQ6. This event allows for the full assembly of a complex of 1,300 kDa that is responsible for the final product of the pathway, CoQ6 .

  15. Measurements of photo-oxidation products from the reaction of a series of alkyl-benzenes with hydroxyl radicals during EXACT using comprehensive gas chromatography

    Directory of Open Access Journals (Sweden)

    J. F. Hamilton

    2003-01-01

    Full Text Available Photo-oxidation products from the reaction of a series of alkyl-benzenes, (benzene, toluene, p-xylene and 1,3,5-trimethyl-benzene with hydroxyl radicals in the presence of NOx have been investigated using comprehensive gas chromatography (GCxGC. A GCxGC system has been developed which utilises valve modulation and independent separations as a function of both volatility and polarity. A number of carbonyl-type compounds were identified during a series of reactions carried out at the European Photoreactor (EUPHORE, a large volume outdoor reaction chamber in Valencia, Spain. Experiments were carried as part of the EXACT project (Effects of the oXidation of Aromatic Compounds in the Troposphere. Two litre chamber air samples were cryo-focused, with a sampling frequency of 30 minutes, allowing the evolution of species to be followed over oxidation periods of 3-6 hours. To facilitate product identification, several carbonyl compounds, which were possible products of the photo-oxidation, were synthesised and used as reference standards. For toluene reactions, observed oxygenated intermediates found included the co-eluting pair a-angelicalactone/4-oxo-2-pentenal, maleic anhydride, citraconic anhydride, benzaldehyde and p-methyl benzoquinone. In the p-xylene experiment, the products identified were E/Z-hex-3-en-2,5-dione and citraconic anhydride. For 1,3,5-TMB reactions, the products identified were 3,5-dimethylbenzaldehyde, 3,5-dimethyl-3H-furan-2-one and 3-methyl-5-methylene-5H-furan-2-one. Preliminary quantification was carried out on identified compounds using liquid standards. Comparison of FTIR and GCxGC for the measurement of the parent aromatics generally showed good agreement. Comparison of the concentrations observed by GCxGC to concentration-time profiles simulated using the Master Chemical Mechanism, MCMv3, demonstrates that this mechanism significantly over-predicts the concentrations of many product compounds and highlights the

  16. Characterisation of recombinant pyranose oxidase from the cultivated mycorrhizal basidiomycete Lyophyllum shimeji (hon-shimeji

    Directory of Open Access Journals (Sweden)

    Yamabhai Montarop

    2010-07-01

    Full Text Available Abstract Background The flavin-dependent enzyme pyranose 2-oxidase (P2Ox has gained increased attention during the last years because of a number of attractive applications for this enzyme. P2Ox is a unique biocatalyst with high potential for biotransformations of carbohydrates and in synthetic carbohydrate chemistry. Recently, it was shown that P2Ox is useful as bioelement in biofuel cells, replacing glucose oxidase (GOx, which traditionally is used in these applications. P2Ox offers several advantages over GOx for this application, e.g., its much broader substrate specificity. Because of this renewed interest in P2Ox, knowledge on novel pyranose oxidases isolated from organisms other than white-rot fungi, which represent the traditional source of this enzyme, is of importance, as these novel enzymes might differ in their biochemical and physical properties. Results We isolated and over-expressed the p2ox gene encoding P2Ox from the ectomycorrhizal fungus Lyophyllum shimeji. The p2ox cDNA was inserted into the bacterial expression vector pET21a(+ and successfully expressed in E. coli Rosetta 2. We obtained active, flavinylated recombinant P2Ox in yields of approximately 130 mg per L of medium. The enzyme was purified by a two-step procedure based on anion exchange chromatography and preparative native PAGE, yielding an apparently homogenous enzyme preparation with a specific activity of 1.92 U/mg (using glucose and air oxygen as the substrates. Recombinant P2Ox from L. shimeji was characterized in some detail with respect to its physical and catalytic properties, and compared to the well-characterised enzymes from Phanerochaete chrysosporium and Trametes multicolor. Conclusion L. shimeji P2Ox shows properties that are comparable to those of P2Ox from white-rot fungal origin, and is in general characterised by lower Km and kcat values both for electron donor (sugar as well as electron acceptor (ferrocenium ion, 1,4-benzoquinone, 2

  17. Electron transport between plastoquinone and chlorophyll Ai in chloroplasts. II. Reaction kinetics and the function of plastocyanin in situ.

    Science.gov (United States)

    Haehnel, W

    1977-03-11

    The light-induced reaction kinetics of electron carriers between the two light reactions were studied in spinach chloroplasts. 1. The difference spectrum of the absorbance changes of plastocyanin in situ was separated from superimposing absorbance changes by flash titration described in the preceding paper (Haehnel, W. (1973) Biochim. Biophys. Acta 305, 618-631). Relative amounts of 2 : 1 electron equivalents were observed for plastocyanin and chlorophyll a1 (P-700). 2. A balance of the electron equivalents released from reduced plastoquinone and simultaneously accepted by oxidized plastocyanin, cytochrome f and chlorophyll a1 indicated a quantitative electron transfer. Additional electron carriers between plastoquinone and light reaction I can be excluded with an accuracy of about +/-0.3 electron equivalents per light reaction II. 3. The time course of the absorbance changes of plastocyanin was measured at 584 nm with negligible interference with other absorbance changes. The reduction kinetics show an initial lag followed by a rise with a half time of about 20 ms. The redox states of plastocyanin and chlorophyll a1 during this reduction via the rate-limiting step between the light reactions and during oxidation by weak far-red light suggest a true equilibrium constant of about 20. 4. The simultaneous oxidation and reduction kinetics of plastoquinone, cytochrome f, plastocyanin and chlorophyll a1 induced by two successive groups of saturating flashes after far-red illumination were measured. The oxidation kinetics of plastocyanin and the simultaneous reduction kinetics of chlorophyll a1 after the single flashes indicate a quantitative electron transfer with a half time of 200 mus. 5. The fast reduction of chlorophyll a1 by plastocyanin showed no effect of the inhibitors 3-(3',4'-dichlorophenyl)-1,1-dimethylurea and 2,5-dibromo-3-methyl-6-isopropyl-p-benzoquinone or of reduced phenazine methosulfate. But it was completed inhibited after KCN incubation. 6. The

  18. Defensive nature of Sargassum polycystum (Brown alga)against acetaminophen-induced toxic hepatitis in rats: Role of drug metabolizing microsomal enzyme system, tumor necrosis factor-α and fate of liver cell structural integrity

    Institute of Scientific and Technical Information of China (English)

    H Balaji raghavendran; A Sathivel; T Devaki

    2006-01-01

    structural integrity.CONCLUSION: These observations suggest that the animals treated with S. Polycystum extract may have the ability to protect the drug metabolizing enzyme system and mitochondrial functional status from free radical attack, thereby showing its defense mechanism in protecting hepatic cells from acetaminophen toxic metabolite N-acetyl-para-benzoquinone-imine (NAPQI).

  19. Spectrophotometric study of the reaction mechanism between DDQ as π-acceptor and potassium iodate and flucloxacillin and dicloxacillin drugs and their determination in pure and in dosage forms

    Science.gov (United States)

    Mohamed, Gehad G.; Nour El-Dien, F. A.; Farag, Eman U.

    2006-09-01

    Two simple and accurate spectrophotometric methods are presented for the determination of β-lactam drugs, flucloxacillin (Fluclox) and dicloxacillin (Diclox), in pure and in different pharmaceutical preparations. The charge transfer (CT) reactions between Fluclox and Diclox as electron donors and 2,3-dichloro-5,6-dicyano- p-benzoquinone (DDQ) π-acceptor and potassium iodate via oxidation reduction reaction where the highly coloured complex species or the liberated iodine have been spectrophotometrically studied. The optimum experimental conditions have been studied carefully. Beer's law is obeyed over the concentration range of 2-450 μg ml -1 for Fluclox and 10-450 μg ml -1 for Diclox using DDQ reagent and at 50-550 μg ml -1 for Fluclox and 50-560 μg ml -1 for Diclox using iodate method, respectively. For more accurate results, Ringbom optimum concentration range is calculated and found to be 6-450 and 15-450 μg ml -1 for Fluclox and Diclox using DDQ, respectively, and 65-550 and 63-560 μg ml -1 for Fluclox and Diclox using iodine, respectively. The Sandell sensitivity is found to be 0.018 and 0.011 μg cm -2 for DDQ method and 0.013 and 0.011 μg cm -2 for iodate method for Fluclox and Diclox, respectively, which indicates the high sensitivity of both methods. Standard deviation (S.D. = 0.01-0.80 and 0.07-0.98) and relative standard deviation (R.S.D. = 0.13-0.44 and 0.11-0.82%) ( n = 5) for DDQ and iodate methods, respectively, refer to the high accuracy and precision of the proposed methods. These results are also confirmed by between-day precision of percent recovery of 99.87-100.2 and 99.90-100% for Fluclox and Diclox by DDQ method and 99.88-100.1 and 99.30-100.2% for Fluclox and Diclox by iodate method, respectively. These data are comparable to those obtained by British and American pharmacopoeias assay for the determination of Fluclox and Diclox in raw materials and in pharmaceutical preparations.

  20. Synthesis and electrochemical and spectroscopic properties of a series of binuclear and trinuclear ruthenium and palladium complexes based on a new bridging ligand containing terpyridyl and catechol binding sites

    Energy Technology Data Exchange (ETDEWEB)

    Whittle, B.; Everest, N.S.; Howard, C.; Ward, M.D. [Univ. of Bristol (United Kingdom)

    1995-04-12

    The ligand 4{prime}-(3,4-dimethoxyphenyl)-2,2{prime}:6{prime},2{double_prime}-terpyridine (L{sup 2}), containing a terpyridyl binding site and a masked catechol binding site, was prepared by a standard Kroehnke-type synthesis. From this the complexes [Ru(terpy)-(L{sup 2})][PF{sub 6}]{sub 2} (1) and [Ru(L{sup 2}){sub 2}][PF{sub 6}]{sub 2} (2), containing one and two dimethoxyphenyl substituents, were prepared: demethylation with BBr{sub 3} afforded [Ru(terpy)(H{sub 2}L{sup 1})][PF{sub 6}]{sub 2} (3) and [Ru(H{sub 2}L{sup 1}){sub 2}][PF{sub 6}]{sub 2} (4), respectively, which have one or two free catechol binding sites pendant from the [Ru(terpy){sub 2}]{sup 2+} core. Binuclear complexes (based on 3) and trinuclear complexes (based on 4) were then prepared by attachment of other metal fragments at the catechol sites. In [Ru(terpy)({mu}-L{sup 1})Ru(bipy){sub 2}][PF{sub 6}]{sub 3} (5) and [Ru({mu}-L{sup 1}){sub 2}(Ru(bipy){sub 2}){sub 2}][PF{sub 6}]{sub 4} (6) the pendant (Ru(bipy){sub 2}(O-O)){sup n+} sites (O-O = catecholate, n = 0; o-benzosemiquinone, n = 1; o-benzoquinone, n = 2) are redox active and may be reversibly interconverted between the three oxidation levels. In [Ru(terpy)({mu}-L{sup 1})Pd(bipy)][PF{sub 6}]{sub 2} (7), [Ru({mu}-L{sup 1}){sub 2}(Pd(bipy)){sub 2}][PF{sub 6}]{sub 2} (8), [Ru(terpy)({mu}-L{sup 1})Pd(4,4{prime}-{sup t}Bu{sub 2}-bipy)][PF{sub 6}]{sub 2} (9), and [Ru({mu}-L{sup 1}){sub 2}(Pd(4,4{prime}-{sup t}Bu{sub 2}-bipy)){sub 2}][PF{sub 6}]{sub 2} (10) the pendant (Pd(bipy)(catecholate)) fragments are known to be photocatalysts for production of {sup 1}O{sub 2} in their own right. Electrochemical and UV/vis studies were performed on all complexes and consistently indicate the presence of interactions between the components in 5-10. The EPR spectrum of 6 (which contains two semiquinone radicals) shows that the two spins are coupled by an exchange interaction.

  1. A Novel Therapeutic Strategy for the Treatment of Glioma, Combining Chemical and Molecular Targeting of Hsp90α

    Energy Technology Data Exchange (ETDEWEB)

    Mehta, Adi; Shervington, Leroy; Munje, Chinmay; Shervington, Amal, E-mail: aashervington@googlemail.com [Brain Tumour North West, Faculty of Science and Technology, University of Central Lancashire, Preston, PR1 2HE (United Kingdom)

    2011-12-08

    Hsp90α's vital role in tumour survival and progression, together with its highly inducible expression profile in gliomas and its absence in normal tissue and cell lines validates it as a therapeutic target for glioma. Hsp90α was downregulated using the post-transcriptional RNAi strategy (sihsp90α) and a post-translational inhibitor, the benzoquinone antibiotic 17-AAG. Glioblastoma U87-MG and normal human astrocyte SVGp12 were treated with sihsp90α, 17-AAG and concurrent sihsp90α/17-AAG (combined treatment). Both Hsp90α gene silencing and the protein inhibitor approaches resulted in a dramatic reduction in cell viability. Results showed that sihsp90α, 17-AAG and a combination of sihsp90α/17-AAG, reduced cell viability by 27%, 75% and 88% (p < 0.001), respectively, after 72 h. hsp90α mRNA copy numbers were downregulated by 65%, 90% and 99% after 72 h treatment with sihsp90α, 17-AAG and sihsp90α/17-AAG, respectively. The relationship between Hsp90α protein expression and its client Akt kinase activity levels were monitored following treatment with sihsp90α, 17-AAG and sihsp90α/17-AAG. Akt kinase activity was downregulated as a direct consequence of Hsp90α inhibition. Both Hsp90α and Akt kinase levels were significantly downregulated after 72 h. Although, 17-AAG when used as a single agent reduces the Hsp90α protein and the Akt kinase levels, the efficacy demonstrated by combinatorial treatment was found to be far more effective. Combination treatment reduced the Hsp90α protein and Akt kinase levels to 4.3% and 43%, respectively, after 72 h. hsp90α mRNA expression detected in SVGp12 was negligible compared to U87-MG, also, the combination treatment did not compromise the normal cell viability. Taking into account the role of Hsp90α in tumour progression and the involvement of Akt kinase in cell signalling and the anti-apoptotic pathways in tumours, this double targets treatment infers a novel therapeutic strategy.

  2. A double signal electrochemical human immunoglobulin G immunosensor based on gold nanoparticles-polydopamine functionalized reduced graphene oxide as a sensor platform and AgNPs/carbon nanocomposite as signal probe and catalytic substrate.

    Science.gov (United States)

    Zhang, Si; Huang, Na; Lu, Qiujun; Liu, Meiling; Li, Haitao; Zhang, Youyu; Yao, Shouzhuo

    2016-03-15

    In this paper, a double signal electrochemical Human immunoglobulin G (HIgG) immunosensor based on AgNPs/carbon nanocomposite (Ag/C NC) as the signal probe and catalytic substrate was developed for fast and sensitive detection of HIgG. The as-prepared AuNPs-PDA-rGO nanocomposite and Ag/C NC were confirmed by UV-vis, Fourier transform infrared spectroscopy, scanning electron microscopy and transmission electron microscopy. Electrochemical impedance spectroscopy, cyclic voltammetry and differential pulse voltammetry were used to investigate the electrochemical properties of the proposed immunosensor. The AuNPs-PDA-rGO nanocomposite can improve the electron transfer rate and capture more Ab1. In the sandwich-type immunoassay process, the Ag/C NC functionalized bioconjugates were captured on HIgG/Ab1/AuNPs-PDA-rGO surface and the electrochemical double-signal strategy was employed. These double electrochemical detection signals were directly monitored the oxidation current originated from Ag/C NC and indirectly detected the reduction current of benzoquinone which was produced from the reaction of H2O2 and HQ by catalysis of Ag/C NC in electrochemical detection of HIgG. Under the optimized conditions, the current responses were changed with the concentrations of HIgG for the proposed immunosensor with wide linear ranges of 0.1 to 100 ngmL(-1) and 0.01-100 ngmL(-1) with the lowest detection concentration of 0.001 ng mL(-1) in the absence and presence of H2O2 and HQ. The double-signal strategy is used for detection of HIgG, and the results came from the two signals were well consistent with each other. The proposed immunosensor was successfully applied in analysis of human IgG in real samples and this strategy may provide a relative simple and effective method for construction of other immunsensors in detection of other biomarkers in clinical medicine.

  3. TiO2光催化降解4-氯苯酚过程中的电分析监测%On-Line Monitoring in Photocatalytic Degrad ation of 4-Chlorophenol by Using Cyclic Voltammetry and UV-Vis Spectrometry

    Institute of Scientific and Technical Information of China (English)

    贺飞; 沈伟韧; 方程; 方佑龄

    2001-01-01

    On-line monitoring in photocatalytic degradation process oforganic compound 4-chlorophenol (4-CP) w as carrie d out by using cyclic voltammetry and UV-Vis spectrometry. The result showed th at the degradation process undertook at least a two-route mechanism to the comp lete mineralization: through redox pairs of benzoquinone(BQ) and hydrobenzoquinone(HQ ) and of hydroxybenzoquinone(HBQ) and hydroxyhydrobenzoquinone(HHQ). UV-Vis spe ctra taken at different time showed the breakage of benzene ring and the complet e mineralization. The electroanalysis was proved to be a proper technique for on -line monitoring as it could detect simultaneously both initial reactants and intermed iates, and thus it is suitable for on-line monitoring and complementary for mec hanism study.%采用循环伏安法和紫外光谱法对有机物的光催化降解进行机理研究和在线监测.以标准光催化剂DegussaP25在紫外光照射下催化降解4-氯苯酚,发现在降解过程中至少有两对氧化还原中间产物:对苯二酚-苯醌和羟基氢醌-羟基苯醌.由4-氯苯酚及中间产物的电极响应,可以观测到它们在光催化降解过程中的含量变化,从而对整个过程实现在线监测,并由此全面了解光催化反应机理.从不同反应时间后测得的紫外光谱可以看到,苯环特征峰逐渐消失.这表明4-氯苯酚的苯环逐渐被打开,直至被彻底降解.

  4. A Novel Mechanism for Halogenated Quinone- Mediated and Metal-Independent Organic Fenton-Like Reaction%不依赖于过渡金属离子的卤代醌介导的新型有机类Fenton反应机理

    Institute of Scientific and Technical Information of China (English)

    朱本占; 任福荣; 夏海英; 邵杰

    2012-01-01

    卤代醌是许多卤芳香持久有机污染物的致癌代谢产物和饮用水消毒副产物.羟基自由基(OH)被公认为生物系统中最具活性的活性氧物种,能导致生物体内DNA等生物大分子的氧化损伤.目前,最被广泛接受的OH产生机理是过渡金属离子催化的Fenton反应.综合采用电子自旋共振二级自旋捕获和其他分析方法,发现四氯苯醌和其它卤代醌皆可通过不依赖于过渡金属离子的途径,显著促进氢过氧化物(H2O2或有机氢过氧化物)的分解而产生OH或烷氧自由基,并首次检测到一种新型的、以碳为中心的醌自由基.基于以上研究,提出一类不依赖于过渡金属离子的卤代醌介导的新型有机类Fenton反应机理.%Halogenated quinones are a class of carcinogenic metabolites of many halogenated persistent organic pollutants and new chlorination disinfection byproducts in drinking water. The hydroxyl radical ("OH) has been considered to be one of the most reactive oxygen species produced in biological systems. It has been shown that 'OH can cause oxidative damage to DNA and other macromolecuies. One of the most widely accepted mechanisms for OH production is through the transition metal-catalyzed Fenton reaction. Through the complementary application of electron spin resonance (ESR) secondary spin-trapping and other analytical methods, we found that tetrachloro-1,4-benzoquinone (TCBQ) and other halogenated quinones could markedly enhance the decomposition of hydroperoxides (H2O2 and organic hydroperoxides) and formation of "OH and alkoxyl radicals independent of transition metal ions. A novel carbon-centered quinone ketoxy radical was also detected and identified for the first time. Based on these data, we proposed a novel mechanism for metal-independent and halogenated quinone-mediated organic Fenton-like reaction.

  5. The role of nitrite and nitrate ions as photosensitizers in the phototransformation of phenolic compounds in seawater

    Energy Technology Data Exchange (ETDEWEB)

    Calza, P., E-mail: paola.calza@unito.it [Universita degli Studi di Torino, Dipartimento di Chimica, Via P. Giuria 5, 10125 Torino (Italy); Vione, D. [Universita degli Studi di Torino, Dipartimento di Chimica, Via P. Giuria 5, 10125 Torino (Italy); Universita degli Studi di Torino, Centro Interdipartimentale NatRisk, Via Leonardo da Vinci 44, 10095 Grugliasco (Italy); Novelli, A. [Max Planck Institute for Chemistry, 55128 Mainz (Germany); Pelizzetti, E.; Minero, C. [Universita degli Studi di Torino, Dipartimento di Chimica, Via P. Giuria 5, 10125 Torino (Italy)

    2012-11-15

    Nitrite and nitrate are known to be involved in photochemical processes occurring in natural waters. In this study we have investigated the role played by these photosensitizers towards the transformation of xenobiotic organic matter in marine water, with the goal of assessing the typical transformation routes induced in seawater by irradiated nitrite/nitrate. For this purpose, phenol was chosen as model molecule. Phenol transformation was investigated under simulated solar radiation in the presence of nitrite (in the range of 1 Multiplication-Sign 10{sup -5}-1 Multiplication-Sign 10{sup -2} M) or nitrate ions, in pure water at pH 8, in artificial seawater (containing same dissolved salts as seawater but no organic matter), and in natural seawater. In all experiments, phenol degradation rate and formation of intermediates were assessed. As expected, phenol disappearance rate decreased with decreasing nitrite concentration and was slightly reduced by the presence of chloride. Other salts present in artificial seawater (e.g. HCO{sub 3}{sup -}, CO{sub 3}{sup 2-} and Br{sup -}) had a more marked effect on phenol transformation. Analysis of intermediates formed in the different matrices under study showed generation of hydroxyl-, nitro- and chloroderivatives of phenol, to a different extent depending on experimental conditions. 1,4-Benzoquinone prevailed in all cases, nitroderivatives were only formed with nitrite but were not detected in nitrate-spiked solutions. Competition was observed between halogenation and nitration of phenol, with variable outcome depending on nitrite concentration. The most likely reason is competition between nitrating and halogenating species for reaction with the phenoxyl radical. A kinetic model able to justify the occurrence of different intermediates under the adopted conditions is presented and discussed. -- Highlights: Black-Right-Pointing-Pointer Nitrite and nitrate-mediated solar-driven transformations of pollutant in seawater were

  6. Degradation of tyrosol by a novel electro-Fenton process using pyrite as heterogeneous source of iron catalyst.

    Science.gov (United States)

    Ammar, Salah; Oturan, Mehmet A; Labiadh, Lazhar; Guersalli, Amor; Abdelhedi, Ridha; Oturan, Nihal; Brillas, Enric

    2015-05-01

    Tyrosol (TY) is one of the most abundant phenolic components of olive oil mill wastewaters. Here, the degradation of synthetic aqueous solutions of 0.30 mM TY was studied by a novel heterogeneous electro-Fenton (EF) process, so-called EF-pyrite, in which pyrite powder was the source of Fe(2+) catalyst instead of a soluble iron salt used in classical EF. Experiments were performed with a cell equipped with a boron-doped diamond anode and a carbon-felt cathode, where TY and its products were destroyed by hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton's reaction between Fe(2+) and H2O2 generated at the cathode. Addition of 1.0 g L(-1) pyrite provided an easily adjustable pH to 3.0 and an appropriate 0.20 mM Fe(2+) to optimize the EF-pyrite treatment. The effect of current on mineralization rate, mineralization current efficiency and specific energy consumption was examined under comparable EF and EF-pyrite conditions. The performance of EF-pyrite was 8.6% superior at 50 mA due to self-regulation of soluble Fe(2+) by pyrite. The TY decay in this process followed a pseudo-first-order kinetics. The absolute rate constant for TY hydroxylation was 3.57 × 10(9) M(-1) s(-1), as determined by the competition kinetics method. Aromatic products like 3,4-dihydroxyphenylethanol, 4-hydroxyphenylacetic acid, 4-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid and catechol, as well as o-benzoquinone, were identified by GC-MS and reversed-phase HPLC. Short-chain aliphatic carboxylic acids like maleic, glycolic, acetic, oxalic and formic were quantified by ion-exclusion HPLC. Oxalic acid was the major and most persistent product found. Based on detected intermediates, a plausible mineralization pathway for TY by EF-pyrite was proposed. PMID:25720669

  7. Investigation of redox activities of soil humic acids using 3D excitation emission matrix fluorescence spectroscopy%基于三维荧光光谱特征研究土壤腐殖质氧化还原特性

    Institute of Scientific and Technical Information of China (English)

    姜杰; 李黎; 孙国新

    2012-01-01

    Humic substances serve as electron shuttles in the soil environment. They not only stimulate the element migration, but also accelerate containment degradation and environment remediation. In this study, a standard humic acid and two extracted humic acids from soil samples were reduced by H2, and three-dimensional excitation emission matrix fluorescence spectroscopy (3DEEM) was employed to characterize these humic acids. The results of 3DEEMs revealed the differences between native and reduced humic acids. Fluorescence peak intensity of humic acids in the reduced state was lower than those in the natural state, which can be explained by the changes of chemical structures of humic acids, such as the loss of π-π bonds. As a model compound of quinone groups in humic acids, benzoquinone reduction and 3DEEM analysis were carried out under the same conditions. It was observed that there was a decrease of fluorescence with benzoquinone reduction. Potassium ferricyanide method was used to measure the reducing capacity of native extracted humic acids, which was found to be 0. 998 and 0. 465 meq. g-1 C for Yingtan and Taoyuan soils, respectively. Electron accepting capacities of humic acids were 3. 384 and 1.187 meq-g 1 C for Yingtan and Taoyuan soils, respectively. Determination of electron accepting capacities, quantification of redox-active functional groups and prediction of redox reaction processes in soil are all important applications of 3 DEEM in the investigation of humic acid redox-activities.%以国际腐殖质协会腐殖酸和实验室提纯腐殖酸为研究对象,发现被H2还原前后腐殖酸的三维荧光光谱明显不同,但有共同的变化趋势:还原态腐殖酸的三维荧光光谱图的波峰荧光强度均明显低于还原前,说明腐殖酸还原过程有类似π-π化学键断开的结构变化.对苯醌是腐殖酸氧化还原醌基官能团的代表化合物,将其还原前后与腐殖酸还原前后的荧光光

  8. Phenol wastewater treatment by needle-plate pulsed high voltage discharge in gas-liquid two phase%针-板式高压脉冲气液两相放电降解废水中的苯酚

    Institute of Scientific and Technical Information of China (English)

    董冰岩; 张鹏; 聂亚林; 谢寅寅; 何俊文; 王晖

    2016-01-01

    phenol increased,but,would decrease while each factor was greater than a specific value. Under the best condition of 10mm electrode spacing,7.5mm needle-liquid spacing,26kV pulse voltage,70Hz pulse frequency and 1.5L/min aeration,phenol degradation rate was 64.63% when 100mL concentration of 100mg/L of phenol wastewater was discharged for 60min. In addition,phenol degradation rate reached 85.02% when wastewater was discharged for 140min. The concentration of byproducts such as resorcinol,hydroquinone,benzoquinone and catechol increased firstly,then decreased gradually and eventually disappeared with the increase of discharge time. Besides,concentration of resorcinol was the lowest and appeared in two stages,that of benzoquinone was the largest,and catechol disappeared first. The completeness of phenol degradation could be improved by studying the change of byproducts.

  9. New Class of Flow Batteries for Terrestrial and Aerospace Energy Storage Applications

    Science.gov (United States)

    Bugga, Ratnakumar V.; West, William C.; Kindler, Andrew; Smart, Marshall C.

    2013-01-01

    Future sustainable energy generation technologies such as photovoltaic and wind farms require advanced energy storage systems on a massive scale to make the alternate (green) energy options practical. The daunting requirements of such large-scale energy systems such as long operating and cycle life, safety, and low cost are not adequately met by state-of-the-art energy storage technologies such as vanadium flow cells, lead-acid, and zinc-bromine batteries. Much attention is being paid to redox batteries specifically to the vanadium redox battery (VRB) due to their simplicity, low cost, and good life characteristics compared to other related battery technologies. NASA is currently seeking high-specific- energy and long-cycle-life rechargeable batteries in the 10-to-100-kW range to support future human exploration missions, such as planetary habitats, human rovers, etc. The flow batteries described above are excellent candidates for these applications, as well as other applications that propose to use regenerative fuel cells. A new flow cell technology is proposed based on coupling two novel electrodes in the form of solvated electron systems (SES) between an alkali (or alkaline earth) metal and poly aromatic hydrocarbons (PAH), separated by an ionically conducting separator. The cell reaction involves the formation of such SES with a PAH of high voltage in the cathode, while the alkali (or alkaline earth metal) is reduced from such an MPAH complex in the anode half-cell. During recharge, the reactions are reversed in both electrodes. In other words, the alkali (alkaline earth) metal ion simply shuttles from one M-PAH complex (SES) to another, which are separated by a metal-ion conducting solid or polymer electrolyte separator. As an example, the concept was demonstrated with Li-naphthalene//Li DDQ (DDQ is 2,3-Dichloro-5,6-dicyano- 1,4-benzoquinone) separated by lithium super ion conductor, either ceramic or polymer (solid polymer or gel polymer) electrolytes. The

  10. Determinação de fenol urinário por cromatografia em fase gasosa em trabalhadores que utilizam resinas fenólicas em fundições Determination of urinary phenol by gas chromatography in workers using phenolic resins in foundries

    Directory of Open Access Journals (Sweden)

    Tiago Severo Peixe

    2006-06-01

    Full Text Available O fenol é utilizado na indústria como agente desinfetante no preparo de resinas fenólicas e pigmentos de tintas. Apresenta-se no estado sólido à temperatura ambiente, com coloração fracamente rósea, odor acre e higroscópico. Na exposição ocupacional aguda o composto pode levar a lesões eritematosas e, cronicamente, afetar a maturação celular no compartimento medular ósseo devido à formação de quinonas livres e 1,4-benzoquinona, proveniente do metabolismo hepático da hidroquinona via CYP2E1. A monitorização biológica possui relevância nas situações de exposições ocupacionais. Para tal, utiliza-se o fenol urinário, considerado bioindicador de exposição a este composto. O objetivo do presente trabalho foi validar uma técnica de extração líquido-líquido para quantificar o fenol urinário, por meio da cromatografia em fase gasosa com detetor de ionização por chama (CG/DIC em urina de trabalhadores expostos ao fenol em fundições. O método mostrou-se linear de 5 a 200 µg/mL; coeficiente de regressão linear (r² de 0,999; limites de detecção e quantificação 2,0 e 5,0 µg/mL, respectivamente; precisão intra-ensaio entre 4,5 e 8,9% e inter-ensaio entre 5,7 e 14,2%; exatidão entre 6,2 e 11,9% e recuperação superior a 87%. O método demonstrou ser simples e rápido. Amostras provenientes de trabalhadores expostos ao fenol foram analisadas comprovando a aplicação da técnica na monitorização biológica.Phenol is used as an industrial chemical, disinfectant agent, in the preparation of phenolic resins and paint pigments. When in solid state, it shows a light pink color, ocre odor, and is hygroscopic. In acute occupational exposure, the compound can produce erythemic injuries and burn sensation and, chronically, affect the cellular maturation of bone marrow due the free quinones and 1,4-benzoquinone, deriving from hepatic metabolism of the hydroquinone by P450 isozyme (CYP2E1. The biological monitoring is

  11. Employing Arynes in Diels-Alder Reactions and Transition-Metal-Free Multicomponent Coupling and Arylation Reactions.

    Science.gov (United States)

    Bhojgude, Sachin Suresh; Bhunia, Anup; Biju, Akkattu T

    2016-09-20

    Arynes are highly reactive intermediates having several applications in organic synthesis for the construction of various ortho-disubstituted arenes. Traditionally, arynes are generated in solution from haloarenes under strongly basic conditions. However, the scopes of many of the aryne reactions are limited because of the harsh conditions used for their generation. The renaissance of interest in aryne chemistry is mainly due to the mild conditions for their generation by the fluoride-induced 1,2-elimination of 2-(trimethylsilyl)aryl triflates. This Account is focused on the Diels-Alder reaction of arynes and their transition-metal-free application in multicomponent couplings as well as arylation reactions. The Diels-Alder reaction of arynes is a powerful tool for constructing benzo-fused carbocycles and heterocycles. In 2012, we developed an efficient, broad-scope, and scalable Diels-Alder reaction of pentafulvenes with arynes affording benzonorbornadiene derivatives. Subsequently, we accomplished the Diels-Alder reaction of arynes with dienes such as 1,2-benzoquinones and tropones. Moreover, we uncovered a transition-metal-free protocol for the synthesis of 9,10-dihydrophenanthrenes by the reaction of arynes with styrenes that proceeds via a Diels-Alder/ene-reaction cascade. In addition, we demonstrated the reaction of arynes with indene/benzofurans, which proceeds via a tandem [4 + 2]/[2 + 2] sequence. Multicomponent coupling (MCC) involving arynes mainly comprises the initial addition of a nucleophile to the aryne followed by interception of the aryl anion intermediate with an electrophile (provided the nucleophilic and electrophilic moieties do not belong to the same molecule). We have disclosed aryne MCCs initiated by N-heterocycles such as (iso)quinoline, pyridine, and aziridines. When (iso)quinoline is used as the nucleophilic trigger and N-substituted isatin as the third component, the reaction affords spirooxazino(iso)quinolines via 1,4-dipolar

  12. Coupling of the 4f Electrons in Lanthanide Molecules

    Energy Technology Data Exchange (ETDEWEB)

    Kazhdan, Daniel [Univ. of California, Berkeley, CA (United States)

    2008-09-01

    ;-dimethyl-2,2'-bipyridine) and (C5Me5)2Yb(6-methyl-2,2'-bipyridine), the valence, as measured by XANES, changes as a function of temperature. In general, the magnetism in complexes of the type (C5Me5)2Yb(bipy.-), where bipyo represents 2,2'-bipyridine and substituted 2,2'-bipyridine ligands, is described by a multiconfiguration model, in which the ground state is an open-shell singlet composed of two configurations: Yb(III, f13)(bipy.-) and Yb(II, f14)(bipyo). The relative contributions of the two configurations depends on the substituents on the bipyridine ligand.[(C5Me5)3Ln]2(L) (Ln = Ce, Tb; L = 4,4'-bipyridine, 1,4-benzoquinone) are synthesized in order to study the effect of these ligands on the oxidation states of the metal as well as to study intramolecular coupling between two lanthanides fragments.

  13. Timely resolved measurements on CdSe nanoparticles; Zeitaufgeloeste Messungen an CdSe Nanopartikeln

    Energy Technology Data Exchange (ETDEWEB)

    Holt, B.E. von

    2006-06-06

    By means of infrared spectroscopy the influence of the organic cover on structure and dynamics of CdSe nanoparticles was studied. First a procedure was developed, which allows to get from the static infrared spectrum informations on the quality of the organic cover and the binding behaviour of the ligands. On qualitatively high-grade and well characterized samples thereafter the dynamics of the lowest-energy electron level 1S{sub e} was time-resolvedly meausred in thew visible range. As reference served CdSe TOPO, which was supplemented by samples with the ligands octanthiole, octanic acid, octylamine, naphthoquinone, benzoquinone, and pyridine. The studied nanoparticles had a diameter of 4.86 nm. By means of the excitation-scanning or pump=probe procedure first measurements in the picosecond range were performed. The excitation wavelengths were thereby spectrally confined and so chosen that selectively the transitions 1S{sub 3/2}-1S-e and 1P{sub 3/2}-1P{sub e} but not the intermediately lyingt transition 2S{sub 3/2}-1S{sub e} were excited. The excitation energies were kept so low that the excitation of several excitons in one crystal could be avoided. The scanning wavelength in the infrared corresponded to the energy difference between the electron levels 1S{sub e} and 1P{sub e}. The transients in the picosecond range are marked by a steep increasement of the signal, on which a multi-exponential decay follows. The increasement, which reproduces the popiulation of the excited state, isa inependent on the choice of the ligands. The influence of the organic cover is first visible in the different decay times of the excited electron levels. the decay of the measurement signal of CdSe TOPO can be approximatively described by three time constants: a decay constant in the early picosecond region, a time constant around hundert picoseconds, and a time constant of some nanoseconds. At increasing scanning wavelength the decay constants become longer. By directed excitation

  14. Molecular mechanism of metal-independent decomposition of lipid hydroperoxide by the carcinogenic halogenated quinones%致癌性卤代醌介导的脂质氢过氧化物分解的分子机制

    Institute of Scientific and Technical Information of China (English)

    刘庆林; 覃浩; 黄春华; 刘蒲; 朱本占

    2014-01-01

    Halogenated quinones are a class of carcinogenic intermediates and newly identified chlorination disinfection byproducts in drinking water. 13-Hydroperoxy-9, 11-octadecadienoic acid (13-HPODE) is the most extensively studied endogenous lipid hydroperoxide. Although it is well known that the decomposition of 13-HPODE can be catalyzed by transition metal ions, it is not clear whether halogenated quinones could enhance its decomposition independent of metal ions, and if so, what are the unique characteristics and similarities? We found that halogenated quinones such as 2,5-dichloro-1,4-benzoquinone ( DCBQ) could markedly enhance the decomposition of 13-HPODE and formation of the reactive lipid alkyl radicals such as pentyl and 7-carboxyheptyl radicals, and the genotoxic 4-hydroxy-2-nonenal ( HNE ) , through the complementary application of ESR spin-trapping, HPLC-MS and GC-MS methods. Interestingly, two chloroquinone-lipid alkoxyl conjugates were also detected and identified from the reaction between DCBQ and 13-HPODE. We propose that the enhanced decomposition of the endogenous lipid hydroperoxide 13-HPODE by halogenated quinones and formation of reactive lipid alkyl radicals and genotoxic HNE is through a novel metal-independent nucelophilic substitution coupled with homolytic decomposition mechanism, which may partly explain their potential genotoxicity and carcinogenicity.%卤代醌是许多卤芳香持久有机污染物的致癌代谢产物和饮用水消毒副产物.13-过氧羟基-9,11-十八碳二烯酸(13-HPODE)是最为广泛研究的内源性脂质过氧化物.众所周知,过渡金属离子可以催化分解13-HPODE,但尚不清楚卤代醌是否可以通过不依赖金属离子的途径促进其分解;若是如此,又有什么特异性和相似性?我们发现卤化醌如2,5-二氯-1,4-苯醌( DCBQ)可显著促进13-HPODE的分解.综合采用电子自旋共振-自旋捕获、HPLC-MS和GC-MS等分析方法,可检测到反

  15. Design and synthesis of polymer, carbon and composite electrodes for high energy and high power supercapacitors

    Science.gov (United States)

    Arcila Velez, Margarita Rosa

    ordered structure of the VACNTs showed superior performance compared to randomly oriented CNTs. To increase the energy density, the second approach was taken, by combining pre-synthesized conducting polymers (CPs) and carbon nanotubes (CNTs) using a facile scalable dispersion filtration method to produce free-standing electrodes. Composites with the three main CPs were prepared, analyzed in various electrolytes, and their performance was comparable with polymer/ CNT films prepared with more complex techniques such as in-situ polymerization and pellet pressing. Then, based on the idea that the quinone molecules present in lignin store charge by undergoing a 2 proton, 2 electron redox reaction, a composite between polypyrrole, a stable conducting polymer, and the prototypical molecule p-benzoquinone was fabricated by electropolymerization of pyrrole in the presence of the redox molecule. A significant increase in capacitance and capacity was obtained with respect to polypyrrole films. Furthermore, an important obstacle in the application of CPs in SCs is the lack of easily reduced (n-dopable) polymers. Poly(aminoanthraquinone) (PAQ) is a conjugated polymer that shows electroactivity in the negative potential range of 0 to -2 V, due to the redox moieties of the polymer. PAQ was electropolymerized on free-standing CNT films and its performance as anode for SCs was studied. The materials and processing techniques described in this dissertation are useful to further develop high power/high energy electrodes for SCs.

  16. Applications of hydrogen peroxide in electrochemical technology

    Energy Technology Data Exchange (ETDEWEB)

    Alvarez Gallegos, Alberto Armando

    1998-12-01

    It is demonstrated that hydrogen peroxide can be produced with a current efficiency of 40-70% by the cathodic reduction of oxygen at a reticulated vitreous carbon electrode in a divided flow-cell using catholytes consisting of aqueous chloride or sulphate media, pH >>{sub 2}. The supporting electrolyte does not influence either the current efficiency for H{sub 2}O{sub 2} or its rate of production. The current efficiency for H{sub 2}O{sub 2} is not a strong function of the potential and this suggests that 2e- and 4e- reduction of oxygen occurs in parallel at different sites on the carbon surface. Voltammetry experiments showed that (a) the I-E response for oxygen reduction at pH >>{sub 2} is a function of the electrode surface and/or the supporting electrolyte; (b) both H{sub 2} evolution and oxygen reduction are retarded on carbon with increasing ionic strength; (c) the presence of ferrous ions lead to the homogeneous decomposition of H{sub 2}O{sub 2} away from the cathode surface but their effectiveness as a catalyst for this decomposition depends on their speciation in solution which changes during an electrolysis. The use of a three-dimensional electrode fabricated from reticulated vitreous carbon allows Fenton`s reagent to be electroproduced at a practical rate which makes possible the removal of organics in slightly acidic aqueous media. A wide range of highly toxic organic molecules (phenol, catechol, hydroquinone, p-benzoquinone, oxalic acid, aniline, cresol and amaranth) have been oxidised in mild conditions and a significant fraction of the organic carbon is evolved as CO{sub 2}. In all cases studied the initial chemical oxygen demand (COD) was depleted to levels higher than 85%, indicating a complete mineralisation of the organic pollutants. The life-time of the reticulated vitreous carbon cathode was demonstrated to be over 1000 hours during two and a half years of experiments. During this time the cathode performance was very good, leading to

  17. Catalytic Oxidation of Phenol over Zeolite Based Cu/Y-5 Catalyst: Part 1: Catalyst Preparation and Characterization

    Directory of Open Access Journals (Sweden)

    K. Maduna Valkaj

    2015-01-01

    -Mead method of nonlinear regression. On the basis of the obtained results of characterization process and conducted catalytic tests, the following can be observed. Zeolite structure of the prepared catalyst was confirmed through powder X-ray diffraction, scanning electron microscopy and adsorption techniques. Their catalytic performance was monitored in terms of phenol and total organic carbon (TOC conversions, hydrogen peroxide decomposition, by-product distribution and degree of copper leached into the aqueous solution. The obtained experimental results indicate that in the space of 180 minutes, the use of these catalysts allows almost total elimination of phenol and significant removal of total organic carbon content with the use of small amounts of catalyst (0.1 g dm–3 and substoichiometric level (71.4 % of oxidant required for complete oxidation of organic pollutant. The main product among aromatics was catechol, followed by hydroquinone and benzoquinone, which exhibited the typical pattern for a series reaction scheme. The distribution of carboxylic acids was as follows: maleic, fumaric, acetic and oxalic acids. These low-molecular carboxylic acids and aromatic compounds were responsible for the TOC that remained after almost complete removal of phenol. Moreover, one of the most interesting options was to use CWPO as a pre-treatment prior to biological treatment, for simple organic acids that are highly biodegradable. During the reactions, destabilization of the catalyst was observed in terms of leaching of copper from zeolite into the reaction mixture, but the previous investigations of similar catalytic systems showed that the activity of the solid catalyst was not due to the homogeneous contribution of the copper leached from the catalyst, but was more likely due to the activity of the heterogeneous catalyst. Further investigations on the mechanism of catalyst destabilization and methods of stabilization are the subject of the following article in the series. The

  18. Mechanism and Kinetics of Phenol Degradation by TiO2 Photocatalytic Combined Technologies%TiO2光催化联合技术降解苯酚机制及动力学

    Institute of Scientific and Technical Information of China (English)

    张轶; 黄若男; 王晓敏; 王齐; 丛燕青

    2013-01-01

    catalysis systems, the first-order kinetic model of phenol degradation and intermediate products such as hydroquinone, catechol and benzoquinone formation were established. The kinetic model is validated the phenol degradation pathway in different catalysis systems, and also indicates the TiO2/UV/EC system could enhance phenol and intermediate products degradation.

  19. Performance of the Electro-Oxidation and Electro-Fenton Processes with a BDD Anode for the Treatment of Low Contents of Pharmaceuticals in a Real Water Matrix%掺硼金刚石阳极电氧化和电芬顿工艺处理真实水体中低含量药物的研究

    Institute of Scientific and Technical Information of China (English)

    Ignasi Sirés; José Antonio Garrido; Enric Brillas

    2013-01-01

    Here,we report the performance of electro-oxidation and electro-Fenton with a boron-doped diamond (BDD)anode for the treatment of single and multicomponent solutions containing small amounts of pharmaceutical residues (i.e.,1mg· L-1 paracetamol and/or 1 mg· L-1 salicylic acid) spiked into a real water matrix at pH 3.0.Electro-oxidation was performed in a BDD/Pt cell,whereas electro-Fenton was carried out in a BDD/air-diffusion cell to electrogenerate H2O2 at the cathode,always operating at constant current density.It was found that the decay of both pharmaceuticals by electro-oxidation was more rapid in the real water matrix than in ultrapure water with 0.05 mol ·L-1 Na2SO4 because of their additional reaction with active chlorine species produced at the bulk from the oxidation of C1-ion.Such chlorinated oxidants exhibited even higher reactivity than hydroxyl radicals formed and confined at the anode.The increase in current density largely enhanced the removal of both pollutants.Similar results were found using the real water matrix at natural alkaline pH.When the mixture of both pharmaceuticals was treated by electro-oxidation,their abatement became slower owing to the competitive attack of generated oxidants over them.Only a slight acceleration ofpharmaceutical decay was obtained for the real water matrix using electro-Fenton,since the accumulation of additional homogeneous hydroxyl radical formed from Fenton's reaction between generated H2O2 and added FC+ was inhibited by its reaction with C1-to form much less reactive chlorinated radicals.For the real water matrix with added pharmaceuticals,a high degree of mineralization of the natural organic matter content (NOM)was reached at high current densities by electro-oxidation,which was even improved upon addition of 0.05 mol ·L-1 Na2SO4.Traces of oxidation by-products like p-benzoquinone,as well as NO3-and NH4+ ions,were detected during the electro-oxidation of paracetamol solutions,but the N

  20. Environmental applications of chitosan and its derivatives.

    Science.gov (United States)

    Yong, Soon Kong; Shrivastava, Manoj; Srivastava, Prashant; Kunhikrishnan, Anitha; Bolan, Nanthi

    2015-01-01

    , hydraulic conductivity, permeability, surface area and sorption capacity. Crosslinked chitosan is an excellent sorbent for trace metals especially because of the high flexibility of its structural stability. Sorption of trace metals by chitosan is selective and independent of the size and hardness of metal ions, or the physical form of chitosan (e.g., film, powder and solution). Both -OH and -NH2 groups in chitosan provide vital binding sites for complexing metal cations. At low pH, -NH3 + groups attract and coagulate negatively charged contaminants such as metal oxyanions, humic acids and dye molecules. Grafting certain functional molecules into the chitin structure improves sorption capacity and selectivity for remediating specific metal ions. For example, introducing sulfur and nitrogen donor ligands to chitosan alters the sorption preference for metals. Low molecular weight chitosan derivatives have been used to remediate metal contaminated soil and sediments. They have also been applied in permeable reactive barriers to remediate metals in soil and groundwater. Both chitosan and modified chitosan have been used to phytoremediate metals; however, the mechanisms by which they assist in mobilizing metals are not yet well understood. In addition, microbes have been used in combination with chitosan to remediate metals (e.g., Cu and Zn) in contaminated soils. Chitosan has also been used to remediate organic contaminants, such as oil-based wastewater, dyes, tannins, humic acids, phenols, bisphenoi-A, p-benzoquinone, organo-phosphorus insecticides, among others. Chitosan has also been utilized to develop optical and electrochemical sensors for in-situ detection of trace contaminants. In sensor technology, naturally-derived chitosan is used primarily as an immobilizing agent that results from its enzyme compatibility, and stabilizing effect on nanoparticles. Contaminant-sensing agents, such as enzymes, microbes and nanoparticles, have been homogeneously immobilized in chitosan