WorldWideScience

Sample records for acid abts radicals

  1. Two New Saccharide Fatty Acid Esters from the Fruit of Morinda citrifolia L. and Their ABTS Radical Scavenging Activities

    Directory of Open Access Journals (Sweden)

    Hong-Cai Zhang

    2013-11-01

    Full Text Available Two n ew saccharide fatty acid esters (1 and (2, and six other compounds were isolated from the fruit of Morinda citrifolia L. (Rubiaceae The structures were established as (2E-oct-2-enoate-2-O-?-D - glucopyranosyl-?-D-glucopyranoside(1, (2E-2,6-dimethyl -6-hydroxyl-oct-2,7-dienoate-2-O-?-D-glucopyranosyl-?-D-glucopyranoside(2, saccharumoside C(3, O-?-D-apiofuranosyl-(1?6-O-?-D-glucopyranosides of 3-methyl-2-butenol(4, 3-methyl-but-2-en-1-yl ?-D-glucopyranosyl (1?6-?-D-glucopyranoside(5, benzyl - glucopyranoside(6, Hexyl-O-?-D-glucopyranoside(7, and caproic acid(8. Compound 1 and 2 showed moderate activity against ABTS (2,2’-azino-bis(3-ethylbenzothiazoline-6-sulphonate radical in concentration of 0.1-3.2 mg/mL.

  2. KINETICS PROFILES IN THE REACTION OF ABTS DERIVED RADICALS WITH SIMPLE PHENOLS AND POLYPHENOLS

    Directory of Open Access Journals (Sweden)

    CAROLA HENRIQUEZ

    2004-03-01

    Full Text Available The kinetic profile associated to the reaction of phenols with 2,2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid (ABTS derived radicals is extremely dependent of the characteristics of the substrate. In particular, polyphenols present complex profiles that can be associated to successive reactions of different reactive centers present in the target molecule. Also, changes in the secondary reactions of the produced radicals can lead to a partial recovery of the ABTS radical concentration at intermediate reaction times, as observed employing 1,4-dihydroxybenzene. Although the kinetic profiles of monophenols are considerably simpler, the stoichiometry of the process is unexpected. For example, the data obtained imply that four radicals are consumed by each p-tertbutylphenol molecule introduced into the system. This large stoichiometric coefficient is not compatible with a simple, phenol promoted, back reduction of the ABTS radical. These results, as well as the overshoot observed employing 1,4-dihydroxybencene, cast doubts on the use of ABTS based methodologies to quantitatively measure the capacity of a given compound to trap free radicals or the amount of free radical scavengers present in complex mixtures

  3. SCAVENGING ACTIVITY OF DICLOFENAC: INTERACTION WITH ABTS RADICAL CATION AND PEROXYL RADICALS

    Scientific Electronic Library Online (English)

    C, ROJO; M. J, ÁLVAREZ-FIGUEROA; M, SOTO; A, CAÑETE; D, PESSOA-MAHANA; C, LÓPEZ-ALARCÓN.

    Full Text Available The scavenging activity of diclofenac was estimated by its capability to bleach ABTS radical cation, and ORAC (oxygen radical absorbance capacity) methodology. In addition, GC-MS technique was used to establish if the lactamic derivative of diclofenac was formed as final product in the interaction w [...] ith peroxyl radicals. Diclofenac bleached ABTS radical cation in a concentration-dependent way. In ORAC assays, diclofenac inhibited the consumption of fluorescein and c-phycocyanin mediated by peroxyl radicals. An ORAC-fluorescein, and ORAC-c-phycocyanin value of 0.3, and 0.004 was estimated, respectively. From the downcurvature observed in Stern-Volmer-like plots, we postulated that the low protection of c-phycocyanin is related to secondary damage of c-phycocyanin by the secondary radical of diclofenac. By GC-MS studies only a 2,6-dichloroaniline derivative was detected as product afterthe reaction with peroxyl radicals.

  4. SCAVENGING ACTIVITY OF DICLOFENAC: INTERACTION WITH ABTS RADICAL CATION AND PEROXYL RADICALS

    Directory of Open Access Journals (Sweden)

    C ROJO

    2009-01-01

    Full Text Available The scavenging activity of diclofenac was estimated by its capability to bleach ABTS radical cation, and ORAC (oxygen radical absorbance capacity methodology. In addition, GC-MS technique was used to establish if the lactamic derivative of diclofenac was formed as final product in the interaction with peroxyl radicals. Diclofenac bleached ABTS radical cation in a concentration-dependent way. In ORAC assays, diclofenac inhibited the consumption of fluorescein and c-phycocyanin mediated by peroxyl radicals. An ORAC-fluorescein, and ORAC-c-phycocyanin value of 0.3, and 0.004 was estimated, respectively. From the downcurvature observed in Stern-Volmer-like plots, we postulated that the low protection of c-phycocyanin is related to secondary damage of c-phycocyanin by the secondary radical of diclofenac. By GC-MS studies only a 2,6-dichloroaniline derivative was detected as product afterthe reaction with peroxyl radicals.

  5. Evaluation of Antioxidative Activity of Croatian Propolis Samples Using DPPH? and ABTS?+ Stable Free Radical Assays

    Directory of Open Access Journals (Sweden)

    Ivona Jasprica

    2007-05-01

    Full Text Available Propolis is one of the richest sources of plant phenolics (flavonoids and phenolic acids, which are widely recognized as rather strong antioxidants. The aim of our work was to use colored stable free radical (DPPH· and ABTS·+ spectrophotometric and thin-layer chromatographic (TLC assays to study the antioxidative behavior of the phenolics (caffeic acid, galangin and pinocembrin most commonly present in Croatian propolis samples obtained from different Croatian regions. We propose a mathematical model providing a more sophisticated interpretation of the obtained results and a new parameter named antioxidative efficiency (AOE is introduced. The kinetic behaviour of chosen standards determined by spectrophotometric assays follows the exponential decrease of the absorption curve. Explained numerically, AOE represents the absolute value of the first derivative of an absorbance curve in the point A0/e (where A0 is the absorbance measured at t = 0 and e is the natural logarithm base. The advantage of this newly introduced parameter is that it provides an easy and accurate mutual comparison between the rates of antioxidative efficiency of different propolis samples. A TLC assay was only applicable in the case of the DPPH· radical. Dose-response curves were described using a linear function with AOE expressed as a coefficient of the slope. The chromatographic method was shown to be very rapid, reliable and easy-to-perform.

  6. Doxorubicin inhibits oxidation of 2,2?-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) by a lactoperoxidase/H2O2 system by reacting with ABTS-derived radical

    OpenAIRE

    RESZKA, KRZYSZTOF J.; Britigan, Bradley E.

    2007-01-01

    The effect of doxorubicin on oxidation of 2,2?-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) by lactoperoxidase and hydrogen peroxide has been investigated. It was found that: (1) oxidation of ABTS to its radical cation (ABTS•+) is inhibited by doxorubicin as evidenced by its induction of a lag period, duration of which depends on doxorubicin concentration; (2) the inhibition is due to doxorubicin hydroquinone reducing the ABTS•+ radical (stoichiometry 1: 1.8); (3) concomitant with the...

  7. Alteration of fatty acids content during cow's and goat's milk fermentation with ABT-2 culture

    OpenAIRE

    Vedran Sla?anac; Jovica Hardi; Hrvoje Pavlovi?; Mato Vlaini?; Mirela Lu?an

    2005-01-01

    In this paper, changes in composition and contents of each fatty acid during fermentation with ABT-2 culture were examined. The objective of this study was to determinate the increase of short (SCFA) and medium (MCFA) chain fatty acids in goat's and cow's milk during fermentation with ABT-2 culture. The hypothesis of this study was that higher contents of SCFA and MCFA are produced in goat's milk in comparison with cow's milk, during fermentation with ABT-2 culture. Obtained results have show...

  8. New Derivatives of 3,4-Dihydroisoquinoline-3-carboxylic Acid with Free-Radical Scavenging, D-Amino Acid Oxidase, Acetylcholinesterase and Butyrylcholinesterase Inhibitory Activity

    OpenAIRE

    Jolanta Solecka; Adam Gu?piel; Magdalena Postek; Joanna Ziemska; Robert Kaw?cki; Katarzyna ??czycka; Agnieszka Osior; Bart?omiej Pietrzak; Krzysztof Pypowski; Agata Wyrzykowska

    2014-01-01

    A series of 3,4-dihydroisoquinoline-3-carboxylic acid derivatives were synthesised and tested for their free-radical scavenging activity using 2,2-diphenyl-1-picrylhydrazyl radical (DPPH·), 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) radical (ABTS·+), superoxide anion radical (O2·?) and nitric oxide radical (·NO) assays. We also studied D-amino acid oxidase (DAAO), acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE) inhibitory activity. Almost each of newly synthesised co...

  9. Histamine H3 receptor antagonism by ABT-239 attenuates kainic acid induced excitotoxicity in mice.

    Science.gov (United States)

    Bhowmik, Malay; Saini, Neeru; Vohora, Divya

    2014-09-18

    The multifaceted pathogenesis of temporal lobe epilepsy (TLE) offers a number of adjunctive therapeutic prospects. One such therapeutic strategy could be targeting H3 receptor (H3R) by selective H3R antagonists which are perceived to have antiepileptic and neuroprotective potential. Kainic acid (KA) induced seizure, a reliable model of TLE, triggers epileptogenic events resulting from initial neuronal death and ensuing recurring seizures. The present study aimed to determine whether pre-treatment with ABT-239, a novel H3R antagonist, and its combinations with sodium valproate (SVP) and TDZD-8 (glycogen synthase kinase-3? (GSK3?) inhibitor) can prevent the excitotoxic events in mice exposed to KA (10 mg/kg i.p.). ABT-239 (1 and 3 mg/kg i.p.) significantly attenuated KA-mediated behavioural and excitotoxic anomalies and restored altered expression of Bax, cleaved caspase-3, phospho-Akt (Ser473) and cAMP response element binding protein (CREB). Surprisingly, restoration of Bcl2 and phospho-GSK3? (Ser9) by ABT-239 did not reach the level of statistical significance. Co-administration of ABT-239 (1 and 3 mg/kg) with a sub-effective dose of SVP (150 mg/kg i.p.) yielded improved efficacy than when given alone. Similarly, low and high dose combinations of ABT-239 (1 and 3 mg/kg) with TDZD-8 (5 and 10 mg/kg i.p.) produced greater neuroprotection than any other treatment group. Our findings suggests a neuroprotective potential of ABT-239 and its combinations with SVP and TDZD-8 against KA-induced neurotoxicity, possibly mediated through in part each by modulating Akt/GSK3? and CREB pathways. The use of H3R antagonists as adjuvant in the treatment of human TLE might find potential utility, and can be pursued further. PMID:24952295

  10. Methylseleninic acid potentiates multiple types of cancer cells to ABT-737-induced apoptosis by targeting Mcl-1 and Bad

    DEFF Research Database (Denmark)

    Yin, Shutao; Dong, Yinhui

    2012-01-01

    ABT-737, a novel small molecule inhibitor of Bcl-2 family proteins, holds great promise to complement current cancer therapies. However many types of solid cancer cells are resistant to ABT-737. One practical approach to improve its therapeutic efficacy is to combine with the agents that can overcome such resistance to restore the sensitivity. In the present study, a second-generation selenium compound methylseleninic acid (MSeA) synergistically sensitized MDA-MB-231 human breast cancer cells, HT-29 human colon cancer cells and DU145 human prostate cancer cells to apoptosis induction by ABT-737, as evidenced by greater than additive enhancement of Annexin V/FITC positive (apoptotic) cells and activation of multiple caspases and PARP cleavage. Mechanistic investigation demonstrated that MSeA significantly decreased basal Mcl-1 expression and ABT-737-induced Mcl-1 expression. Knocking down of Mcl-1 with RNAi approach supported the functional significance of this molecular target. More importantly, we identified inactivation of Bad by phosphorylation on ser-136 and ser-112 as a novel mechanism involved in ABT-737 resistance, which can be overcome by combining with MSeA. In addition, we found that expression of Bax was required for the efficient execution of synergistic sensitization. Our findings, for the first time, provide a strong mechanistic rationale for developing MSeA as a novel sensitizing agent of ABT-737.

  11. Characterization of the radical-scavenging reaction of 2-O-substituted ascorbic acid derivatives, AA-2G, AA-2P, and AA-2S: a kinetic and stoichiometric study.

    Science.gov (United States)

    Takebayashi, Jun; Tai, Akihiro; Gohda, Eiichi; Yamamoto, Itaru

    2006-04-01

    The aim of this study was to characterize the antioxidant activity of three ascorbic acid (AA) derivatives O-substituted at the C-2 position of AA: ascorbic acid 2-glucoside (AA-2G), ascorbic acid 2-phosphate (AA-2P), and ascorbic acid 2-sulfate (AA-2S). The radical-scavenging activities of these AA derivatives and some common low molecular-weight antioxidants such as uric acid or glutathione against 1,1-diphenyl-picrylhydrazyl (DPPH) radical, 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) radical cation (ABTS+), or galvinoxyl radical were kinetically and stoichiometrically evaluated under pH-controlled conditions. Those AA derivatives slowly and continuously reacted with DPPH radical and ABTS+, but not with galvinoxyl radical. They effectively reacted with DPPH radical under acidic conditions and with ABTS+ under neutral conditions. In contrast, AA immediately quenched all species of radicals tested at all pH values investigated. The reactivity of Trolox, a water-soluble vitamin E analogue, was comparable to that of AA in terms of kinetics and stoichiometrics. Uric acid and glutathione exhibited long-lasting radical-scavenging activity against these radicals under certain pH conditions. The radical-scavenging profiles of AA derivatives were closer to those of uric acid and glutathione rather than to that of AA. The number of radicals scavenged by one molecule of AA derivatives, uric acid, or glutathione was equal to or greater than that by AA or Trolox under the appropriate conditions. These data suggest the potential usage of AA derivatives as radical scavengers. PMID:16595915

  12. Practical problems when using ABTS assay to assess the radical-scavenging activity of peptides: Importance of controlling reaction pH and time.

    Science.gov (United States)

    Zheng, Lin; Zhao, Mouming; Xiao, Chuqiao; Zhao, Qiangzhong; Su, Guowan

    2016-02-01

    Effects of reaction pH and time on the antioxidant behaviors of Tyr, Trp, Cys, and their related peptides (Tyr-Gly, Tyr-Glu, Tyr-Lys, Trp-Gly, Trp-Glu, Trp-Lys, Cys-Gly and Cys-Gly) in ABTS assay were investigated. Results showed that all these amino acids and peptides displayed a biphasic kinetic pattern with a fast initial step and a slow secondary step. The initial reaction rates of Tyr, Trp and their related peptides were strongly dependent on pH, while those of Cys and Cys-containing peptides were unaffected by pH. They failed to reach equilibrium over the short incubation period of 6-10 min typically used in this assay. Longer incubation time was needed for most of the peptides to approach equilibrium at lower pH. The observed biphasic kinetic pattern as well as the high TEAC values for these amino acids and peptides, could be a result of combined antioxidant behaviors of themselves plus the generated reaction products. PMID:26304349

  13. Isoprene, sulphoxy radical-anions and acidity

    Directory of Open Access Journals (Sweden)

    K. J. Rudzi?ski

    2008-12-01

    Full Text Available Transformation of isoprene coupled with autoxidation of SIV in aqueous solutions was studied experimentally and by chemical-kinetic modelling over broad range of solution acidities (pH=3–9 to complement the research on aqueous-phase and heterogeneous transformation of isoprene reported recently by many laboratories. Isoprene significantly slowed down the autoxidation in acidic and basic solutions, and accelerated it slightly in neutral solutions. Simultaneously, production of sulphate ions and formation of solution acidity were significantly reduced. Formation of sulphite and sulphate derivatives of isoprene – sulphurous acid mono-(2-methyl-4-oxo-but-2-enyl ester (m/z=162.9, sulphurous acid mono-(4-hydroxy-2-methyl-but-2-enyl ester (m/z=164.9, sulphuric acid mono-(2-methyl-4-oxo-but-2-enyl ester (m/z=178.9, sulphuric acid mono-(4-hydroxy-2-methyl-but-2-enyl ester (m/z=180.9 – was indicated by mass spectroscopic analysis of post-reaction mixtures. The results of experiments were explained by changes in a subtle quantitative balance of three superimposed processes whose rates depended in different manner on the acidity of reacting solutions – the scavenging of sulphoxy radicals by isoprene, the formation of sulphoxy radicals during further reactions of isoprene radicals, and the autoxidation of SIV itself. A chemical mechanism based on this idea was explored numerically to show good agreement with experimental data. Interaction of isoprene with sulphur(IV species and oxygen can possibly result in formation of new organosulphate components of atmospheric aerosols and waters, and influence distribution of reactive sulphur and oxygen species in isoprene-emitting organisms exposed to SIV pollutants.

  14. Isoprene, sulphoxy radical-anions and acidity

    Science.gov (United States)

    Rudzi?ski, K. J.; Gmachowski, L.; Kuznietsova, I.

    2008-12-01

    Transformation of isoprene coupled with autoxidation of SIV in aqueous solutions was studied experimentally and by chemical-kinetic modelling over broad range of solution acidities (pH=3-9) to complement the research on aqueous-phase and heterogeneous transformation of isoprene reported recently by many laboratories. Isoprene significantly slowed down the autoxidation in acidic and basic solutions, and accelerated it slightly in neutral solutions. Simultaneously, production of sulphate ions and formation of solution acidity were significantly reduced. Formation of sulphite and sulphate derivatives of isoprene - sulphurous acid mono-(2-methyl-4-oxo-but-2-enyl) ester (m/z=162.9), sulphurous acid mono-(4-hydroxy-2-methyl-but-2-enyl) ester (m/z=164.9), sulphuric acid mono-(2-methyl-4-oxo-but-2-enyl) ester (m/z=178.9), sulphuric acid mono-(4-hydroxy-2-methyl-but-2-enyl) ester (m/z=180.9) - was indicated by mass spectroscopic analysis of post-reaction mixtures. The results of experiments were explained by changes in a subtle quantitative balance of three superimposed processes whose rates depended in different manner on the acidity of reacting solutions - the scavenging of sulphoxy radicals by isoprene, the formation of sulphoxy radicals during further reactions of isoprene radicals, and the autoxidation of SIV itself. A chemical mechanism based on this idea was explored numerically to show good agreement with experimental data. Interaction of isoprene with sulphur(IV) species and oxygen can possibly result in formation of new organosulphate components of atmospheric aerosols and waters, and influence distribution of reactive sulphur and oxygen species in isoprene-emitting organisms exposed to SIV pollutants.

  15. Thiazolidin-4-ones from 3-(Aminomethyl)pyridine, Arenealdehydes and Mercaptoacetic Acid: Synthesis and Radical Scavenger Activity

    Scientific Electronic Library Online (English)

    Adriana M., Neves; Auri R., Duval; Gabriele A., Berwaldt; Daniela P., Gouvêa; Natália P., Flores; Pâmela G. da, Silva; Francieli M., Stefanello; Wilson, Cunico.

    2015-02-01

    Full Text Available The efficient synthesis of fifteen novel thiazolidin-4-ones from reaction of 3-(aminomethyl) pyridine (3-picolylamine), arenealdenhydes and mercaptoacetic acid was described. The desired compounds were obtained in moderated to good yields by two methodologies: conventional heating and ultrasound irr [...] adiation. The thiazolidin-4-ones were fully identified and characterized by nuclear magnetic resonance (NMR), gas chromatography coupled to mass spectrometry (GC?MS) and high resolution mass spectrometry (HRMS) techniques. Four compounds showed radical scavenger activity in the 2,2’-azinobis-3-ethyl-benzothiazoline-6-sulfonic acid (ABTS) assay.

  16. Radical processes in radiolysis of monocarboxylic acids in liquid phase

    International Nuclear Information System (INIS)

    A possibility of investigating short-lived radicals arising at radiolysis of liquid monocarbon acids, particularly, acetic and propionic acids by means of spin traps (c-phenyl-ter.butylnitron, ter.-butylmethylenenitron, ter.-nitroisobuthane, 2, 4, 6-tri-ter.-butyl-nitrosobenzene) is disclosed. Solutions of spin traps have been vacuumized and ?-irradiated with 60Co at 20 deg or - 196 deg, then they have been frozen. EPR spectra have been taken at temperatures from - 24 to 10 deg. Alkyl and acyl radicals are the basic radical products of radiolysis of acetic and propionic acids while CH2COOH and CH3CHCOOH are, probably, formed as secondary products. Additions of effective electron acceptor-benzophenone decrease yield of adducts with acyl radicals in the propionic acid and they do not affect yield of adducts with C2H5

  17. Acid and base catalysed oxidation of 3-substituted 4-hydroxy cinnamic acid by hydroxyl radical

    International Nuclear Information System (INIS)

    Hydroxyl radical reactions of 3,4-dihydroxy cinnamic acid and 3-methoxy-4-hydroxy cinnamic acid were studied in the pH range 3-11. The initial reaction in these cases was formation of a radical adduct followed by elimination of water to yield the corresponding phenoxyl radical which was independently confirmed by one electron oxidation by azide radicals. The water elimination was found to be catalysed by both acid and base in case of 3,4-dihydroxy cinnamic acid, whereas it was only base catalysed in case of 3-methoxy-4-hydroxy cinnamic acid. (author)

  18. Determination of protective properties of Bardejovske Kuple spa curative waters by rotational viscometry and ABTS assay

    Directory of Open Access Journals (Sweden)

    TOPOLSKA Dominika

    2014-02-01

    Full Text Available Mineral waters from Bardejovske Kupele spa are natural, strongly mineralized, with healing effects. They are classified as hydrocarbonic - containing chloride and sodium - carbonic, cold, hypotonic, with a relatively high boric acid content. Potential anti-oxidative effects of curative waters from Bardejovske Kupele were investigated against the hyaluronan (HA degradation. High-molar-mass HA was exposed to the action of ascorbate and cupric ions, which initiate free-radical chain degradation. Time-dependent changes of dynamic viscosity (h of the HA solutions were monitored by rotational viscometry. The radical scavenging capacity of curative waters was determined by the ABTS assay. Despite a significantly high content of transition metal ions, especially iron, remarkable protective effects of the two curative spa waters were found, namely Alzbeta and Klara. Even though “Alzbeta´s“ iron content was 3.5-fold higher than “Klara´s“, “Alzbeta“ was shown to have better protective properties against the HA degradation compared to “Klara“. Bolus addition of ferric ions to the reaction system instead of the natural iron-containing curative water caused a significant HA degradation. The ABTS decolorization assay revealed that the curative spa waters were proven as poorly effective scavengers of the ABTS·+ cation radical.

  19. ESR study of the acid dissociation of NH protons. II. Cyclic peptide radicals and related radicals

    International Nuclear Information System (INIS)

    Free radicals formed by the reaction of OH or O- radicals with alicyclic compounds containing a peptide group (-CONH-) and structurally related compounds have been studied by the in situ radiolysis-steady state ESR method. Eight cyclic peptide radicals resulting from hydrogen abstraction from the C-H bond adjacent to the peptide group have been observed. They are divided into two groups on the basis of the skeletal structure of the radicals: greater than C-NH-CO- and greater than C-CO-NH-. In basic solutions significant changes occur in the ESR parameters of these radicals which can be interpreted in terms of the dissociation of the NH proton in a peptide group. The pK/sub a/ values for the NH proton dissociation have been determined to be in the range of 7.6 to 13.6 for eight cyclic peptide radicals from 5-methyl-2-pyrrolidinone, 2-pyrrolidinone, 2-pyrrolidone-5-carboxylic acid, hydantoin (for both first and second NH proton dissociations), 1-methylhydantoin, 2-thiohydantoin (second dissociation only), succinimide, and 2,5-piperazinedione (first dissociation only) and 10.9 for a related cyclic radical from 2-oxazolidone. These pK/sub a/ values are considerably lower than those for corresponding linear peptide radicals, partly because ?-electron density on the nitrogen atom decreases in cyclic peptide radicals with a more delocalized ?-electron system. Within each group of cyclicpeptide radicals with greater than C-NH-CO- or greater than C-CO-NH- the same trend of changes in ESR parameters was observed upon the dissociation of peptide proton

  20. El ABTS•+ agente oxidante de diversos compuestos químicos y su mecanismo de reciclado entre la lacasa y el sustrato / The ABTS•+ an oxidant agent of different chemical compounds and its recycling process between laccase susbtrate

    Scientific Electronic Library Online (English)

    M, Solís-Oba; E, Bárzana; M, García-Garibay; G, Viniegra-González.

    2007-12-01

    Full Text Available La lacasa comercial obtenida de Myceliophtera termophila y expresada sobre Aspergillus oryzae se empleó para producir un cation radical estable y muy activo del mediador químico ABTS (ácido 2,2'-azino-bis-(3-etillbenzotiazolin-6-sulfonico) con el fin de probar la factibilidad de emplearlo como un in [...] termediario para la oxidación de una variedad de compuestos aromáticos en ausencia de la enzima. Se demostró que el catión radical ABTS•+ por si mismo oxidó al azul índigo, ácido tánico, ácido gálico, azul brillante G, azul de Coomassie, naranja 7 y p-cresol. La reacción de oxidación reveló cambios importantes en sus espectros de absorción en la región del espectro visible. Se demostró también que la oxidación de estos compuestos por la mezcla de lacasa y ABTS se puede efectuar de forma cíclica, de tal forma que la velocidad de reacción fue 94 veces mayor para el índigo, 17 veces mayor para el azul brillante G, 34 veces mayor para el naranja 7 y 5 veces mayor para el p-cresol, comparado con usar el mediador o la lacasa en forma individual. Estos resultados muestran la factibilidad de un esquema de reciclado para la oxidación final de una variedad de compuestos orgánicos en los cuales la enzima no este directamente en contacto con el mismo y que se efectúe a través del mediador ABTS•+. Abstract in english The commercial enzyme laccase cloned from Myceliophtera termophila and expressed in Aspergillus oryzae was used to produce an active, stable and oxidized form of the chemical mediator ABTS (2,2'-azino-bis-(3-ethylbenzothiazoline-6-sulphonic acid)) in order to test the feasibility of using the monoca [...] tion ABTS•+ as a recyclable intermediate for the oxidation of a variety of aromatic chemicals in the absence of the enzyme. It was shown that ABTS•+, by itself, oxidized, indigo blue, tannic and galic acids, brilliant blue G, Coomassie blue, orange 7 and p-cresol. Oxidation was assessed by important changes in their visible absorption spectra. It was also shown that oxidation of these compounds by a mixture of ABTS and laccase can be done in a cyclic manner, such a way the oxidation rate was 94 times higher for indigo, 17 times for brilliant blue G, 34 times for orange 7 and 5 times higher for p-cresol compared with using the mediator or the laccase alone. Those results show the feasibility of a recycling scheme for the final oxidation of a wide variety of aromatic compounds in which the enzyme is not directly in contact with the compound but through the intermediate ABTS•+.

  1. Free radical scavenging activity of ethanolic extracts from herbs and spices commercialized in Brazil

    OpenAIRE

    Lilian Regina Barros Mariutti; Gisela Pizarro de Mattos Barreto; Neura Bragagnolo; Adriana Zerlotti Mercadante

    2008-01-01

    Ethanolic extracts from 23 different dried herbs and spices commercialized in Brazil were investigated for their free radical scavenging properties using the stable free radicals 2,2'-diphenyl-?-picrylhydrazyl (DPPH•) and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS•+), and Trolox as reference (TEAC) for both radicals. The kinetic curves for both radicals showed to follow the first order kinetics model and the decay rate constant (k obs) was calculated. For a...

  2. Free radical scavenging activity of Eagle tea and their flavonoids

    Directory of Open Access Journals (Sweden)

    Qiong Meng

    2012-06-01

    Full Text Available In this study, an online HPLC-DAD-MS coupled with 2,2?-azinobis (3-ethylbenzthiazoline-6-sulfonic acid diammonium salt (ABTS assay was employed for evaluating free radical scavenging activity of Eagle tea and their active components. Twenty-three chromatographic peaks were detected, and nineteen components had free radical scavenging activity. Among them, eight compounds were identified as flavonoids (hyperin, isoquercitrin, quercitrin, quercetin, kaempferol, catechins, chlorogenic acid and epicatechin based on MS data and standard chromatographic characters.

  3. Comparative Evaluation of the Radical-Scavenging Activities of Fucoxanthin and Its Stereoisomers

    Directory of Open Access Journals (Sweden)

    Yiping Zhang

    2014-02-01

    Full Text Available Fucoxanthin (Fuco is a characteristic carotenoid of brown seaweeds. In the present study, Fuco and its stereoisomers 9'Z-Fuco, 13Z- and 13'Z-Fuco were extracted from Laminaria japonica Aresch. They were isolated and purified by silica gel column chromatography, Sephadex LH-20, and reversed-phase HPLC. The radical-scavenging activities of the three stereoisomers were evaluated toward 1,1-diphenyl-2-picrylhydrazyl (DPPH radical, 2-2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid (ABTS radical, hydroxyl radical, and superoxide radical. The order of 1,1-diphenyl-2-picrylhydrazyl (DPPH radical-scavenging activity was 13Z- and 13'Z-Fuco > (all-E-Fuco > 9'Z-Fuco. The order of 2-2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid (ABTS and hydroxyl radical-scavenging activities were 9'Z-Fuco > (all-E-Fuco > 13Z-and 13'Z-Fuco. The order of superoxide radical-scavenging activity was 13Z- and 13'Z-Fuco > (all-E-Fuco > 9'Z-Fuco. The scavenging activities of Fuco and its stereoisomers toward the four radical types were all dose-dependent. The ABTS, DPPH, and superoxide radical-scavenging activities were all weaker than that of tocopherol (VE, while their hydroxyl radical-scavenging activities were stronger than that of VE. The results confirmed that Fuco and its stereoisomers have potent antioxidant activities.

  4. Comparative evaluation of the radical-scavenging activities of fucoxanthin and its stereoisomers.

    Science.gov (United States)

    Zhang, Yiping; Fang, Hua; Xie, Quanling; Sun, Jipeng; Liu, Rui; Hong, Zhuan; Yi, Ruizao; Wu, Hao

    2014-01-01

    Fucoxanthin (Fuco) is a characteristic carotenoid of brown seaweeds. In the present study, Fuco and its stereoisomers 9'Z-Fuco, 13Z- and 13'Z-Fuco were extracted from Laminaria japonica Aresch. They were isolated and purified by silica gel column chromatography, Sephadex LH-20, and reversed-phase HPLC. The radical-scavenging activities of the three stereoisomers were evaluated toward 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical, 2-2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radical, hydroxyl radical, and superoxide radical. The order of 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical-scavenging activity was 13Z- and 13'Z-Fuco > (all-E)-Fuco > 9'Z-Fuco. The order of 2-2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) and hydroxyl radical-scavenging activities were 9'Z-Fuco > (all-E)-Fuco > 13Z-and 13'Z-Fuco. The order of superoxide radical-scavenging activity was 13Z- and 13'Z-Fuco > (all-E)-Fuco > 9'Z-Fuco. The scavenging activities of Fuco and its stereoisomers toward the four radical types were all dose-dependent. The ABTS, DPPH, and superoxide radical-scavenging activities were all weaker than that of tocopherol (VE), while their hydroxyl radical-scavenging activities were stronger than that of VE. The results confirmed that Fuco and its stereoisomers have potent antioxidant activities. PMID:24549234

  5. Automatic flow system for sequential determination of ABTS scavenging capacity and Folin-Ciocalteu index: A comparative study in food products

    OpenAIRE

    Luís M. Magalhães; Segundo, Marcela A.; Reis, Salette; Lima, José L. F. C.; Tóth, Ildikó V.; Rangel, António O.S. S.

    2007-01-01

    In the present work, an automatic flow procedure for the sequential spectrophotometric determination of Folin-Ciocalteu reducing capacity (FC assay) and 2,2 -azinobis(3-ethylbenzothiazoline-6-sulfonic acid) radical cation (ABTS•+) scavenging capacity expressed as the trolox equivalent (TEAC assay) is proposed for a comparative study of antioxidant properties in food products. Exploiting the flexibility of flow management associated to the computer control offered by multisyringe flow injectio...

  6. Mechanism of protection of adenosine from sulphate radical anion and repair of adenosine radicals by caffeic acid in aqueous solution

    Indian Academy of Sciences (India)

    M Sudha Swaraga; L Charitha; M Adinarayana

    2005-07-01

    The photooxidation of adenosine in presence of peroxydisulphate (PDS) has been studied by spectrophotometrically measuring the absorbance of adenosine at 260 nm. The rates of oxidation of adenosine by sulphate radical anion have been determined in the presence of different concentrations of caffeic acid. Increase in [caffeic acid] is found to decrease the rate of oxidation of adenosine suggesting that caffeic acid acts as an efficient scavenger of $SO_4^{\\bullet-}$ and protects adenosine from it. Sulphate radical anion competes for adenosine as well as for caffeic acid. The quantum yields of photooxidation of adenosine have been calculated from the rates of oxidation of adenosine and the light intensity absorbed by PDS at 254 nm, the wavelength at which PDS is activated to sulphate radical anion. From the results of experimentally determined quantum yields ($\\phi_{\\text{exptl}}$) and the quantum yields calculated ($\\phi_{\\text{cal}}$) assuming caffeic acid acting only as a scavenger of $SO_4^{\\bullet-}$ show that $\\phi_{\\text{exptl}}$ values are lower than $\\phi_{\\text{cal}}$ values. The $f'$ values, which are experimentally found quantum yield values at each caffeic acid concentration and corrected for $SO_4^{\\bullet-}$ scavenging by caffeic acid, are also found to be greater than $\\phi_{\\text{exptl}}$ values. These observations suggest that the transient adenosine radicals are repaired by caffeic acid in addition to scavenging of sulphate radical anions.

  7. Pulse radiolytic study of the acid dissociation of OH protons in radicals related to salicylic acid

    International Nuclear Information System (INIS)

    The deprotonation of carboxylated benzosemiquinone radicals prepared by pulse radiolytic oxidation of dihydroxybenzoic acids has been examined by time-resolved absorption spectrophotometry. The pK/sub a/ for dissociation of the OH proton in 3-carboxyl-1,4-benzosemiquinone is found to be 6.47 or 2.4 units higher than that in the unsubstituted radical. This pK/sub a/ is, however, well below that of the OH proton in salicyclic acid (13.6) so that hydrogen bonding is appreciably decreased by the delocalization of the unpaired spin in this radical. Protonation of the basic form of the radical occurs at the diffusion-controlled rate. The rate constant for deprotonation by OH- is relatively low, 4.7 X 107 M-1 s-1, so that reaction with base becomes important only above pH 10. As a result this radical provides an excellent system for studying acid-base equilibration processes in near neutral solutions. Azide ion is shown to be an efficient catalyst which allows the acid-base equilibrium to be examined on the 10-?s time scale. Deprotonation is also catalyzed by the dihydroxybenzoic acid used as the radical source. Analogous studies on 4-carboxy-1,3-benzosemiquinone give the pK/sub a/ as 7.9. In spite of this high pK/sub a/, which indicates the rate constant for spontaneous dissociation of this radical to be > 103 s-1, the rate constant for deprotonation by OH-, 4.9 X 108 M-1 s-1, is considerably higher than in the case of 3-carboxy-1,4-benzosemiquinone

  8. Antioxidant activity of selected phenols estimated by ABTS and FRAP methods

    Directory of Open Access Journals (Sweden)

    Izabela Biskup

    2013-09-01

    Full Text Available Introduction: Phenols are the most abundant compounds in nature. They are strong antioxidants. Too high level of free radicals leads to cell and tissue damage, which may cause asthma, Alzheimer disease, cancers, etc. Taking phenolics with the diet as supplements or natural medicines is important for homeostasis of the organism. Materials and methods: The ten most popular water soluble phenols were chosen for the experiment to investigate their antioxidant properties using ABTS radical scavenging capacity assay and ferric reducing antioxidant potential (FRAP assay. Results and discussion: Antioxidant properties of selected phenols in the ABTS test expressed as IC50 ranged from 4.332 ?M to 852.713 ?M (for gallic acid and 4- hydroxyphenylacetic acid respectively. Antioxidant properties in the FRAP test are expressed as ?mol Fe2 /ml. All examined phenols reduced ferric ions at concentration 1.00 x 10-3 mg/ml. Both methods are very useful for determination of antioxidant capacity of water soluble phenols.

  9. Radical and Non-Radical Mechanisms for Alkane Oxidations by Hydrogen Peroxide?Trifluoroacetic Acid

    Energy Technology Data Exchange (ETDEWEB)

    Camaioni, Donald M.; Bays, J. Timothy; Shaw, Wendy J.; Linehan, John C.; Birnbaum, Jerome C.

    2001-02-09

    The oxidation of cyclohexane by the H2O2?trifluoroacetic acid system is revisited. Consistent with a previous report (Deno, N.; Messer, L. A. Chem. Comm. 1976, 1051), cyclohexanol forms initially but then esterifies to cyclohexyl trifluoroacetate. Small amounts of trans-1,2-cyclohexadiyl bis(trifluoroacetate) also form. Although these products form irrespective of the presence or absence of O2, dual mechanisms are shown to operate. In the absence of O2, the dominant mechanism is a radical chain reaction that is propagated by CF3• abstracting H from C6H12 and SH2 displacement of C6H11• on CF3CO2OH. The intermediacy of C6H11• and CF3• is inferred from production of CHF3 and CO2 along with cyclohexyl trifluoroacetate, or CDF3 when cyclohexane-d12 is used. In the presence of O2, fluoroform and CO2 are suppressed, the reaction rate slows, and the rate law approaches second order (first order in peracid and in C6H12). Trapping of cyclohexyl radicals by quinoxaline is inefficient except at elevated (75 °C) temperatures. Fluoroform and CO2, telltale evidence for the chain pathway, were not produced when quinoxaline was present in room temperature reactions. These observations suggest that a parallel, nonfree radical, oxenoid insertion mechanism dominates when O2 is present. A pathway is discussed in which a biradicaloid-zwiterionic transition state is attained by hydrogen transfer from alkane to peroxide oxygen with synchronous O?O bond scission.

  10. treatment with laccase and abts

    Directory of Open Access Journals (Sweden)

    Myrna Solís-Oba

    2008-01-01

    Full Text Available El sistema ABTS (ácido 2,2´-[3-etil benzotiazolin-6-sulfónico]-lacasa se empleó para decolorar tanto tela de mezclilla como una solución preparada de índigo. Después del tratamiento, la mezclilla adquirió un aspecto de usada, sin que las fibras mostraran evidencia de daño, mientras que la solución de índigo se decoloró. Adicionalmente, el análisis de la biodegradación de los desechos acuosos de la decoloración de la mezclilla y la solución decolorada control de índigo mostraron que, en ambos casos el agua residual fue fácilmente biodegradada tanto aeróbica como anaeróbicamente, mientras que la solución control de índigo requirió de 5 días para biodegradarse aeróbicamente y no sufrió ningún cambio en el sistema anaeróbico. El ABTS oxidado ó la lacasa por sí solos no decoloraron la mezclilla ni la solución de índigo bajo las mismas condiciones experimentales en que se empleó la combinación de ambos ABTS-lacasa. Esto se explica porque, durante la reacción de decoloración, el mediador se recicla varias veces entre la enzima y el colorante, de tal forma que en 30 minutos, una molécula de ABTS oxida 800 moléculas de índigo, además la velocidad de decoloración fue dos órdenes de magnitud mayor que la velocidad cuando se empleó el ABTS ó la enzima en forma individual.

  11. Matrix isolation of free radicals from myo-inositol formed by H. reaction in acidic glasses

    Energy Technology Data Exchange (ETDEWEB)

    Krieger, J.; Huettermann, J. (Regensburg Univ. (Germany, F.R.). Inst. fuer Biophysik und Physikalische Biochemie)

    1983-08-01

    Reaction of H radical-atoms produced photolytically in acid glasses with myo-inositol initially results in the formation of three different radical intermediates, two of which give rise to discernable hyperfine interactions in electron spin-resonance spectra whereas one is a non-specific singlet. The two former species correspond to loss of H radicals from all carbon-positions of the polyalcohol. Both intermediates transform into the same secondary radical upon thermal annealing by water elimination.

  12. EPR study of gamma induced radicals in amino and iminodiacetic acid derivatives

    Scientific Electronic Library Online (English)

    Murat, Aydin; M. Halim, Baskan; M. Y., Emre Osmanoglu.

    2009-09-01

    Full Text Available In this study, electron paramagnetic resonance spectroscopy was used to investigate free radicals formed in gamma irradiated L-glutamine hydrochloride, iminodiacetic acid hydrochloride and N-(2-hyroxyethyl) iminodiacetic acid powders. The free radicals produced in L-glutamine hydrochloride powders w [...] ere attributed to the CH2CHCOOH radical; and those in iminodiacetic acid hydrochloride and N-(2-hyroxyethyl) iminodiacetic acid powders to the HNCHCH2(COOH)2 and HOCH2CH2NCHCH2(COOH)2, respectively. The g-values of the radicals and the hyperfine structure constants of the free electron with the environmental protons and 14N nucleus were determined. The samples were not displayed before they were not irradiated. The free radicals were found stable at room temperature for more than six months. Some spectroscopic properties and suggestions concerning possible structure of the radicals are discussed in this paper.

  13. Unexpected reactivity of amidogen radical in the gas phase degradation of nitric acid.

    Science.gov (United States)

    Anglada, Josep M; Olivella, Santiago; Solé, Albert

    2014-05-14

    The gas phase reaction between nitric acid and amidogen radical has been investigated employing high level quantun-mechanical electronic structure methods and variational transition state theory kinetic calculations. Our results show that the reaction proceeds through a proton coupled electron transfer mechanism with a rate constant of 1.81 × 10(-13) cm(3)·molecule(-1)·s(-1) at 298 K. This value is similar to the rate constants for the reactions of hydroxyl radical with either ammonia or nitric acid. An analysis of these data in the context of the chemistry of the atmosphere suggests that the amidogen radical, formed in the oxidation of ammonia by hydroxyl radical, reacts with nitric acid regenerating ammonia. On the basis of these findings, we propose a potential new catalytic-like cycle which couples the oxidation of ammonia by hydroxyl radical and the reaction of nitric acid with amidogen radical in the Earth's atmosphere. PMID:24792039

  14. Reactivity of phenolic compounds towards free radicals under in vitro conditions.

    Science.gov (United States)

    Mathew, Sindhu; Abraham, T Emilia; Zakaria, Zainul Akmar

    2015-09-01

    The free radical scavenging activity and reducing power of 16 phenolic compounds including four hydroxycinnamic acid derivatives namely ferulic acid, caffeic acid, sinapic acid and p-coumaric acid, benzoic acid and its derivatives namely protocatechuic acid, gallic acid and vanillic acid, benzene derivatives namely vanillin, vanillyl alcohol, veratryl alcohol, veratraldehyde, pyrogallol, guaiacol and two synthetic antioxidants, butylated hydroxy anisole (BHA) and propyl gallate were evaluated using 1,1-Diphenyl-2-picrylhydrazyl radical (DPPH(•)), 2,2'-Azinobis-3- ethylbenzothiazoline-6-sulfonic acid radical (ABTS(+•)), Hydroxyl radical ((•)OH) and Superoxide radical (O2 (•-)) scavenging assays and reduction potential assay. By virtue of their hydrogen donating ability, phenolic compounds with multiple hydroxyl groups such as protocatechuic acid, pyrogallol, caffeic acid, gallic acid and propyl gallate exhibited higher free radical scavenging activity especially against DPPH(•) and O2 (•-). The hydroxylated cinnamates such as ferulic acid and caffeic acid were in general better scavengers than their benzoic acid counter parts such as vanillic acid and protocatechuic acid. All the phenolic compounds tested exhibited more than 85 % scavenging due to the high reactivity of the hydroxyl radical. Phenolic compounds with multiple hydroxyl groups also exhibited high redox potential. Exploring the radical scavenging and reducing properties of antioxidants especially those which are found naturally in plant sources are of great interest due to their protective roles in biological systems. PMID:26344993

  15. Comparative Evaluation of the Radical-Scavenging Activities of Fucoxanthin and Its Stereoisomers

    OpenAIRE

    Yiping Zhang; Hua Fang; Quanling Xie; Jipeng Sun; Rui Liu; Zhuan Hong; Ruizao Yi; Hao Wu

    2014-01-01

    Fucoxanthin (Fuco) is a characteristic carotenoid of brown seaweeds. In the present study, Fuco and its stereoisomers 9'Z-Fuco, 13Z- and 13'Z-Fuco were extracted from Laminaria japonica Aresch. They were isolated and purified by silica gel column chromatography, Sephadex LH-20, and reversed-phase HPLC. The radical-scavenging activities of the three stereoisomers were evaluated toward 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical, 2-2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) ra...

  16. Reactions of thiyl radicals from thiols and disulphides with antioxidants. A pulse radiolytic study (Preprint No. RC-5)

    International Nuclear Information System (INIS)

    Absolute rate constants for the reactions of thiyl radicals generated from a variety of thiols and disulphides with 2,2'-azino bis-(3-ethyl-benzthiazoline-6-sulphonate) (ABTS) and ascorbic acid (AH-) using pulse radiolysis technique have been evaluated. (author). 3 refs

  17. Mechanism and kinetics in reactions of caffeic acid with radicals by pulse radiolysis and calculation

    International Nuclear Information System (INIS)

    The interaction of caffeic acid with eaq-, (CH3)2(OH) CCH2·, CO2·-, H·, ·OH and N3· radicals were studied by ?-, pulse radiolysis and molecular orbital calculation. UV-visible spectra of electron/·OH adducts, semi-quinone radicals of caffeic ions, and the stable products from the reactions were derived. The rate constants were determined. The attacked sites and the most favorable structures of the transient radicals were predicted. Reaction mechanisms were proposed. (author)

  18. Evaluation of the Antiradical Properties of Phenolic Acids

    Directory of Open Access Journals (Sweden)

    Olga Koroleva

    2014-09-01

    Full Text Available Antioxidant capacity (AOC against peroxyl radical and 2,2'-azino-bis-(3-ethylbenzothiazoline-6-sulphonic acid diammonium salt (ABTS radical cation was measured for a series of p-hydroxybenzoic (HB and p-hydroxycinnamic (HC acids at different pH. Quantum-chemical computation was performed using Gaussian 3.0 software package to calculate the geometry and energy parameters of the same compounds. Significant correlations were revealed between AOC and a number of calculated parameters. The most significant AOC descriptors for the studied compounds against peroxyl radical were found to be HOMO energy, rigidity (? and Mulliken charge on the carbon atom in m-position to the phenolic hydroxyl. The most significant descriptor of the antioxidant properties against the ABTS radical cation at ?? 7.40 is electron transfer enthalpy from the phenolate ion. The mechanism of AOC realization has been proposed for HB and HC acids against both radicals.

  19. Free radicals in dicarboxylic acids: an e.s.r. study of radical conversions in ?-irradiated single crystals of glutaric acid and glutaric-2,2,4,4-d4 acid

    International Nuclear Information System (INIS)

    The ?-radiation-induced free radicals in single crystals of glutaric acid and glutaric-2,2,4,4-d4 acid were studied in the temperature range 77-300 K by e.s.r. techniques. At 77 K the decarboxylation radical and the anion are stabilized. At higher temperatures the decarboxylation radical is found to be converted into a hydrogen abstraction radical with an activation energy of 6.3 +- 0.5 kcal/mole for the non-deuterated crystal. This radical is stable at room temperature. The anion seems to be converted to a unidentified intermediate radical which in turn is converted to the ?-acyl radical. An analysis of the g-value anisotropy and of the 13C hyperfine splitting variation for this radical in the deuterated crystal is consistent with the assigned radical structure. By heat treatment the ?-acyl radical is converted to another form of the hydrogen abstraction radical with an activation energy of 9.6 +- 0.6 kcal/mole in the deuterated crystal. U.V.-light (lambda= 254 nm) transforms one of the room temperature radicals into the other. (author)

  20. Free radicals in dicarboxylic acids: an e.s.r. study of ?-irradiated single crystals of glutaric acid at 77 K

    International Nuclear Information System (INIS)

    Electron spin resonance techniques were used to study the ?-radiation-induced free radicals in single crystals of glutaric acid in the temperature range from 77 K to 300 K. Three different radicals are stabilized at 77 K. The decarboxylation radical is the dominant species and the other two radicals are assigned to the anion and to the substituted acetyl ?-radical. When the temperature of the crystal was raised, these radicals disappeared and the previously studied room temperature radicals appeared. E.S.R.-data and the results from semi-empirical INDO-MO calculations were compared in order to elucidate the structures of the various radicals. (author)

  1. Evaluation of the Antiradical Properties of Phenolic Acids

    OpenAIRE

    Olga Koroleva; Anna Torkova; Ilya Nikolaev; Ekaterina Khrameeva; Tatyana Fedorova; Mikhail Tsentalovich; Ryszard Amarowicz

    2014-01-01

    Antioxidant capacity (AOC) against peroxyl radical and 2,2'-azino-bis-(3-ethylbenzothiazoline-6-sulphonic acid) diammonium salt (ABTS) radical cation was measured for a series of p-hydroxybenzoic (HB) and p-hydroxycinnamic (HC) acids at different pH. Quantum-chemical computation was performed using Gaussian 3.0 software package to calculate the geometry and energy parameters of the same compounds. Significant correlations were revealed between AOC and a number of calculated parameters. The mo...

  2. ANTIOXIDANT PROPERTIES OF LIGNANS AND FERULIC ACID FROM THE RESINOUS EXUDATE OF LARREA NITIDA

    Directory of Open Access Journals (Sweden)

    RENÉ TORRES

    2003-09-01

    Full Text Available From the resinous exudate of twigs end leaves of Larrea nitida, two lignans nor isoguaiacine 1 and meso-nor-dihydroguaiaretic acid 2 and ferulic acid 3 were isolated. The antioxidant activities of resin and pure compounds were assesed by bleaching of the ABTS derived radical-cation

  3. ANTIOXIDANT PROPERTIES OF LIGNANS AND FERULIC ACID FROM THE RESINOUS EXUDATE OF LARREA NITIDA

    Scientific Electronic Library Online (English)

    RENÉ, TORRES; FRANCISCO, URBINA; CLAUDIA, MORALES; BRENDA, MODAK; FRANCO DELLE, MONACHE.

    2003-09-01

    Full Text Available From the resinous exudate of twigs end leaves of Larrea nitida, two lignans nor isoguaiacine 1 and meso-nor-dihydroguaiaretic acid 2 and ferulic acid 3 were isolated. The antioxidant activities of resin and pure compounds were assesed by bleaching of the ABTS derived radical-cation [...

  4. ANTIOXIDANT PROPERTIES OF LIGNANS AND FERULIC ACID FROM THE RESINOUS EXUDATE OF LARREA NITIDA

    OpenAIRE

    RENÉ TORRES; FRANCISCO URBINA; CLAUDIA MORALES; BRENDA MODAK; FRANCO DELLE MONACHE

    2003-01-01

    From the resinous exudate of twigs end leaves of Larrea nitida, two lignans nor isoguaiacine 1 and meso-nor-dihydroguaiaretic acid 2 and ferulic acid 3 were isolated. The antioxidant activities of resin and pure compounds were assesed by bleaching of the ABTS derived radical-cation

  5. Picosecond Pulse Radiolysis of Highly Concentrated Phosphoric Acid Solutions: Mechanism of Phosphate Radical Formation.

    Science.gov (United States)

    Ma, Jun; Schmidhammer, Uli; Mostafavi, Mehran

    2015-06-18

    Eight solutions containing phosphoric acid with concentrations ranging from 2 mol L(-1) to neat acid have been studied by picosecond pulse radiolysis. The absorbance of the secondary radical H2PO4(•) formed within 7 ps of the electron pulse is observed using pulse-probe method in the visible. Kinetic analysis shows that the radicals of phosphoric acid are formed via two mechanisms: direct electron detachment and oxidation by the radical cation of water, H2O(•+). On the basis of molar extinction coefficient value of 1850 L mol(-1) cm(-1), at 15 ps the radiolytic yield of H2PO4(•) formation by direct energy absorption is 3.7 ± 0.1 × 10(-7) mol J(-1) in neat phosphoric acid. In highly concentrated phosphoric acid solutions, the total yield of phosphate radical at 15 ps exhibits an additional contribution that can be explained by electron transfer from phosphoric acid to H2O(•+). The efficiency of the electron transfer to this strongly oxidizing species in phosphoric acid solutions is lower compared with the one in sulfuric acid solutions. Two explanations are given to account for a relatively low efficiency of H2O(•+) scavenging in concentrated phosphoric acid solutions. PMID:25176139

  6. Free radicals during hypertriglyceridemia treatment by N-3 fatty acids.

    Czech Academy of Sciences Publication Activity Database

    Zeman, M.; Stopka, Pavel; Vecka, M.; Žák, A.

    2006-01-01

    Ro?. 7, ?. 3 (2006), s. 292. ISSN 1567-5688 R&D Projects: GA MZd NR8806 Institutional research plan: CEZ:AV0Z40320502 Keywords : free radicals Subject RIV: CA - Inorganic Chemistry Impact factor: 5.875, year: 2006

  7. Identification of free radicals induced by gamma irradiation in amino acid derivatives

    Scientific Electronic Library Online (English)

    Murat, Aydin.

    2010-09-01

    Full Text Available Powders of N- acetyl- L- leucine and N- methyl- L- glutamic acid were gamma irradiated and the free radicals formed were investigated at room temperature by electron paramagnetic resonance technique. The free radicals formed in compounds were attributed to the (CH3)2CCH2CH(NHCOCH3)COOH and HOOCCH2CH [...] 2C (NHCH3)COOH radicals respectively. Both radicals are very stable and we could observe them for five months without almost intensity diminution at room temperature. The g values of the radicals and the hyperfine structure constants of the free electron with nearby protons and 14N nucleus were determined. The results were found to be in good agreement with the existing literature data.

  8. Study of the structure of free radicals in gamma: irradiated amino acid derivatives

    Scientific Electronic Library Online (English)

    Murat, Aydin.

    2010-12-01

    Full Text Available Electron paramagnetic resonance spectroscopy has been used for the study of the free radicals produced in the powders of L-arginine monohydrochloride, ala-ala and DL-?-leucine gamma-irradiated at room temperature. The structures of the radicals formed in compounds were determined as NH2(NH)NHCHCH2CH [...] 2CH(NH2)COOH, CH3CHCOOH and (CH3)2C CH(NH2)CH2COOH respectively. The paramagnetic species were found to be stable at room temperature more than three months. It was determined that unpaired electron interacted with nearby protons and 14N nucleus in these radicals. The g values of the radicals and the hyperfine structure constants of the free electron were also measured. These results were compared with the earlier studies in amino acid and derivatives radicals and discussed.

  9. OH-radical induced degradation of hydroxybenzoic- and hydroxycinnamic acids and formation of aromatic products-A gamma radiolysis study

    International Nuclear Information System (INIS)

    The OH-radical induced degradation of hydroxybenzoic acids (HBA), hydroxycinnamic acids (HCiA) and methoxylated derivatives, as well as of chlorogenic acid and rosmarinic acid was studied by gamma radiolysis in aerated aqueous solutions. Primary aromatic products resulting from an OH-radical attachment to the ring (hydroxylation), to the position occupied by the methoxyl group (replacement -OCH3 by -OH) as well as to the propenoic acid side chain of the cinnamic acids (benzaldehyde formations) were analysed by HPLC-UV and LC-ESI-MS. A comparison of the extent of these processes is given for 3,4-dihydroxybenzoic acid, vanillic acid, isovanillic acid, syringic acid, cinnamic acid, 4-hydroxycinnamic acid, caffeic acid, ferulic acid, isoferulic acid, chlorogenic acid, and rosmarinic acid. For all cinnamic acids and derivatives benzaldehydes were significant oxidation products. With the release of caffeic acid from chlorogenic acid the cleavage of a phenolic glycoside could be demonstrated. Reaction mechanisms are discussed.

  10. OH-radical induced degradation of hydroxybenzoic- and hydroxycinnamic acids and formation of aromatic products—A gamma radiolysis study

    Science.gov (United States)

    Krimmel, Birgit; Swoboda, Friederike; Solar, Sonja; Reznicek, Gottfried

    2010-12-01

    The OH-radical induced degradation of hydroxybenzoic acids (HBA), hydroxycinnamic acids (HCiA) and methoxylated derivatives, as well as of chlorogenic acid and rosmarinic acid was studied by gamma radiolysis in aerated aqueous solutions. Primary aromatic products resulting from an OH-radical attachment to the ring (hydroxylation), to the position occupied by the methoxyl group (replacement -OCH 3 by -OH) as well as to the propenoic acid side chain of the cinnamic acids (benzaldehyde formations) were analysed by HPLC-UV and LC-ESI-MS. A comparison of the extent of these processes is given for 3,4-dihydroxybenzoic acid, vanillic acid, isovanillic acid, syringic acid, cinnamic acid, 4-hydroxycinnamic acid, caffeic acid, ferulic acid, isoferulic acid, chlorogenic acid, and rosmarinic acid. For all cinnamic acids and derivatives benzaldehydes were significant oxidation products. With the release of caffeic acid from chlorogenic acid the cleavage of a phenolic glycoside could be demonstrated. Reaction mechanisms are discussed.

  11. OH-radical induced degradation of hydroxybenzoic- and hydroxycinnamic acids and formation of aromatic products-A gamma radiolysis study

    Energy Technology Data Exchange (ETDEWEB)

    Krimmel, Birgit; Swoboda, Friederike [University of Vienna, Department of Nutritional Sciences, Section Radiation Biology (Austria); Solar, Sonja, E-mail: sonja.solar@univie.ac.a [University of Vienna, Department of Nutritional Sciences, Section Radiation Biology (Austria); Reznicek, Gottfried [Department of Pharmacognosy, Althanstrasse 14, A-1090 Vienna (Austria)

    2010-12-15

    The OH-radical induced degradation of hydroxybenzoic acids (HBA), hydroxycinnamic acids (HCiA) and methoxylated derivatives, as well as of chlorogenic acid and rosmarinic acid was studied by gamma radiolysis in aerated aqueous solutions. Primary aromatic products resulting from an OH-radical attachment to the ring (hydroxylation), to the position occupied by the methoxyl group (replacement -OCH{sub 3} by -OH) as well as to the propenoic acid side chain of the cinnamic acids (benzaldehyde formations) were analysed by HPLC-UV and LC-ESI-MS. A comparison of the extent of these processes is given for 3,4-dihydroxybenzoic acid, vanillic acid, isovanillic acid, syringic acid, cinnamic acid, 4-hydroxycinnamic acid, caffeic acid, ferulic acid, isoferulic acid, chlorogenic acid, and rosmarinic acid. For all cinnamic acids and derivatives benzaldehydes were significant oxidation products. With the release of caffeic acid from chlorogenic acid the cleavage of a phenolic glycoside could be demonstrated. Reaction mechanisms are discussed.

  12. Measurement of antioxidant activity with trifluoperazine dihydrochloride radical cation

    Scientific Electronic Library Online (English)

    M.N., Asghar; I.U., Khan.

    2008-06-01

    Full Text Available A novel, rapid and cost-effective trifluoperazine dihydrochloride (TFPH) decolorization assay is described for the screening of antioxidant activity. A chromogenic reaction between TFPH and potassium persulfate at low pH produces an orange-red radical cation with maximum absorption at 502 nm in its [...] first-order derivative spectrum. TFPH was dissolved in distilled water to give a 100 mM solution. The TFPH radical cation solution was made by reacting 0.5 mL of the solution with K2S2O8 (final concentration: 0.1 mM) and diluting to 100 mL with 4 M H2SO4 solution. A linear inhibition of color production was observed with linearly increasing amounts of antioxidants, with correlation coefficients (R²) ranging from 0.999 to 0.983. The antioxidant capacity of standard solutions of an antioxidant was evaluated by comparing with the inhibition curve using Trolox as the standard. Comparison of antioxidant capacity determined with this newly developed TFPH assay and with the well-known 2,2'-azinobis-[3-ethylbenzthiazoline-6-sulfonic acid] (ABTS)-persulfate decolorization assay indicated the efficacy and sensitivity of the procedure. The proposed assay is less expensive (costs about US$4 per 100 assays) and requires only 20 min for preparation of radical cation solution in comparison with ABTS assay, in which almost 12-16 h are required for preparation of a stable ABTS radical cation solution. The present assay has the advantage over ABTS assay that it can be used to measure the antioxidant activity of the samples, which are naturally found at a pH as low as 1, because the radical cation itself has been stabilized at low pH.

  13. Matrix isolation of free radicals from myo-inositol formed by H. reaction in acidic glasses

    International Nuclear Information System (INIS)

    Reaction of Hradical-atoms produced photolytically in acid glasses with myo-inositol initially results in the formation of three different radical intermediates, two of which give rise to discernable hyperfine interactions in electron spin-resonance spectra whereas one is a non-specific singlet. The two former species correspond to loss of Hradicals from all carbon-positions of the polyalcohol. Both intermediates transform into the same secondary radical upon thermal annealing by water elimination. (author)

  14. E.s.r. of spin-trapped radicals in ?-irradiated polycrystalline amino acids, N-acetyl amino acids and dipeptides

    International Nuclear Information System (INIS)

    The radicals produced in several polycrystalline amino acids, N-acetyl amino acids and dipeptides by ?-radiolysis at room temperature were investigated by spin-trapping. After irradiation in the solid state, the samples were dissolved in aqueous solutions of t-nitrosobutane and the trapped radicals identified by e.s.r. For ?-amino acids, deamination radicals were found, and in some cases H-abstraction radicals were also observed. No decarboxylation radicals could be detected. For N-acetyl amino acids, except for N-acetylglycine, the major radical was the decarboxylation radical. For N-acetylglycine the H-abstraction radical from the glycine residue was observed. For dipeptides of the type x-glycine, the radical formed by removal of H from the ?-carbon of the carboxyl-terminal residue was always spin-trapped. Some primary deamination radicals and minor amounts of decarboxylation radicals could also be observed. For dipeptides of the type x-alanine, glycine-x and alanine-x, the decarboxylation radical was always the major spin-trapped radical. Some primary and secondary deamination radicals were also detected. (author)

  15. Diagnosis of hydroxyl radicals and the treatment of Acid Orange ? in negative pulsed discharge

    International Nuclear Information System (INIS)

    A kind of device supplied with negative pulsed high voltage was designed for water treatment. The nozzle discharge electrode was supplied with high voltage and the cylinder wall of the treatment chamber was grounded. Since the non-thermal plasma, especially, hydroxyl radicals played the dominant role in removing pollutants in the water by discharge plasma, hydroxyl radicals were measured in the negative pulsed discharge process by the optical emission spectroscopy (OES) effects of the repetition rate and the peak value of the pulsed discharge on the hydroxyl radicals' production and the decomposition rate of the Acid Orange ? solution were studied.

  16. Free radical initiation in proteins and amino acids by ionizing and ultraviolet radiations and lipid oxidation. Part III: free radical transfer from oxidizing lipids

    International Nuclear Information System (INIS)

    Parallels and similarities in chemical and functional damage to proteins by ionizing and uv radiations and oxidizing lipids have been recognized for some time. However, only recently have oxidizing lipids been shown directly by electron spin resonance to be radiomimetic also in their capacity for protein free radical production. Accordingly, this review is a detailed comparison of gamma-radiation, uv radiation, and lipid oxidation for what is presently known concerning (1) the specific modes of energy deposition and free radical formation, (2) the free radicals formed in proteins and amino acids, and (3) the typical damage correlating with these radicals

  17. Antioxidative properties of tronchuda cabbage (Brassica oleracea L. var. costata DC) external leaves against DPPH, superoxide radical, hydroxyl radical and hypochlorous acid

    OpenAIRE

    Vrchovska, V.; Sousa, C; Valentão, P; Ferreres, F.; J. A. Pereira; Seabra, R.M.; Andrade, P.B.

    2006-01-01

    The ability of the aqueous extract of tronchuda cabbage (Brassica oleracea L. var. costata DC) external leaves to act as a scavenger of DPPH- and reactive oxygen species (superoxide radical, hydroxyl radical and hypochlorous acid) was investigated. A phytochemical study was also undertaken, and thirteen phenolic compounds and five organic acids were identified and quantified. Tronchuda cabbage extracts exhibited antioxidant capacity in a concentration-dependent manner in all assays, ...

  18. Concerted effects in the reaction of ·OH radicals with aromatics: radiolytic oxidation of salicylic acid

    International Nuclear Information System (INIS)

    Liquid chromatographic and capillary electrophoretic studies have been used to resolve the products produced in the radiolytic oxidation of salicylic acid in aqueous solution. These studies have shown that, as in the case of phenol, ·OH radicals preferentially add to the positions ortho and para to the OH substituent. However, in contrast to its reaction with phenol, addition at the ortho position is favored over addition at the para position. Because ·OH radical is a strong electrophile this difference suggests that the electron population at the ortho position in the salicylate anion is enhanced as a result of the hydrogen bonding in salicylic acid

  19. Reactions of clofibric acid with oxidative and reductive radicals—Products, mechanisms, efficiency and toxic effects

    International Nuclear Information System (INIS)

    The degradation of clofibric acid induced by hydroxyl radical, hydrated electron and O2??/HO2? reactive species was studied in aqueous solutions. Clofibric acid was decomposed more effectively by hydroxyl radical than by hydrated electron or O2??/HO2?. Various hydroxylated, dechlorinated and fragmentation products have been identified and quantified. A new LC–MS method was developed based on 18O isotope labeling to follow the formation of hydroxylated derivatives of clofibric acid. Possible degradation pathways have been proposed. The overall degradation was monitored by determination of sum parameters like COD, TOC and AOX. It was found that the organic chlorine degrades very effectively prior to complete mineralization. After the treatment no toxic effect was found according to Vibrio fischeri tests. However, at early stages some of the reaction products were more harmful than clofibric acid. - Highlights: • Clofibric acid is effectively degraded by OH radical. • Main primary and secondary products are hydroxylated and dihydroxylated phenyl type derivatives of clofibric acid. • In air saturated aqueous solutions O2 plays an important role in decomposition of the aromatic structure. • A new LC–MS method with 18O-labeling was developed. • Early stage reaction products are more toxic to bacteria Vibrio fischeri than clofibric acid

  20. Radical Scavenging Capacity of Methanolic Phillyrea latifolia L. Extract: Anthocyanin and Phenolic Acids Composition of Fruits

    Directory of Open Access Journals (Sweden)

    Naciye Erkan

    2013-01-01

    Full Text Available Radical scavenging capacity of a crude methanolic extract from the fruits of Phillyrea latifolia L., commonly known as green olive tree or mock privet, was investigated with reference to anthocyanin standards, as flavonoids, and phenolic acid standards, as phenylpropanoids. Characterization with high performance liquid chromatography-diode array detection (HPLC-DAD indicated the presence of keracyanin, kuromanin, cyanidin, ferulic acid, caffeic acid and rosmarinic acid at amounts of 289.1, 90.4, 191.4, 225.2, 221.2 and 190.1 mg/100 g fresh weight (FW of fruits, respectively. Chlorogenic and p-coumaric acids were found to exist in lower amounts. Trolox equivalent antioxidant capacity (TEAC and IC50 values of the plant extract were found to be 1.8 mM Trolox equivalents (TE/g FW of fruits and 69.4 µg/mL, respectively, indicating the close radical scavenging activity of the extract to those of keracyanin and p-coumaric acid. The crude methanolic P. latifolia L. fruit extract was seen to be fairly potent in radical scavenging. Total phenolic content (TPC of the plant extract was found to be 1652.9 mg gallic acid equivalent (GAE/100 g FW of fruits.

  1. Spectral and kinetic characteristics of the ?-propionic acid methyl ester radical in cyclohexane and water

    International Nuclear Information System (INIS)

    The ?-propionic acid methyl ester radical was produced in dissociative electron capture reaction of 2-chloropropionic acid methyl ester. The absorption maxima of the radical are at 310 and 300 nm in cyclohexane and water with extinction coefficients of 440±50 and 400±50 mol-1 dm3 cm-1. The second order decay rate parameter in water is (2.3±0.5)x109 mol-1 dm3 s-1. The peroxy radicals have the characteristics: ?max=265-270 nm, ?max=700-900 mol-1 dm3 cm-1 and 2k = (7±2) x 108 mol-1 dm3 s-1. (author) 6 refs.; 4 figs.; 1 tab

  2. Kinetics of free radical decay reactions in lactic acid homo and copolymers irradiated to sterilization dose

    International Nuclear Information System (INIS)

    The kinetics of free radical decay reactions of poly(L-Lactic acid), poly(DL-Lactic acid) and random copolymer of lactic and glycolic acid have been investigated for decays taking place in air and in vacuum. The change in ESR lines of ?-irradiated polymers have been followed over a long time period. The decay has been found to follow neither simple first-order nor second-order kinetics. Various kinetic approaches including composite first or second-order mechanisms and diffusion-controlled first or second-order equations were determined to be also unsatisfactory. The decay of radicals in bulk irradiated lactic acid homo and copolymers was found to be best described when the second-order non-classical equation with time dependent rate constant approach was used. (Author)

  3. Effect of water and ethanol radicals on the protein part of human hemoglobin. Pt. 2. Damage to amino acid residues

    International Nuclear Information System (INIS)

    This work is devoted to the effect of interactions of water and ethanol radicals with human hemoglobin (Hb) amino acid residues. The OH radicals caused the greatest destruction of human hemoglobin amino acid residues. Among them the most sensitive to irradiation were cysteine tryptophan and histidine residues. (author). 11 refs, 2 tabs

  4. Scavenging of superoxide radical anion with hydroxy-cinnamic acid derivatives. A pulse radiolysis study

    International Nuclear Information System (INIS)

    Using pulse radiolysis techniques the reaction rate constants of hydroxy-cinnamic acid derivatives (HCAD) with superoxide radical anion (O2-.) were obtained by competition reaction kinetic analysis. The reacting mechanism was proposed based on the HPLC analysis of final products and UV spectrophotometry

  5. Enhancing the efficacy of photodynamic cancer therapy by radicals from plant auxin (indole-3-acetic acid).

    OpenAIRE

    Folkes, LK; Wardman, P

    2003-01-01

    Indole-3-acetic acid (plant auxin) has low toxicity but dramatically enhances the killing of mammalian cells on illuminating phenothiazinium dyes with red light. Suitable dyes include toluidine blue, used in cancer diagnosis because of localization in tumors, and methylene blue, used in experimental photodynamic therapy of cancer. The photosensitized oxidation of indole acetic acid forms a free radical that fragments in microseconds, forming reactive cytotoxins. Unlike conventional photodynam...

  6. A Comparative Study of the Radical-scavenging Activity of the Phenolcarboxylic Acids Caffeic Acid, p-Coumaric Acid, Chlorogenic Acid and Ferulic Acid, With or Without 2-Mercaptoethanol, a Thiol, Using the Induction Period Method

    Directory of Open Access Journals (Sweden)

    Seiichiro Fujisawa

    2008-10-01

    Full Text Available Phenolcarboxylic acid antioxidants do not act in vivo as radical-scavengers in isolation, but rather together with GSH (glutathione, a coantioxidant, they constitute an intricate antioxidant network. Caffeic acid, p-coumaric acid, ferulic acid and chlorogenic acid with or without 2-mercaptoethanol (ME, as a substitute for GSH, was investigated by the induction period (IP method for polymerization of methyl methacrylate (MMA initiated by thermal decomposition of 2,2'-azobisisobutyronitrile (AIBN, a source of alkyl radicals, R. and benzoyl peroxide (BPO, a source of peroxy radicals, PhCOO. using differential scanning calorimetry (DSC. Upon PhCOO. radical scavenging, the stoichiometric factors (n, number of free radical trapped by one mole of antioxidant for caffeic acid, ferulic acid, p-coumaric acid and chlorogenic acid were 2.4, 1.8, 1.7 and 0.9, whereas upon R. radical scavenging, the corresponding values were 1.3, 1.2, 1.0 and 0.8, respectively. Antioxidants with n values close to 2 suggest the stepwise formation of semiquinone radicals and quinones. By contrast, those with n values close to 1 suggest the formation of dimers after single-electron oxidation, possibly due to recombination of corresponding aryloxy radicals. The ratio of the rate constant of inhibition to that of propagation (kinh/kp declined in the order chlorogenic acid > p-coumaric acid > ferulic acid > caffeic acid. The ratio of the observed IP for the phenolcarboxylic acid/2-mercapto-ethanol (ME mixture (1:1 molar ratio (A to the calculated IP (the simple sum of phenol acid antioxidant and ME (B was investigated. Upon R. scavenging, the caffeic acid or p-coumaric acid/ME mixture was A/B > 1, particularly the former was 1.2, suggesting a synergic effect. By contrast, upon PhCOO. scavenging, the corresponding mixture was A/B < 1, particularly the latter was 0.7, suggesting an antagonistic effect. Upon both radicals scavenging, the A/B for the ferulic acid or chlorogenic acid/ME mixture was approximately 1. The reported beneficial antioxidant, anti-inflammatory and anticancer effects of caffeic acid and p-coumaric acid may be related to their prooxidant-antioxidant balance in the presence of GSH.

  7. Scavenging of free-radical metabolites of aniline xenobiotics and drugs by amino acid derivatives: toxicological implications of radical-transfer reactions.

    Science.gov (United States)

    Michail, Karim; Baghdasarian, Argishti; Narwaley, Malyaj; Aljuhani, Naif; Siraki, Arno G

    2013-12-16

    We investigated a novel scavenging mechanism of arylamine free radicals by poly- and monoaminocarboxylates. Free radicals of arylamine xenobiotics and drugs did not react with oxygen in peroxidase-catalyzed reactions; however, they showed marked oxygen uptake in the presence of an aminocarboxylate. These free-radical intermediates were identified using the spin trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and electron paramagnetic resonance (EPR) spectrometry. Diethylenetriaminepentaacetic acid (DTPA), a polyaminocarboxylate, caused a concentration-dependent attenuation of N-centered radicals produced by the peroxidative metabolism of arylamines with the subsequent formation of secondary aliphatic carbon-centered radicals stemming from the cosubstrate molecule. Analogously, N,N-dimethylglycine (DMG) and N-methyliminodiacetate (MIDA), but not iminodiacetic acid (IDA), demonstrated a similar scavenging effect of arylamine-derived free radicals in a horseradish peroxidase/H2O2 system. Using human promyelocytic leukemia (HL-60) cell lysate as a model of human neutrophils, DTPA, MIDA, and DMG readily reduced anilinium cation radicals derived from the arylamines and gave rise to the corresponding carbon radicals. The rate of peroxidase-triggered polymerization of aniline was studied as a measure of nitrogen-radical scavenging. Although, IDA had no effect on the rate of aniline polymerization, this was almost nullified in the presence of DTPA and MIDA at half of the molar concentration of the aniline substrate, whereas a 20 molar excess of DMPO caused only a partial inhibition. Furthermore, the yield of formaldehyde, a specific reaction endproduct of the oxidation of aminocarboxylates by aniline free-radical metabolites, was quantitatively determined. Azobenzene, a specific reaction product of peroxidase-catalyzed free-radical dimerization of aniline, was fully abrogated in the presence of DTPA, as confirmed by GC/MS. Under aerobic conditions, a radical-transfer reaction is proposed between aminocarboxylates and arylamine free radicals via the carboxylic group-linked tertiary nitrogen of the deprotonated amino acid derivatives. These findings may have significant implications for the biological fate of arylamine xenobiotic and drug free-radical metabolites. PMID:24191655

  8. Mechanisms leading to oligomers and SOA through aqueous photooxidation: insights from OH radical oxidation of acetic acid and methylglyoxal

    Directory of Open Access Journals (Sweden)

    Y. Tan

    2012-01-01

    Full Text Available Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including pyruvate, oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA. Acetic acid plays a central role in the aqueous oxidation of methylglyoxal and it is a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid (20 ?M–10 mM was oxidized by OH radicals, and pyruvic acid and methylglyoxal experimental samples were analyzed using new analytical methods, in order to better understand the formation of SOA from acetic acid and methylglyoxal. Glyoxylic, glycolic, and oxalic acids formed from acetic acid and OH radicals. In contrast to the aqueous OH radical oxidation of methylglyoxal, the aqueous OH radical oxidation of acetic acid did not produce succinic acid and oligomers. This suggests that the methylgloxal-derived oligomers do not form through the acid catalyzed esterification pathway proposed previously. Using results from these experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols.

  9. Mechanism and kinetics in reactions of caffeic acid with radicals by pulse radiolysis and calculation

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xifeng; Cai, Zhongli; Katsumura, Yosuke [Tokyo Univ., Tokai, Ibaraki (Japan). Nuclear Engineering Research Lab

    2000-03-01

    The interaction of caffeic acid with e{sub aq}{sup -}, (CH{sub 3}){sub 2}(OH) CCH{sub 2}{sup {center_dot}}, CO{sub 2}{sup {center_dot}}{sup -}, H{sup {center_dot}}, {center_dot}OH and N{sub 3}{sup {center_dot}} radicals were studied by {gamma}-, pulse radiolysis and molecular orbital calculation. UV-visible spectra of electron/{center_dot}OH adducts, semi-quinone radicals of caffeic ions, and the stable products from the reactions were derived. The rate constants were determined. The attacked sites and the most favorable structures of the transient radicals were predicted. Reaction mechanisms were proposed. (author)

  10. A Comparative Study of the Radical-scavenging Activity of the Phenolcarboxylic Acids Caffeic Acid, p-Coumaric Acid, Chlorogenic Acid and Ferulic Acid, With or Without 2-Mercaptoethanol, a Thiol, Using the Induction Period Method

    OpenAIRE

    Seiichiro Fujisawa; Yoshinori Kadoma

    2008-01-01

    Phenolcarboxylic acid antioxidants do not act in vivo as radical-scavengers in isolation, but rather together with GSH (glutathione), a coantioxidant, they constitute an intricate antioxidant network. Caffeic acid, p-coumaric acid, ferulic acid and chlorogenic acid with or without 2-mercaptoethanol (ME), as a substitute for GSH, was investigated by the induction period (IP) method for polymerization of methyl methacrylate (MMA) initiated by thermal decomposition of 2,2'-azobisisobutyronitrile...

  11. Free radicals produced by the oxidation of gallic acid: An electron paramagnetic resonance study

    Directory of Open Access Journals (Sweden)

    Wagner Brett A

    2010-08-01

    Full Text Available Abstract Background Gallic acid (3,4,5-trihydroxybenzoic acid is found in a wide variety of plants; it is extensively used in tanning, ink dyes, as well as in the manufacturing of paper. The gallate moiety is a key component of many functional phytochemicals. In this work electron paramagnetic spectroscopy (EPR was used to detect the free radicals generated by the air-oxidation of gallic acid. Results We found that gallic acid produces two different radicals as a function of pH. In the pH range between 7-10, the spectrum of the gallate free radical is a doublet of triplets (aH = 1.00 G, aH = 0.23 G, aH = 0.28 G. This is consistent with three hydrogens providing hyperfine splitting. However, in a more alkaline environment, pH >10, the hyperfine splitting pattern transforms into a 1:2:1 pattern (aH (2 = 1.07 G. Using D2O as a solvent, we demonstrate that the third hydrogen (i.e. aH = 0.28 G at lower pH is a slowly exchanging hydron, participating in hydrogen bonding with two oxygens in ortho position on the gallate ring. The pKa of this proton has been determined to be 10. Conclusions This simple and novel approach permitted the understanding of the prototropic equilibrium of the semiquinone radicals generated by gallic acid, a ubiquitous compound, allowing new insights into its oxidation and subsequent reactions.

  12. Effect of Acid and Base Catalyzed Hydrolysis on the Yield of Phenolics and Antioxidant Activity of Extracts from Germinated Brown Rice (GBR)

    OpenAIRE

    Shahid Iqbal; Kim Wei Chan; Ismaila Muhammad Sani; Maznah Ismail

    2012-01-01

    The influence of both acidic and basic hydrolysis on the yield, total phenolic content and antioxidative capacity of methanolic extract of germinated brown rice (GBR) was studied. Total phenolic content (TPC), total flavonoid content (TFC), 2,2?-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging, 2,2?-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid (ABTS) radical cation scavenging, and ferric reducing antioxidant power (FRAP) tests were used for the measurement of antioxidant ability. Ther...

  13. Study of genotoxic, antigenotoxic and antioxidant activities of the digallic acid isolated from Pistacia lentiscus fruits.

    Science.gov (United States)

    Bhouri, Wissem; Derbel, Safa; Skandrani, Ines; Boubaker, Jihed; Bouhlel, Ines; Sghaier, Mohamed B; Kilani, Soumaya; Mariotte, Anne M; Dijoux-Franca, Marie G; Ghedira, Kamel; Chekir-Ghedira, Leila

    2010-03-01

    The digallic acid obtained from the fruit Pistacia lentiscus exhibits an inhibitory activity against nitrofurantoine and B[a]P induced genotoxicity when tested by the SOS chromotest bacterial assay system in the presence of Escherichia coli PQ37 strain. The antioxidant activity of the tested compound was determined by its ability to scavenge the free radical ABTS(+), to inhibit the xanthine oxidase, involved in the generation of free radicals, and to inhibit the lipid peroxidation induced by H(2)O(2) in the K562 cell line. Our results revealed that digallic acid shows an important free radical scavenging activity towards the ABTS(+) radical (99%) and protection against lipid peroxidation (68%). PMID:19563883

  14. Inhibition of free radical-induced erythrocyte hemolysis by 2-O-substituted ascorbic acid derivatives.

    Science.gov (United States)

    Takebayashi, Jun; Kaji, Hiroaki; Ichiyama, Kenji; Makino, Kazutaka; Gohda, Eiichi; Yamamoto, Itaru; Tai, Akihiro

    2007-10-15

    Inhibitory effects of 2-O-substituted ascorbic acid derivatives, ascorbic acid 2-glucoside (AA-2G), ascorbic acid 2-phosphate (AA-2P), and ascorbic acid 2-sulfate (AA-2S), on 2,2'-azobis(2-amidinopropane) dihydrochloride (AAPH)-induced oxidative hemolysis of sheep erythrocytes were studied and were compared with those of ascorbic acid (AA) and other antioxidants. The order of the inhibition efficiency was AA-2S> or =Trolox=uric acid> or =AA-2P> or =AA-2G=AA>glutathione. Although the reactivity of the AA derivatives against AAPH-derived peroxyl radical (ROO(*)) was much lower than that of AA, the derivatives exerted equal or more potent protective effects on AAPH-induced hemolysis and membrane protein oxidation. In addition, the AA derivatives were found to react per se with ROO(*), not via AA as an intermediate. These findings suggest that secondary reactions between the AA derivative radical and ROO(*) play a part in hemolysis inhibition. Delayed addition of the AA derivatives after AAPH-induced oxidation of erythrocytes had already proceeded showed weaker inhibition of hemolysis compared to that of AA. These results suggest that the AA derivatives per se act as biologically effective antioxidants under moderate oxidative stress and that AA-2G and AA-2P may be able to act under severe oxidative stress after enzymatic conversion to AA in vivo. PMID:17854711

  15. Histone H1- and other protein- and amino acid-hydroperoxides can give rise to free radicals which oxidize DNA

    DEFF Research Database (Denmark)

    Luxford, C; Morin, B; Dean, R T; Davies, Michael Jonathan

    1999-01-01

    Exposure of amino acids, peptides and proteins to radicals, in the presence of oxygen, gives high yields of hydroperoxides. These materials are readily decomposed by transition metal ions to give further radicals. We hypothesized that hydroperoxide formation on nuclear proteins, and subsequent decomposition of these hydroperoxides to radicals, might result in oxidative damage to associated DNA. We demonstrate here that exposure of histone H1 and model compounds to gamma-radiation in the presence...

  16. Products of aqueous vitamin B5 (pantothenic acid) formed by free radical reactions

    International Nuclear Information System (INIS)

    The radiolysis of aqueous vitamin B5 (pantothenic acid) has been investigated under various experimental conditions. The highest vitamin degradation (G=3.22) was observed in solutions saturated with N2O, where 90% OH radicals are operating. As final products, the following were established: aldehydes, carboxylic acids and ammonia. Their yield strongly depends on the presence/absence of air as well as on N2O (used to convert eaq- into OH) and was determined as a function of absorbed radiation dose. HPLC-analysis showed that in all media, a main product is formed, having the highest yield in aerated solutions. Based on the chemical analysis, it appears that the OH radicals are most involved in the degradation process. A precise sequence of the reaction steps could not be given presently, because of the implication of many simultaneous reactions

  17. Radical-scavenging activities of marine-derived xyloketals and related chromanes

    Directory of Open Access Journals (Sweden)

    Zhongliang Xu

    2013-09-01

    Full Text Available Xyloketals, a new type of antioxidants from a marine mangrove fungus, have potential pharmacological properties. In this paper, the radical-scavenging activities of a series of synthetic xyloketals and related chromanes toward 2,2-diphenyl-1-picrylhydrazyl (DPPH and 2,2?-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid (ABTS were evaluated by absorption spectrometry. One of the compounds (compound 10 displayed significant antioxidative action against DPPH and ABTS. A structure-activity analysis showed that the reactive sites on these compounds correlated with a hydroxy-group and also with ketal or aromatic H substituents. Based in part on a density functional theory (DFT calculation of compound 10, the antioxidant mechanism of this chromane was deduced as a possible radical-scavenging mechanism by a sequential proton loss electron-transfer (SPLET process.

  18. Structural Insights into 2,2?-Azino-Bis(3-Ethylbenzothiazoline-6-Sulfonic Acid) (ABTS)-Mediated Degradation of Reactive Blue 21 by Engineered Cyathus bulleri Laccase and Characterization of Degradation Products

    OpenAIRE

    Kenzom, T.; Srivastava, P; Mishra, S.

    2014-01-01

    Advanced oxidation processes are currently used for the treatment of different reactive dyes which involve use of toxic catalysts. Peroxidases are reported to be effective on such dyes and require hydrogen peroxide and/or metal ions. Cyathus bulleri laccase, expressed in Pichia pastoris, catalyzes efficient degradation (78 to 85%) of reactive azo dyes (reactive black 5, reactive orange 16, and reactive red 198) in the presence of synthetic mediator ABTS [2,2?-azino-bis(3-ethylbenzothiazoline-...

  19. Conversion of a positive resist into a negative resist by induced radical reactions in solid methylmethacrylate/methacrylic acid copolymers

    International Nuclear Information System (INIS)

    A study is presented of the lifetime of radicals produced by irradiation of solid methymethacrylate/methacrylic acid copolymers with ?-rays and electron beams. Radical lifetime was investigated as a function of temperature by means of electron-spinresonance spectroscopy and radiothermoluminescence. In the presence of triallylphosphate the investigated polymers are converted into negative resist materials of high radiation sensitivity. (author)

  20. Uric acid a better scavenger of free radicals than vitamin C in rheumatoid arthritis

    OpenAIRE

    Mahajan, Mridula; Kaur, Sukhraj; Mahajan, Shruti; Kant, Ravi

    2009-01-01

    Uric acid an endogenous aqueous antioxidant in normal humans is present in much higher concentrations than vitamin C and has been known to cover 2/3rd of the free radical scavenging capacity in plasma. In the present study average uric acid levels of patients of rheumatoid arthritis were found to be close to the normal individuals. A unique feature was observed after classifying the patients on the basis of the duration of suffering, the patients having longer duration of disease had least ur...

  1. Free radical mediated formation of 3-monochloropropanediol (3-MCPD) fatty acid diesters.

    Science.gov (United States)

    Zhang, Xiaowei; Gao, Boyan; Qin, Fang; Shi, Haiming; Jiang, Yuangrong; Xu, Xuebing; Yu, Liangli Lucy

    2013-03-13

    The present study was conducted to test the hypothesis that a free radical was formed and mediated the formation of 3-monochloropropanediol (3-MCPD) fatty acid diesters, a group of food contaminants, from diacylglycerols at high temperature under a low-moisture condition for the first time. The presence of free radicals in a vegetable oil kept at 120 °C for 20 min was demonstrated using an electron spin resonance (ESR) spectroscopy examination with 5,5-dimethylpyrroline-N-oxide (DMPO) as the spin trap agent. ESR investigation also showed an association between thermal treatment degree and the concentration of free radicals. A Fourier transform infrared spectroscopy (FT-IR) analysis of sn-1,2-stearoylglycerol (DSG) at 25 and 120 °C suggested the possible involvement of an ester carbonyl group in forming 3-MCPD diesters. On the basis of these results, a novel free radical mediated chemical mechanism was proposed for 3-MCPD diester formation. Furthermore, a quadrupole-time of flight (Q-TOF) MS/MS investigation was performed and detected the DMPO adducts with the cyclic acyloxonium free radical (CAFR) and its product MS ions, proving the presence of CAFR. Furthermore, the free radical mechanism was validated by the formation of 3-MCPD diesters through reacting DSG with a number of organic and inorganic chlorine sources including chlorine gas at 120 and 240 °C. The findings of this study might lead to the improvement of oil and food processing conditions to reduce the level of 3-MCPD diesters in foods and enhance food safety. PMID:23425600

  2. Polyphenolic Contents and Free Radical Scavenging Potential of Extracts from Leaves of Ocimum americanum L.

    OpenAIRE

    Afolayan, A. J.; O.I. Oloyede; B.T. Aluko

    2013-01-01

    This study assessed the polyphenolic contents and antioxidant activity of ethanol, butanol and ethyl acetate extracts of Ocimum americanum leaves using in vitro models. The ability of the extracts to scavenge 2,2-diphenyl-1-picrylhydrazyl (DPPH?), 2,2-azino-bis-(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS?+), hydrogen peroxide (H2O2), Nitric Oxide (NO) and hydroxyl radical (OH?) was investigated. The inhibition of lipid oxidation, reducing power, total flavonoids, phenols and flavonols con...

  3. Biotechnological treatment for colorless denim and textil wastewater treatment with laccase and ABTS / Tratamiento biotecnológico para la decoloración de la mezclilla y efluentes textiles empleando lacasa y ABTS

    Scientific Electronic Library Online (English)

    Myrna, SOLÍS-OBA; Javier, ALMENDÁRIZ; Gustavo, VINIEGRA-GONZÁLEZ.

    2008-03-01

    Full Text Available El sistema ABTS (ácido 2,2'-[3-etil benzotiazolin-6-sulfónico])-lacasa se empleó para decolorar tanto tela de mezclilla como una solución preparada de índigo. Después del tratamiento, la mezclilla adquirió un aspecto de usada, sin que las fibras mostraran evidencia de daño, mientras que la solución [...] de índigo se decoloró. Adicionalmente, el análisis de la biodegradación de los desechos acuosos de la decoloración de la mezclilla y la solución decolorada control de índigo mostraron que, en ambos casos el agua residual fue fácilmente biodegradada tanto aeróbica como anaeróbicamente, mientras que la solución control de índigo requirió de 5 días para biodegradarse aeróbicamente y no sufrió ningún cambio en el sistema anaeróbico. El ABTS oxidado ó la lacasa por sí solos no decoloraron la mezclilla ni la solución de índigo bajo las mismas condiciones experimentales en que se empleó la combinación de ambos ABTS-lacasa. Esto se explica porque, durante la reacción de decoloración, el mediador se recicla varias veces entre la enzima y el colorante, de tal forma que en 30 minutos, una molécula de ABTS oxida 800 moléculas de índigo, además la velocidad de decoloración fue dos órdenes de magnitud mayor que la velocidad cuando se empleó el ABTS ó la enzima en forma individual. Abstract in english The ABTS (2,2'-[3-etil benzotiazolin-6-sulphonic]acid)-Laccase system was applied for discoloration of both commercial denim fabric and a synthetic indigo solution. After treatment, the denim fabric looked like an aged one, although fibers did not exhibit any damage and the synthetic indigo solution [...] was bleached. Additionally, an analysis of both the denim discoloration residual water and the synthetic indigo solution biodegradation, showed that in the two cases the residual water was easily biodegraded in either an aerobic or anaerobic mode, while the control indigo solution required 5 days to be biodegraded in an aerobic mode, and it became unaltered in anaerobic mode. The oxidized ABTS or the laccase could not bleach denim or the synthetic indigo solution in the same experimental conditions as when using the system ABTS-laccase. This is explained considering that, during this process, as when using the mediator recycles several times between the laccase and the indigo, in such way that in a 30 min period, one molecule of ABTS oxidized 800 indigo molecules; also, the observed discoloration rate was two orders of magnitude higher than the rates observed when either the oxidized mediator or the enzyme by itself were applied.

  4. Oxygen dependency of one-electron reactions generating ascorbate radicals and hydrogen peroxide from ascorbic acid.

    Science.gov (United States)

    Boatright, William L

    2016-04-01

    The effect of oxygen on the two separate one-electron reactions involved in the oxidation of ascorbic acid was investigated. The rate of ascorbate radical (Asc(-)) formation (and stability) was strongly dependent on the presence of oxygen. A product of ascorbic acid oxidation was measurable levels of hydrogen peroxide, as high as 32.5?M from 100?M ascorbic acid. Evidence for a feedback mechanism where hydrogen peroxide generated during the oxidation of ascorbic acid accelerates further oxidation of ascorbic acid is also presented. The second one-electron oxidation reaction of ascorbic acid leading to the disappearance of Asc(-) was also strongly inhibited in samples flushed with argon. In the range of 0.05-1.2mM ascorbic acid, maximum levels of measurable hydrogen peroxide were achieved with an initial concentration of 0.2mM ascorbic acid. Hydrogen peroxide generation was greatly diminished at ascorbic acid levels of 0.8mM or above. PMID:26593628

  5. Rates and mechanism of the reactions of hydroxyl radicals with acetic, deuterated acetic, and propionic acids in the gas phase

    International Nuclear Information System (INIS)

    Rate constants for the reactions of hydroxyl radicals with the monomer and dimer of acetic acid, deuterated acetic acids, and propionic acid have been determined by a laser photolysis-resonance absorption technique. Hydroxyl radicals were generated by photolysis of the acids at 222 nm with a KrCl laser and their decay was followed by time-resolved resonance absorption. The monomers of acetic and deuterated acetic acids reacted with OH much faster than the dimers, whereas the monomer and dimer of propionic acid reacted with about equal rate constants. A primary isotope effect was observed when carboxylic but not alkyl hydrogen was substituted by deuterium in acetic acid. The results are entirely consistent with the two-channel mechanism that we proposed for the reaction of OH with formic acid. The results are interpreted in terms of the variations in C-H bond strengths and in equilibrium constants for adduct formation of the acids studied

  6. On the reaction of lupulones, hops ?-acids, with 1-hydroxyethyl radical.

    Science.gov (United States)

    de Almeida, Natália E C; do Nascimento, Eduardo S P; Cardoso, Daniel R

    2012-10-24

    Lupulones, hops ?-acids, are one of the main constituents of the hops resin and have an important contribution to the overall bacteriostatic activity of hops during beer brewing. The use of lupulones as natural alternatives to antibiotics is increasing in the food industry and also in bioethanol production. However, lupulones are easy oxidizable and have been shown to be very reactive toward 1-hydroxyethyl radical with apparent bimolecular rate constants close to diffusion control k = 2.9 × 10(8) and 2.6 × 10(8) L mol(-1) s(-1) at 25.0 ± 0.2 °C in ethanol-water solution (10% of ethanol (v/v)) as probed by EPR and ESI-IT-MS/MS spin-trapping competitive kinetics, respectively. The free energy change for an electron-transfer mechanism is ?G° = 106 kJ/mol as calculated from the oxidation peak potential experimentally determined for lupulones (1.1 V vs NHE) by cyclic voltammetry and the reported reduction potential for 1-hydroxyethyl radical. The major reaction products identified by LC-ESI-IT-MS/MS and ultrahigh-resolution accurate mass spectrometry (orbitrap FT-MS) are hydroxylated lupulone derivatives and 1-hydroxyethyl radical adducts. The lack of pH dependence for the reaction rate constant, the calculated free energy change for electron transfer, and the main reaction products strongly suggest the prenyl side chains at the hops ?-acids as the reaction centers rather than the ?,?'-triketone moiety. PMID:23031058

  7. Characterization of fatty acids, bioactive lipids, and radical scavenging activity of Canterbury bells seed oil

    Directory of Open Access Journals (Sweden)

    Hassanien, M. F.R.

    2014-06-01

    Full Text Available The aim of this study was to characterize the chemical composition and radical scavenging activity of Canterbury bells (Campanula medium seed oil. C. medium seeds contained 9.2% extractable oil. The lipid classes, fatty acids, phytosterol and tocopherol composition of C. medium seed oil were determined. The amount of neutral lipids in the oil was the highest, followed by glycolipids and phospholipids. Linoleic and oleic were the main fatty acids. C. medium oil is characterized by high levels of phytosterols and ?-sitosterol was the main compound. ?-Tocopherol constituted 42.5% of the total tocopherol content followed by ?-tocopherol. The radical scavenging activity (RSA toward 1,1-diphenyl-2-picrylhydrazyl (DPPH radicals and galvinoxyl radicals of C. medium oil were higher than those of extra virgin olive oil. The diverse potential uses of C. medium oil may make this plant industrially important.El objetivo de este estudio fue caracterizar la composición química y la actividad de captación de radicales de aceites de semillas de campanillas de Canterbury (Campanula medium. Las semillas de C. medium contenían 9,2 % de aceite extraíble. Se determinó la composición de las diferentes clases de lípidos, ácidos grasos, fitoesteroles y tocoferoles. La cantidad de lípidos neutros en el aceite fue mayoritario, seguido de glicolípidos y fosfolípidos. Linoleico y oleico fueron los ácidos grasos principales. El aceite de C. medium se caracteriza por altos niveles de fitoesteroles y ?-sitosterol fue el compuesto principal. ?-tocoferol constituía 42,5 % del contenido total de tocoferol seguido de ?-tocoferol. La actividad de captación de radicales (RSA a 1,1-difenil-2- picrilhidrazil (DPPH y radicales galvinoxil de C. medium fueron superiores a las de aceite de oliva virgen extra. Los diversos usos potenciales de los aceites de C. medium pueden hacer que esta planta pueda ser importante industrialmente.

  8. Reactivity of chlorine radical with submicron palmitic acid particles: kinetic measurements and products identification

    Directory of Open Access Journals (Sweden)

    M. Mendez

    2013-06-01

    Full Text Available The heterogeneous reaction of Cl. radicals with sub-micron palmitic acid (PA particles was studied in an aerosol flow tube in the presence or in the absence of O2. Fine particles were generated by homogeneous condensation of PA vapors and introduced in the reactor where chlorine atoms are produced by photolysis of Cl2 using UV lamps surrounding the reactor. The effective reactive uptake coefficient (? has been determined from the rate loss of PA measured by GC/MS analysis of reacted particles as a function of the chlorine exposure. In the absence of O2, ? = 14 ± 5 indicates efficient secondary chemistry involving Cl2. GC/MS analyses have shown the formation of monochlorinated and polychlorinated compounds in the oxidized particles. Although, the PA particles are solid, the complete mass can be consumed. In the presence of oxygen, the reaction is still dominated by secondary chemistry but the propagation chain length is smaller than in the absence of O2 which leads to an uptake coefficient ? = 3 ± 1. In the particulate phase, oxocarboxylic acids and dicarboxylic acids are identified by GC/MS. Formation of alcohols and monocarboxylic acids are also suspected. All these results show that solid organic particles could be efficiently oxidized by gas-phase radicals not only on their surface, but also in bulk by mechanisms which are still unclear. Furthermore the identified reaction products are explained by a chemical mechanism showing the pathway of the formation of more functionalized products. They help to understand the aging of primary tropospheric aerosol containing fatty acids.

  9. Antioxidant and Free Radical Scavenging Capacity of Seed and Shell Essential Oils Extracted from Abrus precatorius (L

    Directory of Open Access Journals (Sweden)

    Sunday O. Okoh

    2014-04-01

    Full Text Available Essential oils from plants have been proven safe as natural antioxidants, and few are already marketed as digestive enhancers as well as in prevention of several degenerative diseases. This study evaluated the antioxidant capacity of seed and shell essential oils of Abrus precatorius (L, a herb used for ethno-medicinal practices in Nigeria. The essential oils were obtained by hydro-distillation. The ability of the oils to act as hydrogen/electrons donor or scavenger of radicals were determined by in-vitro antioxidant assays using 2,2-diphenyl-2-picryl-hydrazyl free radical (DPPH. scavenging; 2,2?-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid (ABTS radical scavenging; lipid peroxide and nitric oxide radicals scavenging assays. The IC50 of the seed and shell oils (2.10 mg/mL and 1.20 mg/mL respectively showed that antioxidant activity is higher than that for the standard drugs (3.20 mg/mL and 3.40 mg/mL for the nitric oxide scavenging assay. The lipid peroxidation radical activity of the oils were similar to vitamin C, weak DPPH and ABTS radical scavenging activities were discovered in comparison to vitamin C and rutin. Generally, in the four antioxidant assays, a significant correlation existed between concentrations of the oils and percentage inhibition of free radicals and lipid peroxidation. The composition of A. precatorius essential oils reported earlier may account for their antioxidant capacity.

  10. Electrospray ionization mass spectrometry applied to study the radical acetylation of amino acids, peptides and proteins

    Scientific Electronic Library Online (English)

    Atecla N. L., Alves; Leticia D. L., Jedlicka; Júlio, Massari; Maria A., Juliano; Etelvino J. H., Bechara; Nilson A., Assunção.

    2013-12-01

    Full Text Available Recentemente nosso grupo demostrou experimentalmente que a hipótese de produção de radical acetil em meio tamponado no sistema diacetil/peroxinitrito era possível. Diacetil é um flavorizante em alimentos, cigarros e bebidas. O peroxinitrito é encontrado na mitocôndria, e em certas condições como um [...] processo de infeção em humanos, a concentração aumenta significativamente. Em sistemas biológicos, radicais podem facilmente modificar a estrutura e atividade de ácidos nucleicos, proteínas e outras biomoléculas, causando significativo estres oxidativo. Baseado em dados de ressonância magnética e espectrometria de massas, este artigo apresenta os produtos que provam a produção do radical acetil e a formação de compostos estáveis devido à ligação covalente entre o acetil e os aminoácidos (produtos acetilados), e os adutos de peptídeos e proteínas. Estes materiais foram separados por eletroforese capilar e identificados por espectrometria de massas. O meio reacional consistiu da mistura de diacetil e peroxynitrito em uma relação de 1:2 e em 20 mmol L-1 de fosfato de sódio, no valor de pH 7,2. Estes experimentos também revelam a dupla acetilação da lisina, demonstrando a alta reatividade do composto com biomoléculas contendo grupos de nitrogênio, abundantemente encontradas em sistemas biológicos. A mudança estrutural de uma molécula acetilada é uma fonte de modificações pós-tradução com inúmeras consequências biológicas. Abstract in english Recently, our group proposed a process that generated acetyl radicals in a reaction medium buffered with a diacetyl/peroxynitrite system. Diacetyl is a flavoring agent in food, cigarettes and drinks. Peroxynitrite is found in mitochondria, and in certain conditions, such as an infection in humans, i [...] ts concentration is augmented significantly. In biological systems, radical compounds can easily modify the structure and activity of nucleic acids, proteins and other biomolecules, causing significant oxidative stress. Based on paramagnetic resonance and mass spectrometry data, this work discusses products that prove acetyl radicals are produced and are able to form stable covalent bonds with amino acid (acetylated products), peptide and protein adducts. These materials were separated and detected by capillary electrophoresis coupled with tandem mass spectrometry or offline mass spectrometry. The reaction medium contained a 1:2 mixture of diacetyl and peroxynitrite dissolved in 200 mmol L-1 of pH 7.2 sodium phosphate buffer. These experiments also reveal the double acetylation of lysine, demonstrating the high reactivity of these compounds when in contact with nitrogen-containing biomolecules readily found in biological systems. These structural changes might be an epigenetic source of post-translational protein modification.

  11. Antioxidant Activity of Caffeic Acid against Iron-Induced Free Radical Generation--A Chemical Approach.

    Science.gov (United States)

    Genaro-Mattos, Thiago C; Maurício, Ângelo Q; Rettori, Daniel; Alonso, Antonio; Hermes-Lima, Marcelo

    2015-01-01

    Caffeic acid (CA) is a phenolic compound widely found in coffee beans with known beneficial effects in vivo. Many studies showed that CA has anti-inflammatory, anti-mutagenic, antibacterial and anti-carcinogenic properties, which could be linked to its antioxidant activity. Taking in consideration the reported in vitro antioxidant mechanism of other polyphenols, our working hypothesis was that the CA antioxidant activity could be related to its metal-chelating property. With that in mind, we sought to investigate the chemical antioxidant mechanism of CA against in vitro iron-induced oxidative damage under different assay conditions. CA was able to prevent hydroxyl radical formation promoted by the classical Fenton reaction, as determined by 2-deoxyribose (2-DR) oxidative degradation and DMPO hydroxylation. In addition to its ability to prevent hydroxyl radical formation, CA had a great inhibition of membrane lipid peroxidation. In the lipid peroxidation assays CA acted as both metal-chelator and as hydrogen donor, preventing the deleterious action promoted by lipid-derived peroxyl and alkoxyl radicals. Our results indicate that the observed antioxidant effects were mostly due to the formation of iron-CA complexes, which are able to prevent 2-DR oxidation and DMPO hydroxylation. Noteworthy, the formation of iron-CA complexes and prevention of oxidative damage was directly related to the pH of the medium, showing better antioxidant activity at higher pH values. Moreover, in the presence of lipid membranes the antioxidant potency of CA was much higher, indicating its enhanced effectiveness in a hydrophobic environment. Overall, our results show that CA acts as an antioxidant through an iron chelating mechanism, preventing the formation of free hydroxyl radicals and, therefore, inhibiting Fenton-induced oxidative damage. The chemical properties of CA described here--in association with its reported signaling effects--could be an explanation to its beneficial effects observed in vivo. PMID:26098639

  12. Antioxidant Activity of Caffeic Acid against Iron-Induced Free Radical Generation—A Chemical Approach

    Science.gov (United States)

    Genaro-Mattos, Thiago C.; Maurício, Ângelo Q.; Rettori, Daniel; Alonso, Antonio; Hermes-Lima, Marcelo

    2015-01-01

    Caffeic acid (CA) is a phenolic compound widely found in coffee beans with known beneficial effects in vivo. Many studies showed that CA has anti-inflammatory, anti-mutagenic, antibacterial and anti-carcinogenic properties, which could be linked to its antioxidant activity. Taking in consideration the reported in vitro antioxidant mechanism of other polyphenols, our working hypothesis was that the CA antioxidant activity could be related to its metal-chelating property. With that in mind, we sought to investigate the chemical antioxidant mechanism of CA against in vitro iron-induced oxidative damage under different assay conditions. CA was able to prevent hydroxyl radical formation promoted by the classical Fenton reaction, as determined by 2-deoxyribose (2-DR) oxidative degradation and DMPO hydroxylation. In addition to its ability to prevent hydroxyl radical formation, CA had a great inhibition of membrane lipid peroxidation. In the lipid peroxidation assays CA acted as both metal-chelator and as hydrogen donor, preventing the deleterious action promoted by lipid-derived peroxyl and alkoxyl radicals. Our results indicate that the observed antioxidant effects were mostly due to the formation of iron-CA complexes, which are able to prevent 2-DR oxidation and DMPO hydroxylation. Noteworthy, the formation of iron-CA complexes and prevention of oxidative damage was directly related to the pH of the medium, showing better antioxidant activity at higher pH values. Moreover, in the presence of lipid membranes the antioxidant potency of CA was much higher, indicating its enhanced effectiveness in a hydrophobic environment. Overall, our results show that CA acts as an antioxidant through an iron chelating mechanism, preventing the formation of free hydroxyl radicals and, therefore, inhibiting Fenton-induced oxidative damage. The chemical properties of CA described here—in association with its reported signaling effects—could be an explanation to its beneficial effects observed in vivo. PMID:26098639

  13. Mechanism of benzophenone ketyl radical formation in acid alcohols studied by pulse-radiolysis and rigid-matrix techniques

    International Nuclear Information System (INIS)

    The mechanism of the benzophenone ketyl radical formation in acid methanol, ethanol, and 2-propanol was studied by using pulse-radiolysis and rigid-matrix techniques. When a 0.1 M ethanol solution of benzophenone containing hydrogen chloride (1.2 M) was irradiated at 77 K by ? rays from 60Co, the absorption spectrum of the trapped intermediates was ascribed solely to benzophenone ketyl radicals. The pulse-radiolysis study of the solution at 100 K revealed that the ketyl radicals are produced by protonation of presolvated benzophenone anion radicals. At 153 K, the ketyl radicals were observed to be produced also by hydrogen-atom transfer from CH3CHOH and CH3CH(OH)CH3 to benzophenone; the temperature dependence of the transfer rate constant was studied

  14. Degradation of hyaluronic acid, poly- and monosaccharides, and model compounds by hypochlorite : evidence for radical intermediates and fragmentation

    DEFF Research Database (Denmark)

    Hawkins, C L; Davies, Michael Jonathan

    1998-01-01

    Degradation of hyaluronic acid by oxidants such as HO. and HOCl/CIO- is believed to be important in the progression of rheumatoid arthritis. While reaction of hyaluronic acid with HO. has been investigated extensively, reaction with HOCl/ClO- is less well defined. Thus, little is known about the site(s) of HOCl/ClO- attack, the intermediates formed, or the mechanism(s) of polymer degradation. In this study reaction of HOCl/ClO- with amides, sugars, polysaccharides, and hyaluronic acid has been monitored by UV-visible (220-340 nm) and EPR spectroscopy. UV-visible experiments have shown that HOCl/ClO- reacts preferentially with N-acetyl groups. This reaction is believed to give rise to transient chloramide (R-NCl-C(O)-R') species, which decompose rapidly to give radicals via either homolysis (to produce N. and Cl.) or heterolysis (one-electron reduction, to give N. and Cl.) of the N--C bond. The nature of the radicals formed has been investigated by EPR spin trapping. Reaction of HOCl/ClO- with hyaluronic acid, chondroitin sulphates A and C, N-acetyl sugars, and amides gave novel, carbon-centered, spin adducts, the formation of which is consistent with selective initial attack at the N-acetyl group. Thus, reaction with hyaluronic acid and chondroitin sulphate A, appears to be localized at the N-acetylglucosamine sugar rings. These carbon-centered radicals are suggested to arise from rapid rearrangement of initial nitrogen-centered radicals, formed from the N-acetyl chloramide, by reactions analogous to those observed with alkoxyl radicals. The detection of increasing yields of low-molecular-weight radical adducts from hyaluronic acid and chondroitin sulphate A with increasing HOCl/ClO-concentrations suggests that formation of the initial nitrogen-centered species on the N-acetylglucosamine rings, and the carbon-centered radicals derived from them, brings about polymer fragmentation.

  15. Comparative evaluation of free radical scavenging activity of Boerhaavia diffusa root extracts (BDRE) and determination of dose effectivity against radiation induced damages in Swiss albino mice

    OpenAIRE

    Sharma, J.; Saini, M. R.; P Dhakar

    2012-01-01

    Summary: Purpose of the study was to evaluate free radical scavenging activity (FRSA) of root extracts of Boerhaavia diffusa in different solvents and to examine its dose effectivity against radiation induced damages in Swiss albino mice. Scavenging activities of aqueous, ethanolic and hydroethanolic extracts of B. diffusa roots were evaluated by DPPH (2, 2-diphenyl-1 picryl hydrazyl), ABTS (2,2’-azino-bis-3-ethylbenzothiazoline-6-sulphonic acid) and NO (nitric oxide) assay to find the most e...

  16. Radical-Scavenging Activity of Thiols, Thiobarbituric Acid Derivatives and Phenolic Antioxidants Determined Using the Induction Period Method for Radical Polymerization of Methyl Methacrylate

    OpenAIRE

    Seiichiro Fujisawa; Yoshinori Kadoma

    2012-01-01

    The radical-scavenging activities of two thiols, eight (thio)barbituric acid derivatives and six chain-breaking phenolic antioxidants were investigated using the induction period method for polymerization of methyl methacrylate (MMA) initiated by thermal decomposition of 2,2’-azobisisobutyronitrile (AIBN) and monitored by differential scanning calorimetry (DSC). The induction period (IP) for the thiols 2-mercaptoethanol (ME) and 2-mercapto-1-methylimidazole (MMI) was about half that for pheno...

  17. Electron spin resonance studies of barriers to hindered rotation in acetic acid, acetamide, and peptide radicals

    International Nuclear Information System (INIS)

    Activation energies for methyl group rotation in the radicals of type H3C-C2O) as well as in 8 M NaOD glasses have produced the acetic acid anion, the acetate dianion, and the acetamide anion. ESR spectra of these have revealed a doublet (ca. 32G) at 90 K reversibly interconverting to a 1:3:3:1 quartet, of ca. 15-G hyperfine splitting, at higher temperatures (170 K). This interconversion has been attributed to the hindered internal rotation of the methyl group about the H3C-C< bond. The ESR spectra are analyzed using modified Bloch equations for the three-jump process. The mean lifetime (tau) at each temperature (T) has been estimated by a comparison of experimental and simulated ESR spectra. The activation energy (E/sub a/) for the sixfold barrier to the rotation is found to be 5.0 +- 0.5 kcal/mol in the acetate dianion and is about 3.0 kcal/mol for the acetate and acetamide as well as N-acetylamino acids. ESR spectra characteristic of the tunneling methyl group were observed at low temperature (20 K< T<100K) for the radicals produced in ?-irradiated polycrystalline samples of glycyl-L-alanine and L-alanyl-L-alanine. 3 figures, 1 table

  18. Lipoxygenase-mediated pro-radical effect of melatonin via stimulation of arachidonic acid metabolism

    International Nuclear Information System (INIS)

    We have shown that melatonin immediately and transiently stimulates intracellular free radical production on a set of leukocytes, possibly as a consequence of calmodulin binding. We show here that melatonin-induced ROS are produced by lipoxygenase (LOX), since they are prevented by a set of LOX inhibitors, and are accompanied by increase of the 5-LOX product 5-HETE. LOX activation is accompanied by strong liberation of AA; inhibition of Ca2+-independent, but not Ca2+-dependent, phospholipase A2 (PLA2), prevents both melatonin-induced arachidonic acid and ROS production, whereas LOX inhibition only prevents ROS, indicating that PLA2 is upstream with respect to LOX, as occurs in many signaling pathways. Chlorpromazine, an inhibitor of melatonin-calmodulin interaction, inhibits both ROS and arachidonic acid production, thus possibly placing calmodulin at the origin of a melatonin-induced pro-radical pathway. Interestingly, it is known that Ca2+-independent PLA2 binds to calmodulin: our results are compatible with PLA2 being liberated by melatonin from a steady-state calmodulin sequestration, thus initiating an arachidonate signal transduction. These results delineate a novel molecular pathway through which melatonin may participate to the inflammatory response.

  19. Isolation and Characterisation of in Vitro and Cellular Free Radical Scavenging Peptides from Corn Peptide Fractions

    Directory of Open Access Journals (Sweden)

    Liying Wang

    2015-02-01

    Full Text Available Corn gluten meal, a corn processing industry by-product, is a good source for the preparation of bioactive peptides due to its special amino acid composition. In the present study, the in vitro and cellular free radical scavenging activities of corn peptide fractions (CPFs were investigated. Results indicated that CPF1 (molecular weight less than 1 kDa and CPF2 (molecular weight between 1 and 3 kDa exhibited good hydroxyl radical, superoxide anion radical and 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulphonicacid diammonium salt (ABTS radical scavenging activity and oxygen radical absorbance capacity (ORAC. Meanwhile, the in vitro radical scavenging activity of CPF1 was slightly higher than that of CPF2. Both CPF1 and CPF2 also exhibited significant cytoprotective effects and intracellular reactive oxygen species scavenging activity in Caco-2 cells exposed to hydrogen peroxide (H2O2. The amino acid composition analysis revealed that the CPF were rich in hydrophobic amino acids, which comprised of more than 45% of total amino acids. An antioxidant peptide sequence of Tyr-Phe-Cys-Leu-Thr (YFCLT was identified from CPF1 using matrix-assisted laser desorption/ionization time-of-flight/time-of-?ight mass spectrometry (MALDI TOF/TOF MS. The YFCLT exhibited excellent ABTS radical scavenging activity with a 50% effective concentration (EC50 value of 37.63 µM, which was much lower than that of Trolox. In conclusion, corn gluten meal might be a good source to prepare antioxidant peptides.

  20. The Comparative Ability of Antioxidant Activity of Piper crocatum in Inhibiting Fatty Acid Oxidation and Free Radical Scavenging

    OpenAIRE

    MUHAMMAD ALFARABI; MARIA BINTANG; SURYANI; MEGA SAFITHRI

    2010-01-01

    The excessive number of free radicals in human body could increase lipid peroxides and causes a variety of degenerative diseases. Piper crocatum is a plant containing natural chemicals that may have an antioxidant ability to inhibit fatty acid oxidation and reduce free radicals, however, there is no published scientific reports up to now. Therefore, the objective of this research is to study the ability of ethanol extract of P. crocatum as an antioxidant. The leaves of P. crocatum (25 g) were...

  1. Intraoperative use of tranexamic acid to reduce transfusion rate in patients undergoing radical retropubic prostatectomy: double blind, randomised, placebo controlled trial

    OpenAIRE

    Crescenti, Antonella; Borghi, Giovanni; Bignami, Elena; Bertarelli, Gaia; Landoni, Giovanni; Casiraghi, Giuseppina Maria; Briganti, Alberto; Montorsi, Francesco; Rigatti, Patrizio; Zangrillo, Alberto

    2011-01-01

    Objectives To determine the efficacy of intraoperative treatment with low dose tranexamic acid in reducing the rate of perioperative transfusions in patients undergoing radical retropubic prostatectomy.

  2. A comparison of abts and dpph methods for assessing the total antioxidant capacity of human milk

    Directory of Open Access Journals (Sweden)

    Dorota Martysiak-?urowska

    2012-03-01

    Full Text Available Introduction. The Total Antioxidant Capacity (TAC of human milk reflects the concentration and the activity of many components which prevent oxidative degradation of fats and proteins. This study compares the effectiveness of ABTS and DPPH tests with regard to the recovery, precision and sensitivity (detection and quantification limit of (TAC values in human milk. Material  and methods. TAC values were determined in twenty five samples of human milk obtained from healthy mothers, residents of Gda?sk, on the 14th day postpartum. Results.  The average TAC of human milk determined by ABTS assay was 19.61 ±3.311 mg TE (Trolox Equivalents/100 cm3, the average values obtained by the DPPH assay reached 9.95 ±4.36 mg TE/100 cm3. For each milk sample the TAC determined by the ABTS test was significantly higher than the values pro- duced by the DPPH test. The above findings can be attributed to the presence of substances whose spectra overlap with DPPH• spectra. ABTS test was characterised by a higher sensitivity and repeatability of the determination of TAC in human milk compared to the DPPH test. Conclusions. Comparing the calculated values for the validation parameters of both methods and taking into account the solubility of DPPH only in polar matrices, slower reaction of selected antioxidants with DPPH radical, and the presence in human milk constituents absorbing electromagnetic radiation in the absorption of DPPH be assumed that the ABTS test is more appropriate method of  determining of TAC in breast milk.

  3. The role of alkoxy radicals in the heterogeneous reaction of two structural isomers of dimethylsuccinic acid.

    Science.gov (United States)

    Cheng, Chiu Tung; Chan, Man Nin; Wilson, Kevin R

    2015-09-23

    A key challenge in understanding the transformation chemistry of organic aerosols is to quantify how changes in molecular structure alter heterogeneous reaction mechanisms. Here we use two model systems to investigate how the relative locations of branched methyl groups control the heterogeneous reaction of OH with two isomers of dimethylsuccinic acid (C6H10O4). 2,2-Dimethylsuccinic acid (2,2-DMSA) and 2,3-dimethylsuccinic acid (2,3-DMSA) differ only in the location of the two branched methyl groups, thus enabling a closer inspection of how the distribution of carbon reaction sites impacts the chemical evolution of the aerosol. The heterogeneous reaction of OH with 2,3-DMSA (reactive OH uptake coefficient, ? = 0.99 ± 0.16) is found to be ?2 times faster than that of 2,2-DMSA (? = 0.41 ± 0.07), which is attributed to the larger stability of the tertiary alkyl radical produced by the initial OH abstraction reaction. While changes in the average aerosol oxidation state (OSC) and the carbon number (NC) are similar for both isomers upon reaction, significant differences are observed in the underlying molecular distribution of reaction products. The reaction of OH with the 2,3-DMSA isomer produces two major reaction products: a product containing a new alcohol functional group (C6H10O5) formed by intermolecular hydrogen abstraction and a C5 compound formed via carbon-carbon (C-C) bond scission. Both of these reaction products are explained by the formation and subsequent reaction of a tertiary alkoxy radical. In contrast, the OH reaction with the 2,2-DMSA isomer forms four dominant reaction products, the majority of which are C5 scission products. The difference in the quantity of C-C bond scission products for these two isomers is unexpected since decomposition is assumed to be favored for the isomer with the most tertiary carbon sites (i.e. 2,3-DMSA). For both isomers, there is a much larger abundance of C6 alcohol relative to C6 ketone products, which suggests that the presence of the two branched methyl groups favors alkoxy formation from peroxy radical self-reactions. These results reveal how the isomeric structure ultimately controls the overall competition between functionalization and fragmentation in these model systems. PMID:26356151

  4. Caffeic Acid Inhibits the Formation of 7-Carboxyheptyl Radicals from Oleic Acid under Flavin Mononucleotide Photosensitization by Scavenging Singlet Oxygen and Quenching the Excited State of Flavin Mononucleotide

    Directory of Open Access Journals (Sweden)

    Marie Asano

    2014-08-01

    Full Text Available We examined the effects of caffeic acid (CA and related compounds on 7-carboxyheptyl radical formation. This analysis was performed using a standard D2O reaction mixture containing 4.3 mM oleic acid, 25 ?M flavin mononucleotide (FMN, 160 mM phosphate buffer (pH 7.4, 10 mM cholic acid, 100 mM ?-(4-pyridyl-1-oxide-N-tert-butylnitrone, and 1 mM Fe(SO42(NH42 during irradiation with 7.8 J/cm2 at 436 nm. 7-Carboxyheptyl radical formation was inhibited by CA, catechol, gallic acid, chlorogenic acid, ferulic acid, noradrenalin, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, and 4-hydroxybenzoic acid. Quinic acid, benzoic acid, and p-anisic acid had no effect on radical formation. These results suggest that a phenol moiety is essential for these inhibitory effects. The fluorescence intensity of FMN decreased by 69% ± 2% after CA addition, suggesting that CA quenches the singlet excited state of FMN. When 1 mM CA was added to a standard reaction mixture containing 25 ?M FMN, 140 mM phosphate buffer (pH 7.4, and 10 mM 4-oxo-2,2,6,6-tetramethylpiperidine, the electron spin resonance signal of 4-oxo-2,2,6,6-tetramethylpiperidinooxy disappeared. This finding suggests that singlet oxygen was scavenged completely by CA. Therefore, CA appears to inhibit 7-carboxyheptyl radical formation by scavenging singlet oxygen and quenching the excited state of FMN.

  5. The B-cell lymphoma 2 (BCL2)-inhibitors, ABT-737 and ABT-263, are substrates for P-glycoprotein

    International Nuclear Information System (INIS)

    Highlights: ? The BCL2-inhibitor ABT-263 is a substrate for P-glycoprotein. ? Apoptosis is inhibited by P-glycoprotein expression. ? Overexpression of P-glycoprotein may contribute to resistance to ABT-263 or ABT-737. -- Abstract: Inhibition of BCL2 proteins is one of the most promising new approaches to targeted cancer therapy resulting in the induction of apoptosis. Amongst the most specific BCL2-inhibitors identified are ABT-737 and ABT-263. However, targeted therapy is often only effective for a limited amount of time because of the occurrence of drug resistance. In this study, the interaction of BCL2-inhibitors with the drug efflux transporter P-glycoprotein was investigated. Using 3H labelled ABT-263, we found that cells with high P-glycoprotein activity accumulated less drug. In addition, cells with increased P-glycoprotein expression were more resistant to apoptosis induced by either ABT-737 or ABT-263. Addition of tariquidar or verapamil sensitized the cells to BCL2-inhibitor treatment, resulting in higher apoptosis. Our data suggest that the BCL2-inhibitors ABT-737 and ABT-263 are substrates for P-glycoprotein. Over-expression of P-glycoprotein may be, at least partly, responsible for resistance to these BCL2-inhibitors.

  6. The B-cell lymphoma 2 (BCL2)-inhibitors, ABT-737 and ABT-263, are substrates for P-glycoprotein

    Energy Technology Data Exchange (ETDEWEB)

    Vogler, Meike, E-mail: mv62@le.ac.uk [MRC Toxicology Unit, University of Leicester, LE1 9HN Leicester (United Kingdom); Dickens, David, E-mail: David.Dickens@liverpool.ac.uk [Department of Molecular and Clinical Pharmacology, Institute of Translational Medicine, University of Liverpool, L69 3GL Liverpool (United Kingdom); Dyer, Martin J.S., E-mail: mjsd1@le.ac.uk [MRC Toxicology Unit, University of Leicester, LE1 9HN Leicester (United Kingdom); Owen, Andrew, E-mail: aowen@liverpool.ac.uk [Department of Molecular and Clinical Pharmacology, Institute of Translational Medicine, University of Liverpool, L69 3GL Liverpool (United Kingdom); Pirmohamed, Munir, E-mail: munirp@liv.ac.uk [Department of Molecular and Clinical Pharmacology, Institute of Translational Medicine, University of Liverpool, L69 3GL Liverpool (United Kingdom); Cohen, Gerald M., E-mail: gmc2@le.ac.uk [MRC Toxicology Unit, University of Leicester, LE1 9HN Leicester (United Kingdom)

    2011-05-06

    Highlights: {yields} The BCL2-inhibitor ABT-263 is a substrate for P-glycoprotein. {yields} Apoptosis is inhibited by P-glycoprotein expression. {yields} Overexpression of P-glycoprotein may contribute to resistance to ABT-263 or ABT-737. -- Abstract: Inhibition of BCL2 proteins is one of the most promising new approaches to targeted cancer therapy resulting in the induction of apoptosis. Amongst the most specific BCL2-inhibitors identified are ABT-737 and ABT-263. However, targeted therapy is often only effective for a limited amount of time because of the occurrence of drug resistance. In this study, the interaction of BCL2-inhibitors with the drug efflux transporter P-glycoprotein was investigated. Using {sup 3}H labelled ABT-263, we found that cells with high P-glycoprotein activity accumulated less drug. In addition, cells with increased P-glycoprotein expression were more resistant to apoptosis induced by either ABT-737 or ABT-263. Addition of tariquidar or verapamil sensitized the cells to BCL2-inhibitor treatment, resulting in higher apoptosis. Our data suggest that the BCL2-inhibitors ABT-737 and ABT-263 are substrates for P-glycoprotein. Over-expression of P-glycoprotein may be, at least partly, responsible for resistance to these BCL2-inhibitors.

  7. Effect of UV-C irradiation and low temperature storage on bioactive compounds, antioxidant enzymes and radical scavenging activity of papaya fruit.

    Science.gov (United States)

    Rivera-Pastrana, Dulce M; Gardea, Alfonso A; Yahia, Elhadi M; Martínez-Téllez, Miguel A; González-Aguilar, Gustavo A

    2014-12-01

    Mature green 'Maradol' papaya fruits were exposed to ultraviolet (UV)-C irradiation (1.48 kJ·m(-2)) and stored at 5 or 14 °C. Changes in total phenols, total flavonoids, enzymatic activities of superoxide dismutase (SOD), catalase (CAT) and peroxidase (POD), as well as the scavenging activity against 2,2-diphenyl-1picrylhydrazyl (DPPH) and 3-ethylbenzothiazoline-6-sulfonic acid (ABTS) radicals were investigated in peel and flesh tissues at 0, 5, 10 and 15 days of storage. UV-C irradiation increased significantly (P < 0.05) the flavonoid content (2.5 and 26 %) and ABTS radical scavenging activity (5.7 and 6 %) in flesh and peel at 14 °C respectively; and CAT activity (16.7 %) in flesh at 5 °C. Flavonoid contents, CAT and SOD activities were positively affected under low storage temperature (5 °C). DPPH and ABTS radical scavenging activities increased in both control and UV-C treated papaya peel during storage at 5 °C. UV-C irradiation effect on radical scavenging of papaya peel could be attributed to increased flavonoid content. Papaya antioxidant system was activated by UV-C and cold storage by increasing phenolic content and antioxidant enzymatic activities as a defense response against oxidative-stress. PMID:25477649

  8. Free radical reaction pathway, thermohemistry of peracetic acid homolysis and its application for phenol degradation: spectroscopic sti=udy and quantum chemistry calculations

    OpenAIRE

    Rokhina, E.V.; Makarova, K.; Golovina, E.A.; Van As, H.; Virkutyte, J.

    2010-01-01

    The homolysis of peracetic acid (PAA) as a relevant source of free radicals (e.g., •OH) was studied in detail. Radicals formed as a result of chain radical reactions were detected with electron spin resonance and nuclear magnetic resonance spin trapping techniques and subsequently identified by means of the simulation-based fitting approach. The reaction mechanism, where a hydroxyl radical was a primary product of O?O bond rupture of PAA, was established with a complete assessment of relevant...

  9. New easy method for obtaining approximate redox potentials of radicals, produced by 60Co-?-radiolysis, using heteropoly electrolytes of molybdenum and tungsten as electron acceptors. The redox potential of some alcohol and organic acid radicals

    International Nuclear Information System (INIS)

    The reducing ability of short lived radicals can be studied by reacting them with electron acceptors whose redox potential is known. Heteropoly electrolytes of molybdenum and tungsten are used for this purpose. The reduction of these species proceeds in distinct reduction steps producing the corresponding heteropoly blues until the potential of the next reduction step is more negative than the potential of the radical. The apparent redox potentials of some alcohols and formic acid radicals have been determined. (U.S.)

  10. Free radical scavenging activity of ethanolic extracts from herbs and spices commercialized in Brazil

    Scientific Electronic Library Online (English)

    Lilian Regina Barros, Mariutti; Gisela Pizarro de Mattos, Barreto; Neura, Bragagnolo; Adriana Zerlotti, Mercadante.

    2008-12-01

    Full Text Available Extratos etanólicos de 23 ervas e condimentos desidratados comercializados no Brasil foram analisados quanto as suas propriedades antioxidantes utilizando os radicais 2,2'-difenil-?-picrilhidrazil (DPPH•) e ácido 2,2'-azino-bis(3-etilbenzotiazolina-6-sulfônico) (ABTS•+), Trolox foi usado como referê [...] ncia para ambos radicais. As curvas cinéticas seguiram o modelo cinético de primeira ordem, e a partir destas foram calculadas as constantes de velocidade de (k obs). Os extratos de sálvia e de alecrim apresentaram as maiores capacidades redutoras de radicais livres, enquanto o extrato de cebola praticamente não apresentou atividade e o colorífico, um dos condimentos mais consumidos no Brasil, apresentou baixa atividade de aprisionamento de radicaisABTS•+. Três situações distintas foram observadas em relação à capacidade de aprisionar radicais DPPH•: (1) extratos, como os de alecrim e de louro, que apresentaram as mesmas concentrações eficientes (EC50), porém, valores de TEAC e velocidade de ação (k obs) distintos ; (2) extratos, como os de alho e de manjericão, que apresentaram valores similares de EC50 e TEAC, com valores distintos de k obs e (3) extratos com a mesma velocidade de ação que diferiram totalmente na capacidade de aprisionamento de radicais livres, como de pimenta preta, segurelha, noz moscada, alecrim e sálvia. Considerações semelhantes podem ser feitas para os resultados de ABTS•+. Osdois métodos apresentaram boa correlação de TEAC, indicando que a reatividade dos compostos presentes nos extratos etanólicos foi similar. A atividade redutora de ABTS•+ para pimenta da Jamaica, manjericão, cardamomo, cebolinha, colorífico, cominho, dill, louro, manjerona, salsinha e estragão foi reportada pela primeira vez. Abstract in english Ethanolic extracts from 23 different dried herbs and spices commercialized in Brazil were investigated for their free radical scavenging properties using the stable free radicals 2,2'-diphenyl-?-picrylhydrazyl (DPPH•) and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS•+), and Trolox a [...] s reference (TEAC) for both radicals. The kinetic curves for both radicals showed to follow the first order kinetics model and the decay rate constant (k obs) was calculated. For all the samples, the two methods showed a good linear TEAC correlation, indicating that the average reactivity of the compounds present in the ethanolic extracts was similar. Sage and rosemary extracts showed the highest free radical scavenging capacities, while onion showed negligible activity and colorifico, one of the most consumed spices in Brazil, showed low ABTS•+ scavenging activity. Three distinct situations were found for the extracts concerning the DPPH• scavenging capacities: (1) extracts, like rosemary and laurel, that presented the same efficient concentrations (EC50 ) but differed in the TEAC values and velocities of action (k obs), (2) extracts, such as garlic and basil, that showed similar EC50 and TEAC values, but different k obs values and (3) extracts that reacted at the same velocities but completely differed in the free radical scavenging capacities, like black pepper, savory, nutmeg, rosemary and sage. Similar considerations could be done for the ABTS•+ results. For the first time the ABTS•+ scavenging activity for allspice, basil, cardamom, chives, colorifico, cumin, dill, laurel, marjoram, parsley and tarragon was reported.

  11. Free radical scavenging activity of ethanolic extracts from herbs and spices commercialized in Brazil

    Directory of Open Access Journals (Sweden)

    Lilian Regina Barros Mariutti

    2008-12-01

    Full Text Available Ethanolic extracts from 23 different dried herbs and spices commercialized in Brazil were investigated for their free radical scavenging properties using the stable free radicals 2,2'-diphenyl-?-picrylhydrazyl (DPPH• and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid (ABTS•+, and Trolox as reference (TEAC for both radicals. The kinetic curves for both radicals showed to follow the first order kinetics model and the decay rate constant (k obs was calculated. For all the samples, the two methods showed a good linear TEAC correlation, indicating that the average reactivity of the compounds present in the ethanolic extracts was similar. Sage and rosemary extracts showed the highest free radical scavenging capacities, while onion showed negligible activity and colorifico, one of the most consumed spices in Brazil, showed low ABTS•+ scavenging activity. Three distinct situations were found for the extracts concerning the DPPH• scavenging capacities: (1 extracts, like rosemary and laurel, that presented the same efficient concentrations (EC50 but differed in the TEAC values and velocities of action (k obs, (2 extracts, such as garlic and basil, that showed similar EC50 and TEAC values, but different k obs values and (3 extracts that reacted at the same velocities but completely differed in the free radical scavenging capacities, like black pepper, savory, nutmeg, rosemary and sage. Similar considerations could be done for the ABTS•+ results. For the first time the ABTS•+ scavenging activity for allspice, basil, cardamom, chives, colorifico, cumin, dill, laurel, marjoram, parsley and tarragon was reported.Extratos etanólicos de 23 ervas e condimentos desidratados comercializados no Brasil foram analisados quanto as suas propriedades antioxidantes utilizando os radicais 2,2'-difenil-?-picrilhidrazil (DPPH• e ácido 2,2'-azino-bis(3-etilbenzotiazolina-6-sulfônico (ABTS•+, Trolox foi usado como referência para ambos radicais. As curvas cinéticas seguiram o modelo cinético de primeira ordem, e a partir destas foram calculadas as constantes de velocidade de (k obs. Os extratos de sálvia e de alecrim apresentaram as maiores capacidades redutoras de radicais livres, enquanto o extrato de cebola praticamente não apresentou atividade e o colorífico, um dos condimentos mais consumidos no Brasil, apresentou baixa atividade de aprisionamento de radicaisABTS•+. Três situações distintas foram observadas em relação à capacidade de aprisionar radicais DPPH•: (1 extratos, como os de alecrim e de louro, que apresentaram as mesmas concentrações eficientes (EC50, porém, valores de TEAC e velocidade de ação (k obs distintos ; (2 extratos, como os de alho e de manjericão, que apresentaram valores similares de EC50 e TEAC, com valores distintos de k obs e (3 extratos com a mesma velocidade de ação que diferiram totalmente na capacidade de aprisionamento de radicais livres, como de pimenta preta, segurelha, noz moscada, alecrim e sálvia. Considerações semelhantes podem ser feitas para os resultados de ABTS•+. Osdois métodos apresentaram boa correlação de TEAC, indicando que a reatividade dos compostos presentes nos extratos etanólicos foi similar. A atividade redutora de ABTS•+ para pimenta da Jamaica, manjericão, cardamomo, cebolinha, colorífico, cominho, dill, louro, manjerona, salsinha e estragão foi reportada pela primeira vez.

  12. Relative redox reactivity of radicals from substituted carboxylic acids and glycol towards heteropoly electrolytes of molybdenum and tungsten

    International Nuclear Information System (INIS)

    The reducing ability of various radicals is manifested by the extent of reduction they cause on various well characterized heteropoly compounds serving as electron acceptors. The reducing ability of several short lived radicals produced by 60Co-?-radiolysis of aqueous solution of mono and dicarboxylic acids, glycolic acid, glycol, and aminoacids have been determined. Whereas in most cases this test given as comparative measurement of the reducing ability, reaction of the radicals with the substrates in some cases complicates the matter presenting several exceptions to the rule. This is characteristic of all efforts to correlate kinetic and thermodynamic parameters such as rate and equilibrium constants, or similar parameters that are obtained by different methods such as E1/2 and E0. (orig.) 891 HK

  13. Edaravone, a free radical scavenger, protects liver against valproic acid induced toxicity

    Directory of Open Access Journals (Sweden)

    Cakmak Neziha Hacihasanoglu

    2015-01-01

    Full Text Available Valproic acid (VPA, is a well established anticonvulsant drug that has been increasingly used in the treatment of many forms of generalized epilepsy. Edaravone (EDA; 3-methyl-1-phenyl-2-pyrazoline-5-one is a potent free radical scavenger. In this study, we aimed to investigate the effects of EDA on VPA-induced hepatic damage. Male Sprague Dawley rats were divided into four groups. Group I was control animals. Group II was control rats given valproic acid (500 mg kg-1 day for seven days. Group III was given only EDA (30 mg kg-1day for seven days. Group IV was given VPA+EDA (in same dose and time. EDA and VPA were given intraperitoneally. On the 8th day of experiment, blood samples and liver tissue were taken. Serum aspartate and alanine aminotransferase, alkaline phosphatase and bilirubin levels, liver myeloperoxidase, xanthine oxidase, adenosine deaminase, Na+/K+ATPase, sorbitol dehydrogenase, glutamate dehydrogenase, DT-diaphorase, arginase and thromboplastic activities, lipid peroxidation, protein carbonyl levels were increased whereas paraoxonase, biotinidase activities and glutathione levels were decreased in VPA group. Application of EDA with VPA protected against VPA-induced effects. These results demonstrated that administration of EDA is a potentially beneficial agent to reduce hepatic damage in VPA induced hepatotoxicity, probably by decreasing oxidative stress.

  14. On the Origin of the Methyl Radical Loss from Deprotonated Ferulic and Isoferulic Acids: Electronic Excitation of a Transient Structure

    Science.gov (United States)

    Zhang, Xiaoping; Li, Fei; Lv, Huiqing; Wu, Yanqing; Bian, Gaofeng; Jiang, Kezhi

    2013-06-01

    Formation of radical fragments from even-electron ions is an exception to the "even-electron rule". In this work, ferulic acid (FA) and isoferulic acid (IFA) were used as the model compounds to probe the fragmentation mechanisms and the isomeric effects on homolytic cleavage. Elimination of methyl radical and CO2 are the two competing reactions observed in the CID-MS of [FA - H]- and [IFA - H]-, of which losing methyl radical violates the "even-electron rule". The relative intensity of their product ions is significantly different, and thereby the two isomeric compounds can be differentiated by tandem MS. Theoretical calculations indicate that both the singlet-triplet gap and the excitation energy decrease in the transient structures, as the breaking C-O bond is lengthened. The methyl radical elimination has been rationalized as the intramolecular electronic excitation of a transient structure with an elongating C-O bond. The potential energy diagrams, completed by the addition of the energy barrier of the radical elimination, have provided a reasonable explanation of the different CID-MS behaviors of [FA - H]- and [IFA - H]-.

  15. The formation and reaction of methyl radicals produced by direct photolysis of aqueous solutions of N-acetyl substituted aliphatic amino acids at 77 K

    International Nuclear Information System (INIS)

    Photolysis of amino acids, peptides and their derivatives leads to the formation of free radicals in these substances. The electron-spin-resonance spectra obtained directly after irradiation at 77 K were not very well resolved. They were recognizable as the superposition of the spectra of different types of photoproduced radicals. CH3 radicals are formed by U.V. irradiation if methyl groups are present in the molecule. These radicals were easily detectable because of their four line spectrum. The formation of methyl radicals and their reaction with undamaged molecules of N-acetyl-substituted amino acids have been investigated. The number of CH3 radicals present after a 30 min U.V. irradiation was higher if preceding U.V. irradiations and heat treatments were performed. The overall concentration of radicals was reduced only partially during this heat-treatment, while the CH3 radicals decayed completely. Other experiments showed that the rate of and the yield of CH3 radicals by U.V. irradiation increased with the dose of a preceding ?-irradiation. The results suggest that there are substances present which are responsible for the higher production rate of methyl radicals after a preceding treatment. It is assumed that radicals are precursors of the fast-formed CH3 radicals. (author)

  16. Picosecond pulse radiolysis of highly concentrated sulfuric acid solutions: evidence for the oxidation reactivity of radical cation H2O(•+).

    Science.gov (United States)

    Ma, Jun; Schmidhammer, Uli; Mostafavi, Mehran

    2014-06-12

    Aqueous solution of sulfuric acid is used as a suitable system to investigate the reactivity of the short-lived radical cation H2O(•+) which is generated by radiation in water. Ten aqueous solutions containing sulfuric acid with concentration from 1 to 18 mol?L(-1) are studied by picosecond pulse radiolysis. The absorbance of the secondary radical SO4(•-) (or HSO4(•)) formed within the 10 ps electron pulse is measured by a pulse-probe method in the visible range. The analysis of the kinetics show that the radicals of sulfuric acid are formed within the picosecond electron pulse via two parallel mechanisms: direct electron detachment by the electron pulse and oxidation by the radical cation of water H2O(•+). In highly concentrated solution when SO4(2-) is in contact with H2O(•+), the electron transfer becomes competitive against proton transfer with another water molecule. Therefore, H2O(•+) may act as an extremely strong oxidant. The maximum radiolytic yield of scavenged H2O(•+) is estimated to be 5.3 ± 0.1 × 10(-7) mol?J(-1). PMID:24824373

  17. Effects of gamma-ray-induced free radicals on the metal content and amino acid composition of human metallothionein-1

    Indian Academy of Sciences (India)

    Lieven Goossens

    2011-06-01

    Metallothioneins (MTs), a low-mass class of metalloproteins, are characterized by a high thiolate sulphur and metal content. MTs are involved in metal homeostasis and heavy metal detoxification, and are efficient scavengers of free radicals. This article describes zinc release from human MT-1 and modification of its amino acid composition when subjected to free radicals generated during gamma ray radiolysis. The effect of gamma ray radiolysis of untreated and metal-depleted human MT-1 was tested under multiple aerobic and anaerobic conditions at increasing irradiation doses. Under all conditions, a rapid increase of serine in the early stages of irradiation was observed. Irradiation for longer times led to cysteic acid formation, except under argon atmosphere. Several other amino acid concentrations gradually decreased. Formation of limited amounts of hydroxyproline, hydroxylysine and ornithine as well as some less common derivatives such as cystathionine occurred as side-effects.

  18. Polyphenolic Contents and Free Radical Scavenging Potential of Extracts from Leaves of Ocimum americanum L.

    Directory of Open Access Journals (Sweden)

    A.J. Afolayan

    2013-01-01

    Full Text Available This study assessed the polyphenolic contents and antioxidant activity of ethanol, butanol and ethyl acetate extracts of Ocimum americanum leaves using in vitro models. The ability of the extracts to scavenge 2,2-diphenyl-1-picrylhydrazyl (DPPH?, 2,2-azino-bis-(3-ethylbenzothiazoline-6-sulphonic acid (ABTS?+, hydrogen peroxide (H2O2, Nitric Oxide (NO and hydroxyl radical (OH? was investigated. The inhibition of lipid oxidation, reducing power, total flavonoids, phenols and flavonols contents of the extracts were also determined using spectrophotometric methods. The result revealed highest concentration of polyphenolic compounds in the ethanol extract followed by n-butanol while ethyl acetate extract contained the least concentration. Free radical scavenging potentials of the extracts were found to be proportional to their respective polyphenolic contents. This study provides evidence that O. americanum leaves contain biologically active components with effective antioxidant activity and thus could be used for the management of radical related diseases.

  19. Studies of cationic radicals in ?-irradiated single crystals of ?-aminoisobutyric acid and related ?-amino acids by electron spin resonance and SCF MO INDO calculation

    International Nuclear Information System (INIS)

    The cationic radical of the single crystal of ?-aminoisobutyric acid ? irradiated at 770K was identified as the deprotonated cation radical, NH2C(CH3)2COO, by X- and Q-band ESR including photobleaching measurement. The eigenvalues of the g tensor were determined to be 2.0052, 2.0021, and 2.0013. The eigenvector of g/sub max/(2.0052) is perpendicular to the molecular plane and the density axis of the unpaired electron orbital, i.e., the eigenvector of g/sub int/(2.0021), is parallel to the molecular axis (Y axis). The eigenvector of g/sub min/(2.0013) is on the molecular plane and perpendicular to the molecular axis. In addition to the hyperfine coupling by methyl protons, the hyperfine coupling by N was estimated, which is axially symmetric to the molecular axis and gives the unpaired electron density on N as 0.1 for 2p/sub y/ and 0.01 for 2s. These features were supported by SCF MO INDO calculations. The deprotonated cation radical and the hydrogen bonded cation radical, the precursor of the former, show similar unpaired electron orbitals consisting of 2p/sub y/s of the skeleton atoms, but the g anisotropy of the deprotonated cation radical is smaller compared with that of the cation radical. The cationic radicals of L-?-alanine and glycine were also similarly investigated and assigned to the deprotonated cation radicals as mentioned above

  20. Characterization of the Peroxidase Mechanism upon Reaction of Prostacyclin Synthase with Peracetic Acid. Identification of a Tyrosyl Radical Intermediate†

    OpenAIRE

    Yeh, Hui-Chun; Gerfen, Gary J.; Wang, Jinn-Shyan; Tsai, Ah-Lim; Wang, Lee-Ho

    2009-01-01

    Prostacyclin synthase (PGIS) is a membrane-bound class III cytochrome P450 that catalyzes an isomerization of prostaglandin H2, an endoperoxide, to prostacyclin. We report here the characterization of the PGIS intermediates in reactions with other peroxides, peracetic acid (PA), and iodosylbenzene. Rapid-scan stopped-flow experiments revealed an intermediate with an absorption spectrum similar to that of compound ES (Cpd ES), which is an oxo–ferryl (Fe(IV)=O) plus a protein-derived radical. C...

  1. Pulse radiolysis studies of short-lived species in solid amino acids as precursors of radicals detected by ESR

    International Nuclear Information System (INIS)

    The aim of the study was to bring closer solid state radiation chemistry and ESR spectroscopy by looking for precursors of free radicals which give ESR signals. It has been performed using time-resolved spectrophotometry (pulse radiolysis of the solid state) and diffuse reflection spectrophotometry. Alanine has been especially considered as the most investigated amino acid, important for radiation dosimetry. Absorption of the transient (? maximum at 460 nm) is identified as the species during deamination. The stable absorption spectrum with the ? maximum at 345 nm is due to the same radical as the one detected by ESR. Other amino acids: valine, threonine, glutamine and arginine show similar behaviour: microsecond spectrum of the intermediate appears always at longer wavelengths. The transient spectrum changes into stable absorption in UV of a lower wavelength. Along with the optical spectrum, the ESR spectrum appears, of similar stability. Also, other features indicate that the same radical is responsible for both the electronic and ESR spectrum. Some amino acids, like methionine give intensive transient absorption in the microsecond range but no ESR signal, after completion of consecutive fast reactions. In that case any optical absorption is due to the stable product of radiolysis, i.e. compounds with paired electrons only. (author)

  2. ABT-089, but not ABT-107, ameliorates nicotine withdrawal-induced cognitive deficits in C57BL6/J mice.

    Science.gov (United States)

    Yildirim, Emre; Connor, David A; Gould, Thomas J

    2015-04-01

    Nicotine withdrawal produces cognitive deficits that can predict relapse. Amelioration of these cognitive deficits emerges as a target in current smoking cessation therapies. In rodents, withdrawal from chronic nicotine disrupts contextual fear conditioning (CFC), whereas acute nicotine enhances this hippocampus-specific learning and memory. These modifications are mediated by ?2-subunit-containing (?2*) nicotinic acetylcholine receptors in the hippocampus. We aimed to test ABT-089, a partial agonist of ?4?2*, and ABT-107, an ?7 nicotinic acetylcholine receptor agonist, for amelioration of cognitive deficits induced by withdrawal from chronic nicotine in mice. Mice underwent chronic nicotine administration (12.6?mg/kg/day or saline for 12 days), followed by 24?h of withdrawal. At the end of withdrawal, mice received 0.3 or 0.6?mg/kg ABT-089 or 0.3?mg/kg ABT-107 (doses were determined through initial dose-response experiments and prior studies) and were trained and tested for CFC. Nicotine withdrawal produced deficits in CFC that were reversed by acute ABT-089, but not ABT-107. Cued conditioning was not affected. Taken together, our results suggest that modulation of hippocampal learning and memory using ABT-089 may be an effective component of novel therapeutic strategies for nicotine addiction. PMID:25426579

  3. Electron transfer from aromatic amino acids to guanine and adenine radical cations in pi stacked and T-shaped complexes.

    Science.gov (United States)

    Butchosa, Cristina; Simon, Sílvia; Voityuk, Alexander A

    2010-04-21

    Similar redox properties of the natural nucleobases and aromatic amino acids make it possible for electron transfer (ET) to occur between these sites in protein-nucleic acid complexes. Using DFT calculations, we estimate the ET rate from aromatic amino acid X (X = Phe, His, Tyr and Trp) to radical cations of guanine (G) and adenine (A) in dimers G-X and A-X with different arrangement of the subunits. We show that irrespective of the mutual orientation of the aromatic rings, the electronic interaction in the systems is strong enough to ensure effective ET from X to G(+) or A(+). Surprisingly, relatively high ET rates are found in T-shaped dimers. This suggests that pi stacking of nucleobases and aromatic amino acids is not required for feasible ET. In most complexes [G-X](+) and [A-X](+), we find the excess charge to be confined to a single site, either the nucleobase or amino acid X. Then, conformational changes may initiate migration of the radical cation state from the nucleobase to X and back. The ET process from Trp and Tyr to G(+) is found to be faster than deprotonation of G(+). Because the last reaction may lead to the formation of highly mutagenic species, the efficient repair of G(+) may play an important role in the protection of genomic DNA from oxidative damage. PMID:20449491

  4. E.s.r. of spin-trapped radicals in aqueous solutions of deuterated amino acids and alcohols

    International Nuclear Information System (INIS)

    Selectively deuterated compounds can be utilized in spin-trapping to obtain conclusive evidence for the structures of the trapped radicals. Radicals formed from DL-alanine-2-d1, DL-alanine-3,3,3-d3, DL-alanine-d4, glycine-d5, isopropyl-2-d1 alcohol, isopropyl-d7 alcohol and t-butyl-d9 alcohol were studied. The hydrogen abstraction, deamination and decarboxylation radicals generated from deuterated alanines were investigated by spin-trapping using t-nitrosobutane. Since nitroxides of the type XYZC-CH2-N(O)-tBu which contain an asymmetric centre next to the CH2 group exhibit unequal ?-proton splittings and temperature-dependent line width alternations, the effects of temperature on the e.s.r. spectra were studied. By these methods the structures of the trapped radicals were verified and the hyperfine coupling constants could be assigned without ambiguity. In ?-irradiated polycrystalline amino acids, the observed deuterium exchange can be conveniently surveyed by dissolution in aqueous solutions containing t-nitrosobutane. (author)

  5. Spectroscopic studies on the antioxidant activity of p-coumaric acid

    Science.gov (United States)

    Kiliç, Ismail; Ye?ilo?lu, Ye?im

    2013-11-01

    p-coumaric acid (4-hydroxycinnamic acid), a phenolic acid, is a hydroxyl derivative of cinnamic acid. It decreases low density lipoprotein (LDL) peroxidation and reduces the risk of stomach cancer. In vitro radical scavenging and antioxidant capacity of p-coumaric acid were clarified using different analytical methodologies such as total antioxidant activity determination by ferric thiocyanate, hydrogen peroxide scavenging, 1,1-diphenyl-2-picryl-hydrazyl free radical (DPPH) scavenging, 2,2?-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) (ABTS) radical scavenging activity and superoxide anion radical scavenging, ferrous ions (Fe2+) chelating activity and ferric ions (Fe3+) reducing ability. p-Coumaric acid inhibited 71.2% lipid peroxidation of a linoleic acid emulsion at 45 ?g/mL concentration. On the other hand, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), ?-tocopherol and ascorbic acid displayed 66.8%, 69.8%, 64.5% and 59.7% inhibition on the peroxidation of linoleic acid emulsion at the same concentration, respectively. In addition, p-coumaric acid had an effective DPPHrad scavenging, ABTSrad + scavenging, superoxide anion radical scavenging, hydrogen peroxide scavenging, ferric ions (Fe3+) reducing power and ferrous ions (Fe2+) chelating activities. Also, those various antioxidant activities were compared to BHA, BHT, ?-tocopherol and ascorbic acid as references antioxidant compounds. These results suggested that p-coumaric acid can be used in the pharmacological and food industry because of these properties.

  6. Influence of fatty acid on lipase-catalyzed synthesis of ascorbyl esters and their free radical scavenging capacity.

    Science.gov (United States)

    Stojanovi?, Marija; Carevi?, Milica; Mihailovi?, Mladen; Veli?kovi?, Dušan; Dimitrijevi?, Aleksandra; Milosavi?, Nenad; Bezbradica, Dejan

    2015-07-01

    Fatty acid (FA) ascorbyl esters are recently emerging food, cosmetic, and pharmaceutical additives, which can be prepared in an eco-friendly way by using lipases as catalysts. Because they are amphiphilic molecules, which possess high free radical scavenging capacity, they can be applied as liposoluble antioxidants as well as emulsifiers and biosurfactants. In this study, the influence of a wide range of acyl donors on ester yield in lipase-catalyzed synthesis and ester antioxidant activity was examined. Among saturated acyl donors, higher yields and antioxidant activities of esters were achieved when short-chain FAs were used. Oleic acid gave the highest yield overall and its ester exhibited a high antioxidant activity. Optimization of experimental factors showed that the highest conversion (60.5%) in acetone was achieved with 5 g L(-1) of lipase, 50 mM of vitamin C, 10-fold molar excess of oleic acid, and 0.7 mL L(-1) of initial water. Obtained results showed that even short- and medium-chain ascorbyl esters could be synthesized with high yields and retained (or even exceeded) free radical scavenging capacity of l-ascorbic acid, indicating prospects of broadening their application in emulsions and liposomes. PMID:25224149

  7. Antioxidant capacity of hydrolyzed animal by-products and relation to amino acid composition and peptide size distribution.

    Science.gov (United States)

    Damgaard, Trine; Lametsch, René; Otte, Jeanette

    2015-10-01

    The antioxidative capacity of six different tissue hydrolysates (porcine colon, heart and neck and bovine lung, kidney and pancreas) were tested by three different assays monitoring iron chelation, ABTS radical scavenging and inhibition of lipid oxidation in emulsions, respectively. The hydrolysates were also investigated with respect to amino acid composition and peptide size distribution. The hydrolysates contained peptides ranging from 20 kDa to below 100 Da with a predominance of peptides with low molecular weight (53.8 to 89.0 % below 3 kDa). All hydrolysates exhibited antioxidant activity as assessed with all three methods; inhibition of lipid oxidation ranging from 72 to 88 % (at a final protein concentration of 7 mg/mL), iron chelation capacity from 23 to 63 % (at 1.1 mg/mL), and ABTS radical scavenging from 38 to 50 % (at 10 ?g /mL). The antioxidant activity did not correlate with the proportion of low molecular weight peptides in the hydrolysed tissues, but with the content of specific amino acid residues. The ABTS radical scavenging capacity of the tissues was found to correlate with the content of Trp, Tyr, Met and Arg, whereas the ability to inhibit the oxidation of lineoleic acid correlated with the content of Glu and His. The chosen animal by-products thus represent a natural source of antioxidants with potential for food application. PMID:26396396

  8. Reaction pathway of the degradation of the p-hydroxybenzoic acid by sulfate radical generated by ionizing radiations

    International Nuclear Information System (INIS)

    The degradation of p-hydroxybenzoic acid (HBA) in aqueous solutions by ionizing radiation was studied. The phenolic pollutant was easily removed by the electron beam irradiation, as more than 80% of the initial 100 µM introduced was degraded for a dose of 600 Gy. It was shown that the addition of persulfate, producing the sulfate radical as additional reactive species, induced a change in the reaction pathway. LC–MS analyses were performed in order to identify the different by-products formed. In the absence of persulfate, the main by-product formed was 3,4-dihydroxybenzoic acid, while in presence of persulfate, 1,4-benzoquinone was detected and the hydroxylated by-products were not present. A reaction pathway of HBA degradation by hydroxyl and sulfate radicals was proposed from the identification of the chemical structure of the different by-products detected. The influences of pH and dissolved oxygen were also studied. A high decline of HBA degradation was observed at pH 11 compared to pH 4.5, this decrease was minimized in the presence of persulfate. The dissolved oxygen concentration was found to be a limiting parameter of HBA degradation, however an excess of dissolved oxygen in solution did not improve the degradation to a large extent. - Highlights: • p-Hydroxybenzoic acid (HBA) is easily removed by e-beam irradiation. • The sulfate radicals formed from persulfate induce loss of the benzoic acid skeleton. • The dissolved oxygen concentration is a limiting parameter of the HBA degradation. • The effect of pH is minimized in presence of persulfate

  9. Reactivity of OH radicals with chlorobenzoic acids-A pulse radiolysis and steady-state radiolysis study

    DEFF Research Database (Denmark)

    Zona, Robert; Solar, Sonja; Getoff, Nikola; Sehested, Knud; Holcman, Jerzy

    2010-01-01

    The reactions of OH radicals with 2-, 3-, 4-chlorobenzoic acids (ClBzA) and chlorobenzene (ClBz), k(OH+substrates)=(4.5?6.2)×109 dm3 mol?1 s?1, have been studied by pulse radiolysis in N2O saturated solutions. The absorption maxima of the OH-adducts were in the range of 320?340 nm. Their decay was according to a second-order reaction, 2k=(1?9)×108 dm3 mol?1 s?1. In the presence of N2O/O2 the formation of peroxyl radicals was detectable for 2-, 4-ClBzA and ClBz, k(OH-adduct+O2)=(2?4)×107 dm3 mol?...

  10. Reactions of OH-radicals with hydroxylated and methoxylated benzoic acids and cinnamic acids. Radiation-induced chemical changes in mushrooms

    International Nuclear Information System (INIS)

    In the first part of this work the radiation induced chemical changes of methoxylated and hydroxylated benzoic acids and cinnamic acids were investigated. Methoxylated compounds were also used as model components for acid derivatives with no free-OH groups. The latter are essentials parts of vegetable foodstuff. A comparison of the radiolytic behaviour of single substituted methoxy- and hydroxybenzoic acids was given at first, data of literature was included. The priority of the investigation was the hydroxylation process induced by OH-radicals. The OH-adduct distribution is generally the same for the hydroxy- as well as for the methoxybenzoic acid isomers. This could be proved by oxidation of these OH-adducts with K3Fe(CN)6. In the presence of air 68-77 % of the hydroxybenzoic acids are converted into hydroxylation products, whereas with the methoxylated acids this reaction leads only to about 10%. An explanation gives the different decay pathways of the intermediate peroxylradical. The multiple methoxy- and hydroxybenzoic acids show three different reaction possibilities: hydroxylation, replacement of -OCH3 by -OH and -in case of the cinnamic acids-oxidative decomposition of the rest of the propenic acid under formation of the corresponding benzaldehydes. All these reactions can be expected when irradiating foodstuff, containing these acid compounds. The characteristic formation of these components and their linear dose/concentration relationship make these substrates very promising for the use as markers for irradiation treatment of foodstuff. The second part of this work deals with the gamma-radiation induced chemical changes in mushrooms. The irradiated and non-irradiated samples were freeze-dried and purified from matrix components chromatographically on polyamid columns. In case of the phenolic compounds for 4-hydroxybenzoic acid and three unknown components linear dose/concentration relationships could be obtained. Two of these unknown compounds seem to be promising for a use as marker for irradiation treatment of mushrooms. (author)

  11. Measurments of nitrous acid, nitrate radicals, formaldehyde and nitrogen dioxide for the Southern California Air Quality Study by differential optical

    International Nuclear Information System (INIS)

    This paper reports that two rapid scanning (?3000 scan min-1) differential optical absorption spectrometers were interfaced to 25 m basepath open, multiple reflection systems operated routinely at a total optical path of 800 m at Long Beach and Claremont, CA during the 1987 Southern California Air Quality Study. These instruments permitted measurements of atmospheric concentrations of nitrous acid, nitrogen dioxide and formaldehyde at the part per billion levels, and detection of the nitrate radicals with sensitivity of several tens of parts per trillion

  12. Photoinitiated Radical Carbonylation Using [11C]Carbon Monoxide : 11C-Labelling of Aliphatic Carboxylic Acids, Esters, and Amides

    OpenAIRE

    Itsenko, Oleksiy

    2005-01-01

    One-step photoinitiated free radical carbonylation was employed for the rapid (5–7 min) labelling of aliphatic carboxylic acids, esters, and amides with a short-lived positron emitter 11C (t½ = 20.3 min) at the carbonyl position. The labelled compounds were synthesized from alkyl iodides (0.05–0.1 mmol), [11C]carbon monoxide, and appropriate nucleophiles. Decay-corrected radiochemical yields were up to 74%; conversion of [11C]carbon monoxide reached 85–90%; specific radioactivity was 158–192 ...

  13. Block-gradient copolymers of styrene and acrylic acid synthesized by nitroxide-mediated radical polymerization.

    Czech Academy of Sciences Publication Activity Database

    Borisova, O.; Billon, L.; Zaremski, M.; Grassl, B.; Bakaeva, Zulfiya; Lapp, A.; Št?pánek, Petr; Borisov, O.

    Granada : European Polymer Federation, 2011. s. 513. ISBN 978-84-694-3124-5. [European Polymer Congress 2011, Congress of the Specialized Group of Polymers /12./. 26.06.2011-01.07.2011, Granada] Institutional research plan: CEZ:AV0Z40500505 Keywords : block-gradient copolymers * radical polymerization Subject RIV: CD - Macromolecular Chemistry

  14. Caracterização físico-química de polpas de frutos da Amazônia e sua correlação com a atividade anti-radical livre Physical and chemical characterization of fruit pulps from Amazonia and their correlation to free radical scavenger activity

    Directory of Open Access Journals (Sweden)

    Gisele André Baptista Canuto

    2010-12-01

    Full Text Available Características físico-químicas (cor, pH, acidez total titulável, sólidos solúveis totais, conteúdo de lipídios e umidade e níveis de compostos bioativos (ácido ascórbico, fenólicos totais foram determinados em quinze amostras de polpas de frutos procedentes da região Amazônica (abiu, acerola, açaí, araçá-boi, bacaba, bacuri, buriti, cajá, cajarana, caju, cupuaçu, graviola, murici, noni e tamarindo. A atividade de radicais livres foi avaliada pelo método de ABTS. Algumas polpas apresentaram alta potencialidade antioxidante, associada com a atividade antirradicais livres obtida e os conteúdos dos componentes bioativos como compostos fenólicos e ácido ascórbico, destacando-se acerola e acaí. O conteúdo total de compostos fenólicos foi correlacionado à capacidade antioxidante das polpas.Physical and chemical characteristics (color, pH, titratable acidity, total soluble solids, lipid content, moisture and levels of bioactive compounds (ascorbic acid, total phenolics were determined in fifteen samples of fruit pulps from Amazonia (abiu, acerola, açaí, araça-boi, bacaba, bacuri, buriti, cajá, cajarana, caju, cupuaçu, graviola, murici, noni e tamarindo. The free radical scavenger activity was evaluated by the ABTS assay. Some pulps presented high antioxidant potential, associated with the free radical scavenger activity measured and the content of bioactive components, such as phenolic compounds and ascorbic acid, especialy in acerola and açaí. The total phenolic content was correlated to antioxidant capacity of pulps.

  15. Immobilized transition metal-based radical scavengers and their effect on durability of Aquivion® perfluorosulfonic acid membranes

    Science.gov (United States)

    D'Urso, C.; Oldani, C.; Baglio, V.; Merlo, L.; Aricò, A. S.

    2016-01-01

    A simple and broadly applicable preparation procedure to obtain silica-supported transition metal (namely Cr, Co and Mn)-based radical scavengers, containing sulfonic acid functionalities, is reported. These systems are widely characterised in terms of structure, bulk and surface composition and morphology by X-Ray Diffraction (XRD), X-Ray Fluorescence (XRF), X-Ray Photoelectron Spectroscopy (XPS) and Transmission Electron Microscopy (TEM). The scavenger material is loaded in ePTFE reinforced membranes prepared from Aquivion® perfluorosulfonic acid (PFSA) dispersions. All these composite membranes show longer lifetime in Accelerated Stress Tests (AST) and reduced fluoride release in Fenton's tests than the scavenger-free membranes without any loss in electrochemical performance. The Cr-scavenger-based polymer electrolyte shows a three-time larger stability than the pristine membrane.

  16. Tropospheric chemistry of natural hydrocarbons, aldehydes, and peroxy radicals: Their connections to sulfuric acid production and climate effects

    International Nuclear Information System (INIS)

    Recent work has shown that natural hydrocarbon emissions can significantly affect the levels of urban and regional tropospheric ozone. We report on the reactivities of these biogenic trace gases, particularly isoprene, focusing on their importance in the production of aldehydes and peroxy radicals, leading to increased levels of hydrogen over regional forests. Hydrogen peroxide can lead to the wet oxidation of sulfur dioxide to acidic sulfate in aerosols, fogs, and clouds. In turn, acidic sulfate can act to as a light scattering aerosol and a source of cloud condensation nuclei (CCN), potentially leading to global cooling. Aerosol sulfate and other dissolved organic and inorganic compounds can also play important roles as a greenhouse species in the lower troposphere

  17. Reactivity of OH radicals with chlorobenzoic acids-A pulse radiolysis and steady-state radiolysis study

    Energy Technology Data Exchange (ETDEWEB)

    Zona, Robert [University of Vienna, Department of Nutritional Sciences, Section Radiation Biology, UZAII, Althanstrasse 14, A-1090 Vienna (Austria); Solar, Sonja, E-mail: sonja.solar@univie.ac.a [University of Vienna, Department of Nutritional Sciences, Section Radiation Biology, UZAII, Althanstrasse 14, A-1090 Vienna (Austria); Getoff, Nikola [University of Vienna, Department of Nutritional Sciences, Section Radiation Biology, UZAII, Althanstrasse 14, A-1090 Vienna (Austria); Sehested, Knud; Holcman, Jerzy [RISO National Laboratory Environmental Science and Technology Department, DK-4000, Roskilde (Denmark)

    2010-05-15

    The reactions of OH radicals with 2-, 3-, 4-chlorobenzoic acids (ClBzA) and chlorobenzene (ClBz), k({sup c}entre dotOH+substrates)=(4.5-6.2)x10{sup 9} dm{sup 3} mol{sup -1} s{sup -1}, have been studied by pulse radiolysis in N{sub 2}O saturated solutions. The absorption maxima of the OH-adducts were in the range of 320-340 nm. Their decay was according to a second-order reaction, 2k=(1-9)x10{sup 8} dm{sup 3} mol{sup -1} s{sup -1}. In the presence of N{sub 2}O/O{sub 2} the formation of peroxyl radicals was detectable for 2-, 4-ClBzA and ClBz, k(OH-adduct+O{sub 2})=(2-4)x10{sup 7} dm{sup 3} mol{sup -1} s{sup -1}, while this reaction for 3-ClBzA was too slow to be registered. In the presence of N{sub 2}O the degradation rates induced by gamma radiation were very similar for all chlorobenzoic acids, yet the chloride formation was distinctly higher for 3-ClBzA. In the presence of oxygen the initial degradation of 2-and 4-ClBzA equaled the OH-radical concentration, whereas in case of 3-ClBzA only approx60% of {sup c}entre dotOH led to degradation. The order for the efficiency of dehalogenation was 4->2->3-ClBzA. Several primary radiolytic products could be detected by HPLC. To evaluate the toxicity of final products a bacterial bioluminescence test was carried out.

  18. Characterization of the Peroxidase Mechanism upon Reaction of Prostacyclin Synthase with Peracetic Acid. Identification of a Tyrosyl Radical Intermediate†

    Science.gov (United States)

    Yeh, Hui-Chun; Gerfen, Gary J.; Wang, Jinn-Shyan; Tsai, Ah-Lim; Wang, Lee-Ho

    2010-01-01

    Prostacyclin synthase (PGIS) is a membrane-bound class III cytochrome P450 that catalyzes an isomerization of prostaglandin H2, an endoperoxide, to prostacyclin. We report here the characterization of the PGIS intermediates in reactions with other peroxides, peracetic acid (PA), and iodosylbenzene. Rapid-scan stopped-flow experiments revealed an intermediate with an absorption spectrum similar to that of compound ES (Cpd ES), which is an oxo–ferryl (Fe(IV)=O) plus a protein-derived radical. Cpd ES, formed upon reaction with PA, has an X-band (9 GHz) EPR signal of g = 2.0047 and a half-saturation power, P1/2, of 0.73 mW. High-field (130 GHz) EPR reveals the presence of two species of tyrosyl radicals in Cpd ES with their g-tensor components (gx, gy, gz) of 2.00970, 2.00433, 2.00211 and 2.00700, 2.00433, 2.00211 at a 1:2 ratio, indicating that one is involved in hydrogen bonding and the other is not. The line width of the g = 2 signal becomes narrower, while its P1/2 value becomes smaller as the reaction proceeds, indicating migration of the unpaired electron to an alternative site. The rate of electron migration (~0.2 s?1) is similar to that of heme bleaching, suggesting the migration is associated with the enzymatic inactivation. Moreover, a g = 6 signal that is presumably a high-spin ferric species emerges after the appearance of the amino acid radical and subsequently decays at a rate comparable to that of enzymatic inactivation. This loss of the g = 6 species thus likely indicates another pathway leading to enzymatic inactivation. The inactivation, however, was prevented by the exogenous reductant guaiacol. The studies of PGIS with PA described herein provide a mechanistic model of a peroxidase reaction catalyzed by the class III cytochromes P450. PMID:19187034

  19. Reactivity of OH radicals with chlorobenzoic acids-A pulse radiolysis and steady-state radiolysis study

    DEFF Research Database (Denmark)

    Zona, Robert; Solar, Sonja

    2010-01-01

    The reactions of OH radicals with 2-, 3-, 4-chlorobenzoic acids (ClBzA) and chlorobenzene (ClBz), k(OH+substrates)=(4.5?6.2)×109 dm3 mol?1 s?1, have been studied by pulse radiolysis in N2O saturated solutions. The absorption maxima of the OH-adducts were in the range of 320?340 nm. Their decay was according to a second-order reaction, 2k=(1?9)×108 dm3 mol?1 s?1. In the presence of N2O/O2 the formation of peroxyl radicals was detectable for 2-, 4-ClBzA and ClBz, k(OH-adduct+O2)=(2?4)×107 dm3 mol?1 s?1, while this reaction for 3-ClBzA was too slow to be registered. In the presence of N2O the degradation rates induced by gamma radiation were very similar for all chlorobenzoic acids, yet the chloride formation was distinctly higher for 3-ClBzA. In the presence of oxygen the initial degradation of 2-and 4-ClBzA equaled the OH-radical concentration, whereas in case of 3-ClBzA only 60% of OH led to degradation. The order for the efficiency of dehalogenation was 4->2->3-ClBzA. Several primary radiolytic products could be detected by HPLC. To evaluate the toxicity of final products a bacterial bioluminescence test was carried out.

  20. Antioxidant activity and free radical-scavenging capacity of Gynura divaricata leaf extracts at different temperatures

    Directory of Open Access Journals (Sweden)

    Wan Chunpeng

    2011-01-01

    Full Text Available Background: Extraction temperature influences the total phenolic content (TPC, total flavonoid content (TFC of medicinal plant extracts to a great extend. TPC and TFC are the principle activity constituents present in the plant. The effects of extraction temperature on TPC, TFC and free radical-scavenging capacity of Gynura divaricata leaf extracts are worth to study. Materials and Methods: Folin-Ciocalteu and aluminum chloride colorimetric assay were used to determine the TPC and TFC of Gynura divaricata leaf extracts at different temperatures. The antioxidant and free radical-scavenging activity were measured by 1,1-diphenyl-2-picrylhydrazyl (DPPH, 2,2-azino-bis-(3-ethylbenzthiazoline-6-sulfonic acid (ABTS and phosphomolybdenum methods. Results: TPC and TFC were significantly elevated with increasing extraction temperature (from 40°C to 100°C. However, TPC and TFC were not significantly different (P > 0.05 at the extraction temperatures 90°C and 100°C. Also, the extracts obtained at a higher temperature exhibited a significant free radical-scavenging activity compared with extraction at lower temperatures (P < 0.05. The TPCs (13.95-36.68 mg gallic acid equivalent/g dry material were highly correlated with DPPH (R2 = 0.9229, ABTS (R2 = 0.9951 free radical-scavenging capacity, and total antioxidant activity (R2 = 0.9872 evaluated by phosphomolybdenum method. Conclusion: The TPC and TFC of G. divaricata leaf was significantly influenced by the extraction temperatures, which were the main antioxidant constituents present in the G. divaricata plant.

  1. Radical Couplings as Key Steps for the Preparation of Derivatives of Nonactic Acid

    OpenAIRE

    Loiseau, François; Simone, Jean-Mary; Carcache, David; Bobal, Pavel; Neier, Reinhard

    2010-01-01

    Free radical couplings from furan, as cheap starting material, were studied in view of developing a rapid strategy en route to the synthesis of derivatives of nonactin. The chain containing the alcohol function was introduced in one or two steps in 86% yield. For the introduction of the second chain with the ester function two different coupling methods were tested. Starting from the advanced intermediates obtained nonactin derivatives can be prepared by catalytic hydrogenation of the furan r...

  2. Oxidation of Amino Acids by Chlorpromazine Cation Radical and Co-Catalysis by Chlorpromazine

    OpenAIRE

    Manoel L. de Menezes; Fernanda S. Graciani; Giovana B. Quaggio; Ximenes, Valdecir F.

    2012-01-01

    The long-tem use of chlorpromazine (CPZ) may cause severe side effects. This property of CPZ might be related to pro-oxidant effects of the chlorpromazine cation radical (CPZ·+), which can be easily generated by catalytic action of peroxidases, including the neutrophil myeloperoxidase (MPO) and by methemoglobin. Aiming the comprehension of a putative physiological effect of CPZ·+ upon biomolecules, in this work we studied the reactivity of CPZ<...

  3. Chemical Constituents with Free-Radical-Scavenging Activities from the Stem of Microcos paniculata

    Directory of Open Access Journals (Sweden)

    Yu Chen

    2010-08-01

    Full Text Available The free-radical-scavenging activities of various solvent extracts of Microcos paniculata were evaluated through in vitro model systems, such as 1,1-diphenyl-2-picrylhydrazyl (DPPH, 2,2'-azino-bis-(3-ethylbenzothiazoline-6-sulfonate (ABTS and Co (II EDTA-induced luminol chemiluminescence by flow injection. In all three of these systems the ethyl acetate (EtOAc extract showed the highest free-radical-scavenging activity compared with the other three (n-BuOH, water and petroleum ether extracts. Free-radical-scavenging assay-guided chromatographic separation of the EtOAc extract, using a normal-phase and reverse-phase silica gel column chromatography yielded five compounds: a new triterpene named methyl 3b-O-p-hydroxy-E-cinnamoyloxy-2a,23-dihydroxyolean-12-en-28-oate (1, whose spectral data are presented for the first time, together with four known compounds, epicatechin (2, 3-trans-feruloyl maslinic acid (3, maslinic acid (4 and sucrose (5. All of the compounds were isolated from Microcos paniculata for the first time. The compounds were identified by spectroscopic methods. Among them, compound 2 displayed significant free-radical-scavenging activity which is similar to that of standard antioxidant ascorbic acid (VC and therefore may be a promising natural antioxidant.

  4. Neuroprotective and free radical scavenging activities of phenolic compounds from Hovenia dulcis.

    Science.gov (United States)

    Li, Gao; Min, Byung-Sun; Zheng, Changji; Lee, Joongku; Oh, Sei-Ryang; Ahn, Kyung-Seop; Lee, Hyeong-Kyu

    2005-07-01

    The EtOAc-soluble fraction from a methanolic extract of Hovenia dulcis Thunb. exhibited neuroprotective activity against glutamate-induced neurotoxicity in mouse hippocampal HT22 cells. The neuroprotective activity-guided isolation resulted in 8 phenolic compounds (1-8), such as vanillic acid (1), ferulic acid (2), 3,5-dihydroxystilbene (3), (+)-aromadendrin (4), methyl vanillate (5), (-)-catechin (6), 2,3,4-trihydrobenzoic acid (7), and (+)-afzelechin (8). Among these, compounds 6 and 8 had a neuroprotective effect on the glutamate-induced neurotoxicity in HT22 cells. Furthermore, compound 6 had a DPPH free radical scavenging effect with an IC50 value of 57.7 microM, and a superoxide anion radical scavenging effect with an IC50 value of 8.0 microM. Both compounds 6 and 8 had ABTS cation radical scavenging effects with IC50 values of 7.8 microM and 23.7 microM, respectively. These results suggest that compounds 6 and 8 could be neuroprotectants owing to their free radical scavenging activities. PMID:16114495

  5. Radical-scavenging compounds from olive tree (Olea europaea L.) wood.

    Science.gov (United States)

    Pérez-Bonilla, Mercedes; Salido, Sofía; van Beek, Teris A; Altarejos, Joaquín

    2014-01-01

    The purpose of this study was to complete knowledge on the chemical composition and radical-scavenging activity of olive tree wood. Two new monoterpene glycosides, (-)-oleuropeic acid 6'-O-?-D-glucopyranosyl ester (6a) and (-)-perillic acid 1'-O-?-D-primeverosyl ester (8), together with the known compounds (-)-oleuropeic acid (1), (-)-olivil (2), the aldehydic form of oleuropein aglycone (3), (+)-1-hydroxypinoresinol 1-O-?-D-glucopyranoside (4), (-)-oleuropeic acid 1'-O-?-D-glucopyranosyl ester (5), (-)-oleuropeic acid 6'-O-?-D-glucopyranosyl ester (6b), and (-)-olivil 4-O-?-D-glucopyranoside (7) were isolated from an ethyl acetate extract. The radical scavengers found (2-4 and 7) were detected and isolated with the help of the online HPLC-DAD-DPPH/ABTS technique. Compounds 2-4 and 7 displayed a higher antioxidative effect against the free radical DPPH than the reference BHT and lower than hydroxytyrosol, whereas compounds 1, 5, 6a, 6b, and 8 showed no activity. PMID:24328093

  6. AVALIAÇÃO DO RADICAL N,N-DIETIL-1,4-FENILENODIAMINO (DEPD•+ COMO SONDA ESPECTROFOTOMÉTRICA PARA DETERMINAÇÃO DA CAPACIDADE ANTIOXIDANTE EM BEBIDAS

    Directory of Open Access Journals (Sweden)

    Rosicleide Viturina dos Santos

    2015-08-01

    Full Text Available AbstractMany well-established methods for determining the antioxidant capacities in several samples have been described in literature. However, DPPH (2,2-diphenyl-1-picrylhydrazyl and ABTS (2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid are the main two methods that utilize radicals as spectrophotometric probes for analysis. Nevertheless, these methods have certain limitations because of their slower kinetics, solvent polarity effects, the hydrophilicity and lipophilicity of the compounds, chemical costs, etc. In this study, a spectrophotometric method for determining the antioxidant capacity in beverages was developed based on an exploration of the cation radical derived from DEPD. This method was based on the oxidation of aromatic amines with Fe(III ions at pH 4.0, which leads to their corresponding purple cation radicals (DEPD•+ with ?max values at 500 and 540 nm. The addition of an antioxidant after the formation of the radical leads to a reduction in color intensity that is proportional to the antioxidant concentration in the medium. Results obtained using this method were compared with the Folin-Ciocalteau, ABTS and DPPH methods in terms of applications in wines, teas, and infusions samples. Linear correlation analysis at a 95% confidence level was employed to compare the results, which were in good agreement with a correlation coefficient of r > 0.9000. Thus, the developed method was simple, accurate, and consistent with other assays for the determination of the total amount of phenolic compounds and antioxidant capacity.

  7. beta-Scission of C-3 (beta-carbon) alkoxyl radicals on peptides and proteins : a novel pathway which results in the formation of alpha-carbon radicals and the loss of amino acid side chains

    DEFF Research Database (Denmark)

    Headlam, H A; Mortimer, A

    2000-01-01

    Exposure of proteins to radicals in the presence of O(2) brings about multiple changes in the target molecules. These alterations include oxidation of side chains, fragmentation, cross-linking, changes in hydrophobicity and conformation, altered susceptibility to proteolytic enzymes, and formation of new reactive groups, including hydroperoxides. These processes can result in the loss of structural or enzymatic activity. Backbone fragmentation is known to occur via a number of mechanisms, most of which involve hydrogen abstraction from the alpha-carbon site on the backbone. In this study, we demonstrate that initial attack at a side chain site, the beta-position (C-3), can give rise to formation of alpha-carbon radicals, and hence backbone cleavage, via the formation and subsequent beta-scission of C-3 alkoxyl radicals. This beta-scission reaction is rapid (k estimated to be >10(7) s(-)(1)) even with primary alkoxyl radicals derived from Ala residues, and occurs when the alkoxyl radicals are generated from a variety of precursors, including hydroperoxides and nitrate esters. These reactions release the former side chain as a reactive aldehyde or ketone; thus, Ala peptides release high yields of methanal (formaldehyde). This product has been quantified with a number of oxidized peptides and proteins, and can account for up to 64% of the initial attacking radicals with some Ala peptides. When quantified together with the hydroperoxide precursors, these species account for up to 80% of the initial radicals, confirming that this is a major process. Methanal causes cell toxicity and DNA damage and is an animal carcinogen and a genotoxic agent in human cells. Thus, the formation and subsequent reaction of alkoxyl radicals formed at the C-3 position on aliphatic amino acid side chains on peptides and proteins can give rise to both backbone fragmentation and the release of further reactive species which can cause cell toxicity and mutagenicity.

  8. Peroxyacetic acid in urban and rural atmosphere: concentration, feedback on PAN-NOx cycle and implication on radical chemistry

    Directory of Open Access Journals (Sweden)

    J. L. Li

    2009-10-01

    Full Text Available Peroxyacetic Acid (PAA is one of important atmospheric organic peroxides, which have received increasing attention for their potential contribution to the oxidation capacity of the troposphere and the formation of secondary aerosols. We report here that, for the first time, a series of data for atmospheric PAA concentrations at urban and rural sites, from five field campaigns carried out in China in summer 2006, 2007 and 2008. For these five measurements, daytime mean PAA concentrations on sunlit days were 0.02–0.14 ppbv with a maximum level of ~1 ppbv. The various meteorological and chemical parameters influencing PAA concentrations were examined using the Principal Factor Analysis. This statistical analysis shows that the local photochemical production was the major source of PAA, and its concentration increased with increasing temperature, solar radiation and ozone but decreased with increasing NOx (NO and NO2, CO, SO2, and relative humidity. Based on the dataset, several issues are highlighted in this study: (i because PAA is a product from the photochemical oxidation of some specific volatile organic compounds (VOCs that lead to acetyl peroxy radicals, the importance of various VOCs with respect to the PAA formation is therefore ranked using the incremental reactivity method. (ii The contribution of PAN thermal degradation to PAA formation under conditions of different NOx concentrations is estimated based on the chemical kinetics analysis. The result shows that PAN seems to play an important role in the formation of PAA when the NO/NO2 concentration ratio was less than 0.2 and PAA would correspondingly have feedback on the PAN-NOx cycle. (iii PAA and other peroxides, such as methyl hydroperoxide (MHP and H2O2, usually exhibited a similar asymmetric shape typically shifted to the afternoon. However, at a high SO2 level, H2O2 showed a profile different from those of MHP and PAA. The combination of linear regression and chemical kinetics analysis reveals that a possible unknown pathway results in the significant removal of H2O2 and the extent of H2O2 undergoing this pathway needs a further study. (iv Considering that PAA is the reservior of free radicals, its fate is expected to have an effect on the free radical budget in the atmosphere. A box model based on the CBM-IV mechanism has been performed to access its influence on the radical budget. We suggest that the detailed information on PAA in the atmosphere is of importance to better understand the free radical chemistry.

  9. Peroxyacetic acid in urban and rural atmosphere: concentration, feedback on PAN-NOx cycle and implication on radical chemistry

    Science.gov (United States)

    Zhang, X.; Chen, Z. M.; He, S. Z.; Hua, W.; Zhao, Y.; Li, J. L.

    2010-01-01

    Peroxyacetic acid (PAA) is one of the most important atmospheric organic peroxides, which have received increasing attention for their potential contribution to the oxidation capacity of the troposphere and the formation of secondary aerosols. We report here, for the first time, a series of data for atmospheric PAA concentrations at urban and rural sites, from five field campaigns carried out in China in summer 2006, 2007 and 2008. For these five measurements, daytime mean (08:00-20:00 LT) PAA concentrations on sunlit days were 21.4-148.0 pptv with a maximum level of ~1 ppbv. The various meteorological and chemical parameters influencing PAA concentrations were examined using Principal Factor Analysis. This statistical analysis shows that the local photochemical production was the major source of PAA, and its concentration increased with increasing temperature, solar radiation and ozone but decreased with increasing NOx (NO and NO2), CO, SO2, and relative humidity. Based on the dataset, several issues are highlighted in this study: (i) Because PAA is a product from the photochemical oxidation of some specific volatile organic compounds (VOCs) that lead to acetyl peroxy radicals, the importance of various VOCs with respect to the PAA formation is therefore ranked using the incremental reactivity method. (ii) The contribution of PAN thermal degradation to PAA formation under conditions of different NOx concentrations is estimated based on the chemical kinetics analysis. The result shows that PAN seems to play an important role in the formation of PAA when the NO/NO2 concentration ratio was less than 0.2 and PAA would correspondingly have feedback on the PAN-NOx cycle. (iii) PAA and other peroxides, such as methyl hydroperoxide (MHP) and H2O2, usually exhibited a similar asymmetric shape typically shifted to the afternoon. However, under some conditions, H2O2 diurnal cycle was out of phase with MHP and PAA. The combination of linear regression and kinetics analysis indicate that the formation and removal processes of H2O2 may be different from those of MHP and PAA. (iv) Considering that PAA is the reservior of free radicals, its fate is expected to have an effect on the free radical budget in the atmosphere. A box model based on the CBM-IV mechanism has been performed to access its influence on the radical budget. We suggest that the detailed information on PAA in the atmosphere is of importance to better understand the free radical chemistry.

  10. Peroxyacetic Acid in Urban and Rural Atmosphere: Feedback on PAN-NO-NO2 Cycle and Implication on Radical Chemistry

    Science.gov (United States)

    Chen, Z.; Zhang, X.

    2009-12-01

    Peroxyacetic Acid (PAA) is one of important atmospheric organic peroxides, which have received increasing attention for their contribution to the oxidizing power of the troposphere and the formation of secondary sulfate and organic aerosols. We report here, for the first time, a series of data of atmospheric PAA concentrations at urban and rural sites, from five field campaigns carried out in China in summer 2006, 2007 and 2008. For these five measurements, daytime mean PAA concentrations on sunlit days were 0.02 to 0.14 ppbv with a maximum level of ~ 1 ppbv. The various meteorological and chemical parameters influencing PAA concentrations were examined using the Principal Factor Analysis. This statistical analysis shows that the local photo-chemical production was the major source of PAA, and its concentration increased with increasing temperature, solar radiation and ozone but decreased with increasing NOx (NO and NO2), CO, SO2, and relative humidity. Because PAA is a product from the photo-chemical oxidation of some specific volatile organic compounds (VOCs) that lead to acetyl peroxy radicals, the importance of various VOCs with respect to the PAA formation was therefore ranked using the incremental reactivity method. Moreover, the contribution of PAN thermal degradation to PAA formation under different NOx concentrations was estimated using a chemical kinetics analysis. The result shows that PAN played an important role in the formation of PAA when NO/NO2 concentration ratio was less than 0.2 and PAA would correspondingly give a feedback on the PAN-NO-NO2 cycle by consuming acetyl peroxy radicals. Like other peroxides measured in these campaigns, such as methyl hydroperoxide (MHP) and H2O2, PAA usually exhibited an asymmetric shape typically shifted to the afternoon. However, under a high SO2 level, H2O2 showed a different trend from MHP and PAA. The combination of linear regression and chemical kinetics analysis reveals that a potentially unknown pathway results in the significant removal of H2O2 and the extent of H2O2 undergoing this pathway needs a further study. Considering that PAA is both source and sink of free radicals, its fate is expected to have an effect on the free radical burden in the atmosphere. A box model based on the CBM-IV mechanism has been employed to make a preliminary estimation on this effect. We suggest that the detailed information on PAA in the atmosphere is of importance to better understand the free radical chemistry.

  11. Peroxyacetic acid in urban and rural atmosphere: concentration, feedback on PAN-NOx cycle and implication on radical chemistry

    Directory of Open Access Journals (Sweden)

    J. L. Li

    2010-01-01

    Full Text Available Peroxyacetic acid (PAA is one of the most important atmospheric organic peroxides, which have received increasing attention for their potential contribution to the oxidation capacity of the troposphere and the formation of secondary aerosols. We report here, for the first time, a series of data for atmospheric PAA concentrations at urban and rural sites, from five field campaigns carried out in China in summer 2006, 2007 and 2008. For these five measurements, daytime mean (08:00–20:00 LT PAA concentrations on sunlit days were 21.4–148.0 pptv with a maximum level of ~1 ppbv. The various meteorological and chemical parameters influencing PAA concentrations were examined using Principal Factor Analysis. This statistical analysis shows that the local photochemical production was the major source of PAA, and its concentration increased with increasing temperature, solar radiation and ozone but decreased with increasing NOx (NO and NO2, CO, SO2, and relative humidity. Based on the dataset, several issues are highlighted in this study: (i Because PAA is a product from the photochemical oxidation of some specific volatile organic compounds (VOCs that lead to acetyl peroxy radicals, the importance of various VOCs with respect to the PAA formation is therefore ranked using the incremental reactivity method. (ii The contribution of PAN thermal degradation to PAA formation under conditions of different NOx concentrations is estimated based on the chemical kinetics analysis. The result shows that PAN seems to play an important role in the formation of PAA when the NO/NO2 concentration ratio was less than 0.2 and PAA would correspondingly have feedback on the PAN-NOx cycle. (iii PAA and other peroxides, such as methyl hydroperoxide (MHP and H2O2, usually exhibited a similar asymmetric shape typically shifted to the afternoon. However, under some conditions, H2O2 diurnal cycle was out of phase with MHP and PAA. The combination of linear regression and kinetics analysis indicate that the formation and removal processes of H2O2 may be different from those of MHP and PAA. (iv Considering that PAA is the reservior of free radicals, its fate is expected to have an effect on the free radical budget in the atmosphere. A box model based on the CBM-IV mechanism has been performed to access its influence on the radical budget. We suggest that the detailed information on PAA in the atmosphere is of importance to better understand the free radical chemistry.

  12. Free radical grafting of gallic acid (GA) on cellulose nanocrystals (CNCS) and evaluation of antioxidant reinforced gellan gum films

    Science.gov (United States)

    Criado, P.; Fraschini, C.; Salmieri, S.; Becher, D.; Safrany, A.; Lacroix, M.

    2016-01-01

    Antiradical properties were introduced on cellulose nanocrystals (CNCs) by redox pair (RP) initiator and ?-radiation treatments. Different procedures were tested on CNC, first a 2 h reaction of hydrogen peroxide (H2O2)/ascorbic acid (AA) was performed on CNC solution. ?-Radiation treatment at 20 kGy dose was then applied and immediately after GA was reacted during 24 h with the pretreated CNCs, giving CNC-H2O2-AA-?-GA. The formation of new carboxylic acids and carbonyl groups were characterized by FT-IR at 1650 and 1730 cm-1 respectively. Carboxylic acid functionalities were also analyzed by conductometric titration where an increase from 49 to 134 mmol COOH kg-1 was found from native to irradiated CNCs. A similar increase in the carboxylic acid content (132 mmol kg-1) was observed for CNC-H2O2-AA-?-GA, showing the highest radical scavenging properties (8 mM Trolox eq/mg CNC). Thermogravimetric analysis confirmed the structural changes onto CNC. Film packaging containing 20% of CNC-H2O2-AA-?-GA was then added to a gellan-based film packaging. A significant improvement (p<0.05) of the tensile strength (TS), the tensile modulus (TM) and the elongation at break (EB) and water vapor permeability reduction was observed when CNC-H2O2-AA-?-GA was added to the film packaging formulation.

  13. AVALIAÇÃO DA ATIVIDADE ANTIOXIDANTE DE DIFERENTES CERVEJAS APLICANDO OS MÉTODOS ABTS E DPPH

    Directory of Open Access Journals (Sweden)

    G. L. FREITAS

    2009-01-01

    Full Text Available

    Os compostos fenólicos são substâncias presentes naturalmente nos vegetais que podem atuar como antioxidantes. Na cerveja desempenham um papel importante nas características sensoriais (cor, aroma e sabor e nutricionais da cerveja. O objetivo deste trabalho foi determinar o conteúdo de compostos fenólicos totais e flavonóis em diversos tipos de cervejas comercializada no Brasil, assim como determinar a capacidade antioxidante in vitro realizada por dois métodos, o radical ABTS•+ (ácido 2,2'-azino-bis (3-etilbenzotiazolin 6-sulfônico e o radical DPPH• (2,2-Difenil-1-picrilhidrazilo. Para determinar os polifenóis totais foi utilizado o método de Folin-Ciocalteau e o método DMACA para os flavanóis. Os resultados mostraram que o conteúdo de compostos fenólicos nas cervejas analisadas variou de 249,73 ± 8,44 a 808,58 ± 7,42 mg/L. A cerveja escura de trigo, apresentou os maiores valores de polifenóis totais, seguida das cervejas escura de cevada, da clara de trigo e das cervejas clara de cevada. Foram encontrados resultados significativos para atividade antioxidante aplicando o método ABTS, valores de 911,79 ± 2,21 a 3857,66 ± 6,07 Mol TEAC/L dependendo do tipo de cerveja e pelo método DPPH, de 2840,12 ± 1,09 a 4290,77± 6,19 Mol TEAC/L. O conteúdo de flavanóis (equivalente a mg catequina/L de amostra., variaram em média de 1,93 ± 0,07 mg/L a 2,79 ± 0,08 mg/L para as cervejas claras e de 2,14 ± 0,04 mg/L a 5,09 ± 0,08 mg/L para as cervejas escuras.

  14. Identification of essential amino-acid residues in Azotobacter vinelandii isocitrate dehydrogenase by radical anions and H atoms

    International Nuclear Information System (INIS)

    Pure TPN+-specific isocitrate dehydrogenase from Azotobacter vinelandii was irradiated with H atoms generated in a ?-irradiated solution at pH 6.5. A G(-activity) = 0.12 +- 0.01 was found. At the same time no corresponding loss in free sulfhydryls was observed. These results confirmed the essentiality of methionine for the enzymatic activity as known from previous studies. Irradiation with the radical anions, (CNS)2- and Br2- generated in ?-irradiated solutions at pH 6.5, strongly inactivated isocitrate dehydrogenase with yields of G(-activity) of 2.1 and 3.9, respectively. Part of the inactivating effect, however, is due to oxidation of sulfhydryl groups. These results lead to the conclusion that tryptophan is an essential amino-acid residue to isocitrate dehydrogenase from A. vinelandii. The presence of tryptophan in the enzyme was demonstrated by pulse radiolysis

  15. Characterization of the peroxidase mechanism upon reaction of prostacyclin synthase with peracetic acid. Identification of a tyrosyl radical intermediate.

    Science.gov (United States)

    Yeh, Hui-Chun; Gerfen, Gary J; Wang, Jinn-Shyan; Tsai, Ah-Lim; Wang, Lee-Ho

    2009-02-10

    Prostacyclin synthase (PGIS) is a membrane-bound class III cytochrome P450 that catalyzes an isomerization of prostaglandin H(2), an endoperoxide, to prostacyclin. We report here the characterization of the PGIS intermediates in reactions with other peroxides, peracetic acid (PA), and iodosylbenzene. Rapid-scan stopped-flow experiments revealed an intermediate with an absorption spectrum similar to that of compound ES (Cpd ES), which is an oxo-ferryl (Fe(IV)O) plus a protein-derived radical. Cpd ES, formed upon reaction with PA, has an X-band (9 GHz) EPR signal of g = 2.0047 and a half-saturation power, P(1/2), of 0.73 mW. High-field (130 GHz) EPR reveals the presence of two species of tyrosyl radicals in Cpd ES with their g-tensor components (g(x), g(y), g(z)) of 2.00970, 2.00433, 2.00211 and 2.00700, 2.00433, 2.00211 at a 1:2 ratio, indicating that one is involved in hydrogen bonding and the other is not. The line width of the g = 2 signal becomes narrower, while its P(1/2) value becomes smaller as the reaction proceeds, indicating migration of the unpaired electron to an alternative site. The rate of electron migration ( approximately 0.2 s(-1)) is similar to that of heme bleaching, suggesting the migration is associated with the enzymatic inactivation. Moreover, a g = 6 signal that is presumably a high-spin ferric species emerges after the appearance of the amino acid radical and subsequently decays at a rate comparable to that of enzymatic inactivation. This loss of the g = 6 species thus likely indicates another pathway leading to enzymatic inactivation. The inactivation, however, was prevented by the exogenous reductant guaiacol. The studies of PGIS with PA described herein provide a mechanistic model of a peroxidase reaction catalyzed by the class III cytochromes P450. PMID:19187034

  16. Antioxidant Activity and Mechanism of Protocatechuic Acid in vitro

    Directory of Open Access Journals (Sweden)

    Shuzhi Chen

    2011-07-01

    Full Text Available Background: Protocatechuic acid (PCA is a natural phenolic acid widely distributed in plantsand is considered as an active component of some traditional Chinese herbal medicines such as Cibotium barometz (L. J.Sm, Stenoloma chusanum (L. Ching, Ilex chinensis Sims. PCA was reported to possess various pharmacological effects which may be closely correlated with its antioxidant activities. However, the antioxidant of PCA has not been investigatedsystematically yet. Methods: In the study, the antioxidant activities of protocatechuic acid were measured in vitrousing various antioxidant assays including 1,1-diphenyl-2-picryl-hydrazyl (DPPH•, 2,2’-azino-bis (3-ethylbenzthiazoline-6-sulfonic acid (ABTS+•, superoxide anion radicals (•O2- and hydroxyl radical (•OH scavenging activity, ferric ions (Fe3+ and cupric ions (Cu2+ reducing power, ferrous ions (Fe2+ and cupric ions (Cu2+ chelating activity, compared with the positive controls Trolox or BHT.Results: In all assays, PCA along with positive controls exhibited dose-dependently antioxidant ability. Comparing to a standard antioxidant Trolox, the relative antioxidant activity of PCA (i.e. the ratio of IC50(Trolox/IC50(PCA was calculated as 2.8, 2.3, 3.7, 6.1, 4.2, 1.0, 2.7, 1.5, respectively, for DPPH, ABTS, reducing power (Fe3+, reducing power (Cu2+, superoxide anion radical-scavenging, hydroxyl radical-scavenging, chelating ability (Fe2+ and chelating ability (Cu2+. Functional Foods in Health and Disease 2011; 7:232-244 Conclusion: Comparing to Trolox, PCA shows much more effective antioxidant activity in vitro in both lipid and aqueous media. Hence, it could therefore be used in pharmacological or food industry as a natural antioxidant. It may exhibit antioxidant activity by both chelating metal transition ions as well as by scavenging free radicals via donating hydrogen atom (H• or electron (e.

  17. Isolation of Lactic Acid Bacteria Showing Antioxidative and Probiotic Activities from Kimchi and Infant Feces.

    Science.gov (United States)

    Ji, Keunho; Jang, Na Young; Kim, Young Tae

    2015-09-28

    The purpose of this study was to investigate lactic acid bacteria with antioxidative and probiotic activities isolated from Korean healthy infant feces and kimchi. Isolates A1, A2, S1, S2, and S3 were assigned to Lactobacillus sp. and isolates A3, A4, E1, E2, E3, and E4 were assigned to Leuconostoc sp. on the basis of their physiological properties and 16S ribosomal DNA sequence analysis. Most strains were confirmed as safe bioresources through nonhemolytic activities and non-production of harmful enzymes such as ?-glucosidase, ?- glucuronidase and tryptophanase. The 11 isolates showed different resistance to acid and bile acids. In addition, they exhibited antibacterial activity against foodborne bacteria, especially Bacillus cereus, Listeria monocytogenes, and Escherichia coli. Furthermore, all strains showed significantly high levels of hydrophobicity. The antioxidant effects of culture filtrates of the 11 strains included 2,2-diphenyl-1-picryl-hydrazyl (DPPH) radical scavenging capacity, 2.2'- azino-bis (2-ethylbenzthiazoline-6-sulfonic acid) (ABTS) radical cation scavenging activity, and superoxide dismutase activity. The results revealed that most of the culture filtrates have effective scavenging activity for DPPH and ABTS radicals. All strains appeared to have effective superoxide dismutase activity. In conclusion, the isolated strains A1, A3, S1, and S3 have significant probiotic activities applicable to the development of functional foods and health-related products. These strains might also contribute to preventing and controlling several diseases associated with oxidative stress, when used as probiotics. PMID:25951843

  18. Pulse radiolytic and product analysis studies of the reaction of hydroxyl radicals with cinnamic acid. The relative extent of addition to the ring and side chain

    Energy Technology Data Exchange (ETDEWEB)

    Bobrowski, K.; Raghavan, N.V.

    1982-10-28

    Using pulse radiolysis with optical detection and high-pressure liquid chromatography (HPCL), it has been shown that reaction of OH radicals with cinnamic acid (CA in aqueous solutions leads to addition to both the ring and the olefinic group. The relative extent of the above two pathways was estimated as 3:7, respectively. Benzyl- and hydroxycyclohexadienyl-type radicals were observed with absorption maxima at 320 (310) and 370 (365) nm depending on the pH of the solution. In the pH region 4.9 to 5.7 the absorption at 305 to 315 nm decays during the first 5 ..mu..s after the pulse. The dependence of the rate constants and absorption spectra on pH suggests that this decay is due to an equilibration process between acid-base forms of benzyl-type radicals formed through OH addition to te olefinic group.

  19. Pulse radiolytic and product analysis studies of the reaction of hydroxyl radicals with cinnamic acid. The relative extent of addition to the ring and side chain

    International Nuclear Information System (INIS)

    Using pulse radiolysis with optical detection and high-pressure liquid chromatography (HPCL), it has been shown that reaction of OH radicals with cinnamic acid (CA in aqueous solutions leads to addition to both the ring and the olefinic group. The relative extent of the above two pathways was estimated as 3:7, respectively. Benzyl- and hydroxycyclohexadienyl-type radicals were observed with absorption maxima at 320 (310) and 370 (365) nm depending on the pH of the solution. In the pH region 4.9 to 5.7 the absorption at 305 to 315 nm decays during the first 5 ?s after the pulse. The dependence of the rate constants and absorption spectra on pH suggests that this decay is due to an equilibration process between acid-base forms of benzyl-type radicals formed through OH addition to te olefinic group

  20. Antioxidant activity and free radical scavenging capacity of phenolic extracts from Helicteres isora L. and Ceiba pentandra L.

    Science.gov (United States)

    Loganayaki, Nataraj; Siddhuraju, Perumal; Manian, Sellamuthu

    2013-08-01

    In the present study, antioxidant activities of the phenolic extracts from H. isora fruits and C. pentandra seeds were investigated by employing established in vitro systems, which included reducing power, OH(?), DPPH(?), ABTS(?+), linoleic acid emulsion, metal chelation and antihemolytic activity. The extracts of C. pentandra contained relatively higher levels of total phenolics and flavonoids than those of H. isora. All the extracts showed dose dependent reducing power activity and moreover, they were well correlated with the total phenolic substances. A similar dose dependant trend has also been observed for hydroxyl radical scavenging activity and DPPH(?) radical scavenging activity. Further, addition of 250 ?g of extracts to the reaction mixture produced 41.3-54.6% peroxidation inhibiting activity during 60 h of incubation. The potential of multiple antioxidant activity of samples can be further evidenced by inhibition of reactive oxygen mediated erythrocyte cell lysis and metal ion chelating activity. PMID:24425970

  1. Effect of free-radical spin trap N-tert-butyl-alpha-phenylnitrone on seizures induced in immature rats by homocysteic acid.

    Czech Academy of Sciences Publication Activity Database

    Folbergrová, Jaroslava; Druga, Rastislav; Otáhal, Jakub; Haugvicová, Renata; Mareš, Pavel; Kubová, Hana

    2005-01-01

    Ro?. 46, ?. S6 (2005), s. 375-375. ISSN 0013-9580. [International Epilepsy Congress /26./. 28.08.2005-01.09.2005, Paris] R&D Projects: GA ?R(CZ) GA309/02/1238; GA ?R(CZ) GA309/05/2015 Keywords : free radical scavenger * epilepsy * immature rats * homocysteic acid Subject RIV: ED - Physiology

  2. The ratio of oleic-to-stearic acid in the prostate predicts biochemical failure after radical prostatectomy for localized prostate cancer

    Science.gov (United States)

    Our study examined lifestyle-related factors that may influence the prognosis of clinically localized prostate cancer, we evaluated the relative impact of obesity and prostatic fatty acid concentrations at diagnosis on risk of biochemical failure following radical prostatectomy. Height and weight w...

  3. Prostatic Fatty Acids and Cancer Recurrence Following Radical Prostatectomy for Early-Stage Prostate Cancer

    Science.gov (United States)

    Objective: Results from some observational studies suggest that diet and energy balance influence the clinical course of early-stage prostate cancer. To evaluate possible mechanisms, we prospectively examined the relation between prostatic concentrations of fatty acids at diagnosis and cancer recurr...

  4. Automatic flow system for sequential determination of ABTS*+ scavenging capacity and Folin-Ciocalteu index: a comparative study in food products.

    Science.gov (United States)

    Magalhães, Luís M; Segundo, Marcela A; Reis, Salette; Lima, José L F C; Tóth, Ildikó V; Rangel, António O S S

    2007-06-01

    In the present work, an automatic flow procedure for the sequential spectrophotometric determination of Folin-Ciocalteu reducing capacity (FC assay) and 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) radical cation (ABTS*+) scavenging capacity expressed as the trolox equivalent (TEAC assay) is proposed for a comparative study of antioxidant properties in food products. Exploiting the flexibility of flow management associated to the computer control offered by multisyringe flow injection analysis, both methodologies were carried out in the same manifold using gallic acid and trolox as standard compounds. The proposed system configuration allowed the performance of each method separately or in tandem, providing 24 determinations per hour, which accounts for its application in routine analysis. The present methodology was applied to a large number of beverages (n=72), namely red and white wines, herbal and tea infusions, juices and beers. The results obtained showed that FC reducing capacity and TEAC values of red wines were significantly different from those obtained for the other beverages, while tea infusions provided significantly higher TEAC values when compared to white wines, herbal infusions, juices and beers. A good correlation was found between TEAC and FC reducing capacity (R>0.9) for red wines, herbal and tea infusions, and beers. For these beverages, similar slope values were found (106-140 mg L(-1) of gallic acid per mM of Trolox), except for beers that showed a higher response for FC assay. These results provided evidence that the correlation between these assays vary according to the type of sample, reinforcing the idea that more than one method should be used for evaluation of antioxidant capacity. PMID:17512826

  5. The ABT Methodology Employment For VET of Quality Auditors

    Directory of Open Access Journals (Sweden)

    Liviu Moldovan

    2011-11-01

    Full Text Available This paper presents some achievements of the project entitled ???Disseminating Open and Innovative Tools and Services for Vocational Education and Training in Quality Assurance??? (acronym Do-IT financed by European Commission. The recent developments and results obtained during pilot testing of new pedagogical models and services, in Do-IT project, targeting engineering education in Romania are presented. This includes the activity Based Training methodology (ABT for quality management system audit course according to ISO 19011 and ISO 9001. ABT focuses on delivering theoretical content linking directly theory and practice according to the industrial production path of an object. The testing of the theoretical and practical achievements has been done using Student Response System (SRS, by using individual voting systems

  6. Antioxidant Activity of Caffeic Acid against Iron-Induced Free Radical Generation—A Chemical Approach

    OpenAIRE

    Genaro-Mattos, Thiago C.; Maurício, Ângelo Q.; Rettori, Daniel; Alonso, Antonio; Hermes-Lima, Marcelo

    2015-01-01

    Caffeic acid (CA) is a phenolic compound widely found in coffee beans with known beneficial effects in vivo. Many studies showed that CA has anti-inflammatory, anti-mutagenic, antibacterial and anti-carcinogenic properties, which could be linked to its antioxidant activity. Taking in consideration the reported in vitro antioxidant mechanism of other polyphenols, our working hypothesis was that the CA antioxidant activity could be related to its metal-chelating property. With that in mind, we ...

  7. About formation of radicals by the photolysis of uranyl salts in aliphatic carbon acids

    International Nuclear Information System (INIS)

    The photolysis of UO2(NO3)2x6H2O and UO2(RCOO)2 (R=CH3, C2H5, C3H7, and CH(CH3)2) has been studied by ESR spin trapping technique using nitrosodurene as a spin trap. Evidences for electron transfer from both coordinated anions and carboxylic acid to U(VI) were found. (author)

  8. The structure and properties of free radicals: An electron spin resonance study of radiation damage to nucleic acid and protein components and to some sulfur-substituted derivitives

    International Nuclear Information System (INIS)

    When cellular systems are exposed to ionizing radiation the long-term effects may range from minor disturbances to such dramatic changes as mutations and cell death. The processes leading to these macroscopical injuries are primarily confined at the molecular level. In all models aimed at a description of the action of radiation at the molecular level the formation of free radicals (which are species containing unpaired electrons) is a central concept. The technique of ESR spectroscopy is uniquely suited to study free radicals, as it is based on resonance absorption of energy by unpaired electrons in a magnetic field. ESR spectroscopy makes it possible to detect free radicals and, in some cases, to identify them. In order to study free radicals by ESR it is necessary to build up a sufficient number of unpaired spins in the sample (approximately 1011 or more, depending on the shape of the resonance). This may be different techniques have been used to trap the induced radicals or to attain a sufficient steady state concentration level. A procedure which seems to contain a large amount of information is to irradiate at low temperatures, and, by subsequent heat-treatment of the sample to study the reactions and fate of the induced radicals. In this thesis single crystal studies of aromatic amino acids and pyrimidine derivitives together with some substituted purine derivitives are presented, and the results are discussed in relation to the present knowledge about radical formation in these classes of compounds. Single crystal studies of some sulfur-containing aromatic compounds have been presented with the purpose of shedding light on the electronic structure of sulfur-centred radicals. (JIW)

  9. DEGRADATION OF ACRYLIC ACID-GRAFTED CELLULOSE IN AQUEOUS MEDIUM WITH RADICAL INITIATORS

    Scientific Electronic Library Online (English)

    AÍDA, NEIRA; MIGUEL, TARRAGA; ROSA, CATALAN.

    2008-03-01

    Full Text Available The chemical modification of cellulose by grafting reaction with Acrylic Acid (AA) considering different reaction factors was investigated. Natural polymers such as Santa Fe Cellulose, Microcrystalline Cellulose (Avicell) and Secondary Pulp were studied as substrates. pH effect; Ce (IV), Mn(VII) and [...] Fenton as initiators; time and temperature polymerization were investigated. Grafting reachs a maximum, 90 % graft, at pH 7. A medium to weak C=0 band at 1715 cm"¹ for carboxylic group in FTIR spectroscopy is presented. Santa Fe and Avicel cellulose grafted whith AA at 17 hours are degraded. Secondary pulp with Fenton at 50-60 and 70 °C at 17 hours are degraded too. The degradation of polymers at long reaction times at 17 hours and 70°C were analized by FTIR spectroscopy and electronic microscopy analysis (SEM).

  10. Rate constants for the reactions of halogenated organic radicals

    International Nuclear Information System (INIS)

    Absolute rate constants have been measured by means of pulse radiolysis for the reactions of various halogenated aliphatic compounds (ethane derivatives, including the anaesthetics halothane, enflurane, isoflurane and methoxyflurane) with hydrated electrons and OH anion radicals, the reactions of halogenated carbon-centred radicals, derived thereby, with molecular oxygen, and the reactions of halogenated peroxyl radicals with various antioxidants (ascorbate, chlorpromazine promethazine, propyl gallate, ABTS) in aqueous solutions. All oxygen addition reactions occur essentially diffusion-controlled. This finding is correlated with the stereoelectronic properties of the primary carbon-centred radicals. The oxidative power of the halogenated peroxyl radicals reflects the inductive-l effect of the halogens and accordingly increases with the degree of halogen substitution, with fluorine substituents being particularly effective. The peroxyl radicals derived from freon 113, namely CClF2CClFOO radical and CCl2FCF2OO radical, have been identified as the best oxidants among these species. (author)

  11. Melt Free-Radical Grafting of Maleic Anhydride onto Biodegradable Poly(lactic acid by Using Styrene as A Comonomer

    Directory of Open Access Journals (Sweden)

    Piming Ma

    2014-05-01

    Full Text Available Maleic anhydride (MA was grafted onto poly(lactic acid (PLA in the presence of styrene (St by using a free-radical grafting methodology. The grafting degree (Dg of MA was increased from 0.65 wt % to 1.1 wt % with the St/MA ratio up to 2/1, where the grafting efficiency (Eg of MA was 27%. However, both Dg and Eg were decreased with further increasing of the St/MA ratio to 4/1. The Dg of MA increased with MA concentration and showed a maximum at 180 °C in the temperature range of 165 °C–190 °C. The grafting mechanisms of MA in the presence of St are analyzed based on titration, thermogravimetric analysis and infrared results, i.e., MA is grafted onto PLA chains via single monomers and a charge-transfer-complex (CTC at St/MA ratios of ? 1/1, while dominantly via St-co-MA oligomers at St/MA ratios of around 2/1. Copolymerization rather than grafting of St and MA occurs at St/MA ratios of around 4/1. The thermal stability of PLA was compromised to a certain extent by the grafting of MA, resulting in reductions in the decomposition temperature (Td-5% and molecular weight of the PLA. In addition, the crystallization and melting temperatures of the PLA were slightly reduced after the grafting.

  12. Radical scavenging activity against 1,1-diphenyl-2-picrylhydrazyl of ascorbic acid 2-glucoside (AA-2G) and 6-acyl-AA-2G.

    Science.gov (United States)

    Fujinami, Y; Tai, A; Yamamoto, I

    2001-05-01

    The radical scavenging activity of the stable derivatives, which are O-substituted at the C-2 position of ascorbic acid (AA), against 1,1-diphenyl-2-picrylhydrazyl (DPPH) was evaluated in buffer under different pH conditions, and compared with those of AA and alpha-tocopherol. AA was shown to have 50% radical scavenging ability (EC50) at a concentration of 2.2 x 10(-5) M against 0.1 mM DPPH in 60% ethanol. Ascorbyl 6-palmitate, a lipophilic AA derivative which has a free endiol group and is therefore unstable, also showed potent radical scavenging activity with EC50 of 2.9 x 10(-5) M. A typical lipophilic antioxidant, alpha-tocopherol gave a similar EC50 value as that of AA. In contrast, ascorbyl 2,6-dipalmitate, AA 2-phosphate and AA 2-sulfate exhibited negligible scavenging activity. On the other hand, 2-O-alpha-D-glucopyranosyl-L-ascorbic acid (AA-2G) and a series of 6-O-acyl-2-O-alpha-D-glucopyranosyl-L-ascorbic acids (6-Acyl-AA-2G) themselves exhibited the radical scavenging activity of EC50: 6.1 x 10(-5) M and 4.4 x 10(-5)-5.9 x 10(-5) M, respectively, although their activities were lower than that of AA. Among 6-Acyl-AA-2G derivatives, the EC50 values tended to decrease with increasing length of their acyl carbon group. Increasing pH of the buffer resulted in decrease in the scavenging activity of all compounds tested as expected. We speculate that the difference in the radical scavenging activity of derivatives O-substituted at the C-2 position of AA may be ascribed to the linkage type of the substituent group to the endiol-lactone resonance system and the degree of dissociation of the C-3 proton. PMID:11383624

  13. Modeling nitrous acid and its impact on ozone and hydroxyl radical during the Texas Air Quality Study 2006

    Directory of Open Access Journals (Sweden)

    B. H. Czader

    2012-02-01

    Full Text Available Nitrous acid (HONO mixing ratios for the Houston metropolitan area were simulated with the Community Multiscale Air Quality (CMAQ model for an episode during the Texas Air Quality Study (TexAQS II in August/September 2006 and compared to in-situ MC/IC (mist-chamber/ion chromatograph and long path DOAS (Differential Optical Absorption Spectroscopy measurements at three different altitudes. Several HONO sources were accounted for in simulations, such as gas phase formation, direct emissions, nitrogen dioxide (NO2* hydrolysis, photo-induced formation from excited NO2* and photo-induced conversion of NO2 into HONO on surfaces covered with organic materials. Compared to the gas-phase HONO formation there was about a tenfold increase in HONO mixing ratios when additional HONO sources were taken into account, which improved the correlation between modeled and measured values. Concentrations of HONO simulated with only gas phase chemistry did not change with altitude, while measured HONO concentrations decrease with height. A trend of decreasing HONO concentration with altitude was well captured with CMAQ predicted concentrations when heterogeneous chemistry and photolytic sources of HONO were taken into account. Heterogeneous HONO production mainly accelerated morning ozone formation, albeit slightly. Also HONO formation from excited NO2 only slightly affected HONO and ozone (O3 concentrations. Photo-induced conversion of NO2 into HONO on surfaces covered with organic materials turned out to be a strong source of daytime HONO. Since HONO immediately photo-dissociates during daytime its ambient mixing ratios were only marginally altered (up to 0.5 ppbv, but significant increase in the hydroxyl radical (OH and ozone concentration was obtained. In contrast to heterogeneous HONO formation that mainly accelerated morning ozone formation, inclusion of photo-induced surface chemistry influenced ozone throughout the day.

  14. Modeling nitrous acid and its impact on ozone and hydroxyl radical during the Texas Air Quality Study 2006

    Directory of Open Access Journals (Sweden)

    B. H. Czader

    2012-08-01

    Full Text Available Nitrous acid (HONO mixing ratios for the Houston metropolitan area were simulated with the Community Multiscale Air Quality (CMAQ Model for an episode during the Texas Air Quality Study (TexAQS II in August/September 2006 and compared to in-situ MC/IC (mist-chamber/ion chromatograph and long path DOAS (Differential Optical Absorption Spectroscopy measurements at three different altitude ranges. Several HONO sources were accounted for in simulations, such as gas phase formation, direct emissions, nitrogen dioxide (NO2 hydrolysis, photo-induced formation from excited NO2 and photo-induced conversion of NO2 into HONO on surfaces covered with organic materials. Compared to the gas-phase HONO formation there was about a tenfold increase in HONO mixing ratios when additional HONO sources were taken into account, which improved the correlation between modeled and measured values. Concentrations of HONO simulated with only gas phase chemistry did not change with altitude, while measured HONO concentrations decrease with height. A trend of decreasing HONO concentration with altitude was well captured with CMAQ predicted concentrations when heterogeneous chemistry and photolytic sources of HONO were taken into account. Heterogeneous HONO production mainly accelerated morning ozone formation, albeit slightly. Also HONO formation from excited NO2 only slightly affected HONO and ozone (O3 concentrations. Photo-induced conversion of NO2 into HONO on surfaces covered with organic materials turned out to be a strong source of daytime HONO. Since HONO immediately photo-dissociates during daytime its ambient mixing ratios were only marginally altered (up to 0.5 ppbv, but significant increase in the hydroxyl radical (OH and ozone concentration was obtained. In contrast to heterogeneous HONO formation that mainly accelerated morning ozone formation, inclusion of photo-induced surface chemistry influenced ozone throughout the day.

  15. Effects of roasting temperature and duration on fatty acid composition, phenolic composition, Maillard reaction degree and antioxidant attribute of almond (Prunus dulcis) kernel.

    Science.gov (United States)

    Lin, Jau-Tien; Liu, Shih-Chun; Hu, Chao-Chin; Shyu, Yung-Shin; Hsu, Chia-Ying; Yang, Deng-Jye

    2016-01-01

    Roasting treatment increased levels of unsaturated fatty acids (linoleic, oleic and elaidic acids) as well as saturated fatty acids (palmitic and stearic acids) in almond (Prunus dulcis) kernel oils with temperature (150 or 180 °C) and duration (5, 10 or 20 min). Nonetheless, higher temperature (200 °C) and longer duration (10 or 20 min) roasting might result in breakdown of fatty acids especially for unsaturated fatty acids. Phenolic components (total phenols, flavonoids, condensed tannins and phenolic acids) of almond kernels substantially lost in the initial phase; afterward these components gradually increased with roasting temperature and duration. Similar results also observed for their antioxidant activities (scavenging DPPH and ABTS(+) radicals and ferric reducing power). The changes of phenolic acid and flavonoid compositions were also determined by HPLC. Maillard reaction products (estimated with non-enzymatic browning index) also increased with roasting temperature and duration; they might also contribute to enhancing the antioxidant attributes. PMID:26213005

  16. Radical-generating coordination complexes as tools for rapid and effective fragmentation and fluorescent labeling of nucleic acids for microchip hybridization.

    Energy Technology Data Exchange (ETDEWEB)

    Kelly, J. J.; Chernov, B. K.; Tovstanovsky, I.; Mirzabekov, A. D.; Bavykin, S. G.; Biochip Technology Center; Northwestern Univ.; Engelhardt Inst. of Molecular Biology

    2002-12-15

    DNA microchip technology is a rapid, high-throughput method for nucleic acid hybridization reactions. This technology requires random fragmentation and fluorescent labeling of target nucleic acids prior to hybridization. Radical-generating coordination complexes, such as 1,10-phenanthroline-Cu(II) (OP-Cu) and Fe(II)-EDTA (Fe-EDTA), have been commonly used as sequence nonspecific 'chemical nucleases' to introduce single-strand breaks in nucleic acids. Here we describe a new method based on these radical-generating complexes for random fragmentation and labeling of both single- and double-stranded forms of RNA and DNA. Nucleic acids labeled with the OP-Cu and the Fe-EDTA protocols revealed high hybridization specificity in hybridization with DNA microchips containing oligonucleotide probes selected for identification of 16S rRNA sequences of the Bacillus group microorganisms.We also demonstrated cDNA- and cRNA-labeling and fragmentation with this method. Both the OP-Cu and Fe-EDTA fragmentation and labeling procedures are quick and inexpensive compared to other commonly used methods. A column-based version of the described method does not require centrifugation and therefore is promising for the automation of sample preparations in DNA microchip technology as well as in other nucleic acid hybridization studies.

  17. Extremely enhanced contaminant decomposition catalyzed by hemin via the coupling of persistent free radicals and ascorbic acid.

    Science.gov (United States)

    Yao, Yuyuan; Jiang, Bin; Mao, Yajun; Chen, Juan; Huang, Zhenfu; Huang, Sanqing; Zhang, Li

    2015-10-27

    Persistent free radicals (PFRs) have mainly been reported as negative species. Here we report a positive role of PFRs in enhancing reactive oxygen species (ROS) generation for an extreme rate enhancement in environmental pollutant decomposition. PMID:26393410

  18. A non-acid-assisted and non-hydroxyl-radical-related catalytic ozonation with ceria supported copper oxide in efficient oxalate degradation in water

    KAUST Repository

    Zhang, Tao

    2012-06-01

    Oxalate is usually used as a refractory model compound that cannot be effectively removed by ozone and hydroxyl radical oxidation in water. In this study, we found that ceria supported CuO significantly improved oxalate degradation in reaction with ozone. The optimum CuO loading amount was 12%. The molar ratio of oxalate removed/ozone consumption reached 0.84. The catalytic ozonation was most effective in a neutral pH range (6.7-7.9) and became ineffective when the water solution was acidic or alkaline. Moreover, bicarbonate, a ubiquitous hydroxyl radical scavenger in natural waters, significantly improved the catalytic degradation of oxalate. Therefore, the degradation relies on neither hydroxyl radical oxidation nor acid assistance, two pathways usually proposed for catalytic ozonation. These special characters of the catalyst make it suitable to be potentially used for practical degradation of refractory hydrophilic organic matter and compounds in water and wastewater. With in situ characterization, the new surface Cu(II) formed from ozone oxidation of the trace Cu(I) of the catalyst was found to be an active site in coordination with oxalate forming multi-dentate surface complex. It is proposed that the complex can be further oxidized by molecular ozone and then decomposes through intra-molecular electron transfer. The ceria support enhanced the activity of the surface Cu(I)/Cu(II) in this process. © 2012 Elsevier B.V.

  19. Free Radical Scavenging Activity and Reducing Capacity of Five Southern Thai Indigenous Vegetable Extracts

    Directory of Open Access Journals (Sweden)

    Worawan PANPIPAT

    2010-01-01

    Full Text Available The phenolic compounds of five southern Thai indigenous vegetables including Mon-pu (Glochidion wallichianum Muell Arg, Cha-plu (Piper sarmentosum Roxb., white popinac (Leucaena leucocephala de Wit., djenkol tree (Archidendrom jiringa I. C. Nielsen. and stink bean (Parkia speciosa Hassk. were extracted using different solvents (50 % acetone, 80 % methanol and distilled water at a ratio of sample to extracting medium of 1:25 (w/v. The extracts were analyzed for total phenolic content using the Folin-Ciocalteu procedure, free radical scavenging capacity by using 2’,2’-azinobis (3-ethylbenzothiazoline-6-sulphonic acid (ABTS and 1,1-diphenyl-2-picrylhydrazyl (DPPH methods, and reducing capacity by using a ferric reducing antioxidant power (FRAP assay. The acetone extracts of all plants possessed the highest total phenolic content followed by the methanolic and distilled water extracts, respectively. The highest total phenolic content was found in the acetone extracts of Mon-pu and white popinac (p < 0.05. The acetone extracts of all plants showed higher free radical scavenging capacity and reducing capacity than those of their methanolic and water extracts counterparts, respectively (p < 0.05. Among all plants tested, the extracts of Mon-pu extracted with all extracting media exhibited the highest free radical scavenging and reducing abilities (p < 0.05. The present study suggested that the acetone extract of Mon-pu was a potential source of natural antioxidants.

  20. [Research on the Quantitative Analysis for In-Situ Detection of Acid Radical Ions Using Laser Raman Spectroscopy].

    Science.gov (United States)

    Chen, Jing; Li, Ying; Du, Zeng-feng; Gu, Yan-hong; Guo, Jin-jia

    2015-09-01

    Laser Raman spectroscopy as an in situ analytical technology can enable detailed investigation of the ocean environment. It is necessary to set up a quantitative analysis method based on laser Raman spectroscopy to understand the marine status in situ. In the laboratory investigations, varied concentration of HCO3(-), SO4(2-) and coastal waters of Qingdao are taken as the samples, operating 532 nm of laser, using fiber optic probes to simulate detection mode in situ. Raman spectra are analyzed using the method of internal standard normalization, multiple linear regression (MLR), general Partial Least Squares (PLS) and PLS based on dominant factor respectively in data processing. It was found that correlation coefficients of calibration curves are not high in internal standard normalization method and predicted relative errors on the prepared samples are much high, so internal standard normalization method cannot be effectively used in the quantitative analysis of HCO3(-), SO4(2-) in the water. And with the multiple linear regression, the analysis accuracy was improved effectively. The calibration curve of PLS based on dominant factor showed that the SO4(2-) and HCO3(-) of pre-made solution with correlation coefficient R2 of 0.990 and 0.916 respectively. The 30 mmol · L(-1) of SO4(2-) and 20 mmol · L(-1) of HCO3(-) in two target samples were determined with the relative errors lower than 3.262% and 5.267% respectively. SO4(2-) in the coastal waters as the research object was analyzed by above-mentioned methods, comparing with 28.01 mmol · L(-1) by ion chromatography. It was demonstrated that PLS based on dominant factor method is superior to the rest of the three analysis methods, which can be used in situ calibration, with the mean relative error about 1.128%. All the results show that analysis accuracy would be improved by the PLS based on dominant factor method to predict concentration of acid radical ions. PMID:26669165

  1. Impact of Lactic Acid on Cell Proliferation and Free Radical Induced Cell Death in Monolayer Cultures of Neural Precursor Cells

    OpenAIRE

    Lampe, Kyle J.; Namba, Rachael M.; Silverman, Tyler R.; Bjugstad, Kimberly B.; MAHONEY, MELISSA J.

    2009-01-01

    Biomaterials prepared from polyesters of lactic acid and glycolic acid, or a mixture of the two, degrade in the presence of water into the naturally occurring metabolites, lactic acid and glycolic acid. While the lactic acid degradation product that is released from biomaterials is well-tolerated by the body, lactic acid can influence the metabolic function of cells; it can serve as an energy substrate for cells, and has been shown to have antioxidant properties. Neural precursor cells, a cel...

  2. In vitro alpha glucosidase inhibition and free-radical scavenging activity of propolis from Thai stingless bees in mangosteen orchard

    Directory of Open Access Journals (Sweden)

    Boonyadist Vongsak

    2015-10-01

    Full Text Available ABSTRACTThe chemical component and biological activity of propolis depend on flora area of bee collection and bee species. In the study, the propolis from three stingless bee species, Lepidotrigona ventralis Smith, Lepidotrigona terminata Smith, and Tetragonula pagdeni Schwarz, was collected in the same region of mangosteen garden from Thailand. Total phenolic content, alpha glucosidase inhibitory effect, and free-radical scavenging activity using FRAP, ABTS, DPPH assays were determined. The most potent activity of propolis extract was investigated for bioactive compounds and their quantity. The ethanol extract of T. pagdeni propolis had the highest total phenolic content 12.83 ± 0.72 g of gallic acid equivalents in 100 g of the extract, and the strongest alpha glucosidase inhibitory effect with the IC50 of 70.79 ± 6.44 µg/ml. The free-radical scavenging activity evaluated by FRAP, ABTS, DPPH assays showed the FRAP value of 279.70 ± 20.55 µmol FeSO4 equivalent/g extract and the IC50 of 59.52 ± 10.76 and 122.71 ± 11.76 µg/ml, respectively. Gamma- and alpha-mangostin from T. pagdeni propolis extract were isolated and determined for the biological activity. Gamma-mangostin exhibited the strongest activity for both alpha glucosidase inhibitory effect and free-radical scavenging activity. Using HPLC quantitative analysis method, the content of gamma- and alpha-mangostin in the extract was found to be 0.94 ± 0.01 and 2.77 ± 0.08% (w/w, respectively. These findings suggested that T. pagdeni propolis may be used as a more suitable raw material for nutraceutical and pharmaceutical products and these mangostin derivatives as markers.

  3. Protective effect of aqueous extract from Spirulina platensis against cell death induced by free radicals

    Directory of Open Access Journals (Sweden)

    Radhakrishnan Ammu

    2010-09-01

    Full Text Available Abstract Background Spirulina is a commercial alga well known to contain various antioxidants, especially phycocyanin. Apart from being sold as a nutraceutical, Spirulina is incorporated as a functional ingredient in food products and beverages. Most of the previous reports on antioxidant activity of Spirulina were based on chemical rather than cell-based assays. The primary objective of this study was to assess the antioxidant activity of aqueous extract from Spirulina based on its protective effect against cell death induced by free radicals. Methods The antioxidant activity of the cold water extract from food-grade Spirulina platensis was assessed using both chemical and cell-based assays. In the cell-based assay, mouse fibroblast cells (3T3 cells were incubated for 1 h in medium containing aqueous extract of Spirulina or vitamin C (positive control at 25, 125 and 250 ?g/mL before the addition of 50 ?M 1,1-diphenyl-2-picrylhydrazyl (DPPH or 3-ethylbenzothiazoline-6-sulfonic acid (ABTS. The cells were incubated for another 24 h before being assessed for cell death due to apoptosis using the Cell Death Detection ELISA Kit. Spectrophotometric assays based on DPPH and ABTS were also used to assess the antioxidant activity of the extract compared to vitamin C and vitamin E (positive controls. Results Spirulina extract did not cause cytotoxic effect on 3T3 cells within the range of concentrations tested (0 - 250 ?g/mL. The extract reduced significantly (p Conclusions The results showed that aqueous extract of Spirulina has a protective effect against apoptotic cell death due to free radicals. The potential application of incorporating Spirulina into food products and beverages to enhance their antioxidant capacity is worth exploring.

  4. In Vitro Antioxidant Activities, Free Radical Scavenging Capacity, and Tyrosinase Inhibitory of Flavonoid Compounds and Ferulic Acid from Spiranthes sinensis (Pers. Ames

    Directory of Open Access Journals (Sweden)

    Chung Pin Liang

    2014-04-01

    Full Text Available In this study, ultrasound-assisted extraction (UAE and other methods of extracting flavonoid compounds and ferulic acid (FA from S. sinensis were investigated. Five different extraction methods, including water extraction (W, water extraction using UAE (W+U, 75% ethanol extraction (E, 75% ethanol extraction using UAE (E+U, and supercritical CO2 extraction (SFE were applied in the extraction of bioactive compounds (flavonoids and ferulic acid in order to compare their efficiency. The highest yield of flavonoids (4.28 mg/g and ferulic acid (4.13 mg/g content was detected in the E+U extract. Furthermore, S. sinensis extracts obtained by E+U show high antioxidant activity, and IC50 values of 0.47 mg/mL for DPPH radicals and 0.205 mg/mL for metal chelating activity. The total antioxidant assay shows superoxide radical scavenging capacity and in vitro mushroom tyrosinase inhibition in a dose-dependent manner, suggesting that E+U can be used for extraction of bioactive compounds from S. sinensis.

  5. A 1H NMR Investigation of the Interaction between Phenolic Acids Found in Mango (Manguifera indica cv Ataulfo) and Papaya (Carica papaya cv Maradol) and 1,1-diphenyl-2-picrylhydrazyl (DPPH) Free Radicals

    Science.gov (United States)

    López-Martínez, Luis M.; Santacruz-Ortega, Hisila; Navarro, Rosa-Elena; Sotelo-Mundo, Rogerio R.; González-Aguilar, Gustavo A.

    2015-01-01

    The benefits of phenolic acids on human health are very often ascribed to their potential to counteract free radicals to provide antioxidant protection. This potential has been attributed to their acidic chemical structure, which possesses hydroxyl groups in different positions. Phenolic acids can interact between themselves and exhibit an additive, antagonistic or synergistic effect. In this paper, we used 1H NMR to analyze the interactions and mechanisms that are present in major phenolic acids found in mango (gallic, protocatechuic, chlorogenic and vanillic acids) and papaya (caffeic, ferulic and p-coumaric acids), and the DPPH radical was used to evaluate the effect of the antioxidant mixtures. The interactions were found to occur via hydrogen bonds between the -OH and -COOH groups. Moreover, the phenolic acids exhibit two types of mechanisms for the neutralization of the DPPH radical. According to the results, these two mechanisms are Hydrogen Atom Transfer (HAT) and Single Electron Transfer (SET). The ability of the phenolic acid to neutralize the DPPH radical decreases in the following order in mango: gallic > chlorogenic > protocatechuic > vanillic. Moreover, within the acids found in papaya, the order was as follows: caffeic > p-coumaric > ferulic. PMID:26559189

  6. A New Hyaluronic Acid Derivative Obtained from Atom Transfer Radical Polymerization as a siRNA Vector for CD44 Receptor Tumor Targeting.

    Science.gov (United States)

    Palumbo, Fabio Salvatore; Bavuso Volpe, Antonella; Bongiovì, Flavia; Pitarresi, Giovanna; Giammona, Gaetano

    2015-11-01

    Two derivatives of hyaluronic acid (HA) have been synthesized by atom transfer radical polymerization (ATRP), starting from an ethylenediamino HA derivative (HA-EDA) and by using diethylaminoethyl methacrylate (DEAEMA) as a monomer for polymerization. Both samples, indicated as HA-EDA-pDEAEMA a and b, are able to condense siRNA, as determined by gel retardation assay and resulting complexes show a size and a zeta potential value dependent on polymerization number, as determined by dynamic light scattering measurements. In vitro studies performed on HCT 116 cell line, that over express CD44 receptor, demonstrate a receptor mediated uptake of complexes, regardless of their surface charge. PMID:26136372

  7. Free Radical Scavenging Profile and Myeloperoxidase Inhibition of Extracts from Antidiabetic Plants: Bauhinia forficata and Cissus sicyoides

    Scientific Electronic Library Online (English)

    NAJEH M, KHALIL; MARIA T, PEPATO; IGUATEMY L, BRUNETTI.

    Full Text Available There is abundant evidence that reactive oxygen species are implicated in several physiological and pathological processes. To protect biological targets from oxidative damage, antioxidants must react with radicáis and other reactive species faster than biological substrates do. The aim of the prese [...] nt study was to determine the in vitro antioxidant activity of aqueous extracts from leaves of Bauhinia forficata Link (Fabaceae - Caesalpinioideae) and Cissus sicyoides L. (Vitaceae) (two medicinal plants used popularly in the control of diabetes mellitus), using several different assay systems, namely, 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) decolorization, superoxide anión radical (0(2)•-) scavenging and myeloperoxidase (MPO) activity. In the ABTS assay for total antioxidant activity, B. forficata showed IC50 = 8.00±0.07 ?g/mL, while C. sicyoides showed IC50 = 13.0±0.2 ?g/mL. However, the extract of C. sicyoides had a stronger effect on 0(2)•- (IC50 = 60.0±2.3 ?g/mL) than the extract of B. forficata (IC50 = 90.0±4.4 ?g/ mL). B. forficata also had a stronger inhibitory effect on MPO activity, as measured by guaiacol oxidation, than C. sicyoides. These results indicate that aqueous extracts of leaves of B. forficata and C. sicyoides are a potential source of natural antioxidants and may be helpful in the prevention of diabetic complications associated with oxidative stress.

  8. Free Radical Scavenging Profile and Myeloperoxidase Inhibition of Extracts from Antidiabetic Plants: Bauhinia forficata and Cissus sicyoides

    Directory of Open Access Journals (Sweden)

    NAJEH M KHALIL

    2008-01-01

    Full Text Available There is abundant evidence that reactive oxygen species are implicated in several physiological and pathological processes. To protect biological targets from oxidative damage, antioxidants must react with radicáis and other reactive species faster than biological substrates do. The aim of the present study was to determine the in vitro antioxidant activity of aqueous extracts from leaves of Bauhinia forficata Link (Fabaceae - Caesalpinioideae and Cissus sicyoides L. (Vitaceae (two medicinal plants used popularly in the control of diabetes mellitus, using several different assay systems, namely, 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid (ABTS decolorization, superoxide anión radical (0(2•- scavenging and myeloperoxidase (MPO activity. In the ABTS assay for total antioxidant activity, B. forficata showed IC50 = 8.00±0.07 ?g/mL, while C. sicyoides showed IC50 = 13.0±0.2 ?g/mL. However, the extract of C. sicyoides had a stronger effect on 0(2•- (IC50 = 60.0±2.3 ?g/mL than the extract of B. forficata (IC50 = 90.0±4.4 ?g/ mL. B. forficata also had a stronger inhibitory effect on MPO activity, as measured by guaiacol oxidation, than C. sicyoides. These results indicate that aqueous extracts of leaves of B. forficata and C. sicyoides are a potential source of natural antioxidants and may be helpful in the prevention of diabetic complications associated with oxidative stress.

  9. Dosimetric Applications of Electronic Paramagnetic Resonance Measurements of Free Radicals Formed in Amino Acids: Construction of a Tissue-Equivalent Dosimeter Based on Alanine

    International Nuclear Information System (INIS)

    In the case of amino acids rupture of the molecules due to the action of radiation is found to produce free radicals. The number of these radicals can be measured by means of an electronic paramagnetic resonance spectrometer and this number is proportional to the dose absorbed. Alanine has been used for this purpose since it possesses this property over a wide dose range (from 10 to 5 x 106 rads). The present paper covers essentially the following points: (a) Pre-irradiation effect in non-irradiated alanine: this dose limits the minimum measurable dose to approximately 10 rads. The origin of this dose and means of re- ducing it have been studied; (b) Energy response of the alanine: by virtue of the close similarity of its composition to that of tissue, this dosimeter has a good energy response for gamma radiations; the loss of efficiency at low energies can be corrected by the addition of a higher Z material (Ba or Ca); (c) Response to neutrons: with neutrons the radical yield is lower than in the case of gamma radiation, although this yield can be increased by adding a hydrogenated substance (paraffin); (d) Construction of a dosimeter in pellet form: the addition of paraffin improves the response to neutrons and enables moulded pellets of the mixture to be produced. These are easier to use than alanine in powder form and the dosimeters can be produced in any desired form. (author)

  10. Effects of chloride ion on degradation of Acid Orange 7 by sulfate radical-based advanced oxidation process: implications for formation of chlorinated aromatic compounds.

    Science.gov (United States)

    Yuan, Ruixia; Ramjaun, Sadiqua N; Wang, Zhaohui; Liu, Jianshe

    2011-11-30

    Sodium chloride is a common salt used during textile wet processes. Here a dual effect of chloride (i.e. inhibitory and accelerating effect) on azo dye (Acid Orange 7, AO7) degradation in an emerging cobalt/peroxymonosulfate (Co/PMS) advanced oxidation process (AOP) was reported. Compared to OH-based AOPs, high concentrations of chloride (>5mM) can significantly enhance dye decoloration independent of the presence of the Co(2+) catalyst, but did greatly inhibit dye mineralization to an extent which was closely dependent upon the chloride content. Both UV-vis absorbance spectra and AOX determination indicated the formation of some refractory byproducts. Some chlorinated aromatic compounds, including 3-chloroisocoumain, 2-chloro-7-hydroxynaphthalene, 1,3,5-trichloro-2-nitrobenzene and tetrachlorohydroquione, were identified by GC-MS measurement in both Co/PMS/Cl(-) and PMS/Cl(-) reaction systems. Based on those experimental results, two possible branched (SO(4)(-)radical-based and non-radical) reaction pathways are proposed. This is one of the very few studies dealing with chlorinated organic intermediates formed via chlorine radical/active chlorine species (HOCl/Cl(2)) attack on dye compounds. Therefore, this finding may have significant technical implications for utilizing Co/PMS regent to detoxify chloride-rich azo dyes wastewater. PMID:21968121

  11. Studies on the syntheses, structural characterization, antimicrobial-, and DPPH radical scavenging activity of the cocrystals caffeine:cinnamic acid and caffeine:eosin dihydrate

    Science.gov (United States)

    Suresh Kumar, G. S.; Seethalakshmi, P. G.; Bhuvanesh, N.; Kumaresan, S.

    2013-10-01

    Two organic cocrystals namely, caffeine:cinnamic acid [(caf)(ca)] (1) and caffeine:eosin dihydrate [(caf)(eos)]·2H2O (2) were synthesized and studied by FT-IR, TGA/DTA, and single crystal XRD. The crystal system of cocrystal 1 is triclinic with space group P-1 and Z = 2 and that of cocrystal 2 is monoclinic with space group P21/C and Z = 4. An imidazole-carboxylic acid synthon is observed in the cocrystal 1. The intermolecular hydrogen bond, O-H⋯N and ?-? interactions play a major role in stabilizing 1 whereas the intermolecular hydrogen bonds, O-H⋯O, O-H⋯N, and intramolecular hydrogen bond, O-H⋯Br; along with ?-? interactions together play a vital role in stabilizing the structure of 2. The antimicrobial- and DPPH radical scavenging activities of both the cocrystals were studied.

  12. Scavenger Activity Evaluation of the Clove Bud Essential Oil (Eugenia caryophyllus) and Eugenol Derivatives Employing ABTS Decolorization.

    Science.gov (United States)

    Merchán Arenas, Diego R; Acevedo, Amner Muñoz; Vargas Méndez, Leonor Y; Kouznetsov, Vladimir V

    2011-01-01

    The essential oil (EO) of clove bud dried fruits from Eugenia caryophyllus was obtained by a conventional hydrodistillation process in an excellent yield (11.7 %). Its chemical composition was analyzed by GC-MS, identifying eugenol as a main constituent (60.5%). Four eugenol-like molecules, ?-diisoeugenol, hydroxymethyleugenol, dihydroeugenol and 1,3-dioxanylphenol, were synthesized using eugenol or isoeugenol as initial precursors under green chemistry protocols. To evaluate the possible antioxidant capacity of eugenol compounds including the clove bud EO, the Trolox® Equivalent Antioxidant Capacity value, obtained by the ABTS(+•) radical-cation discoloration method, was employed. The methodology was performed in a UV-Vis reader of 96-well microplates (dilution methodology), using well-known antioxidant agents (BHA, BHT and vitamin E) as reference compounds. It was found that the prepared eugenol derivatives had a more potent free radical scavenger activity than the reference compounds. In particular, the most active molecules, ?-diisoeugenol and 1,3-dioxanylphenol, were ca. 3-fold more potent than vitamin E. PMID:22145105

  13. Growth of ABT-5 bacteria culture in whey supplemented with whey protein concentrate

    OpenAIRE

    Bojan Matijevi?; Rajka Božani?; Ljubica Tratnik

    2010-01-01

    The objective of this research was to decrease the duration of whey fermentation and to analyze the impact of whey protein concentrates (WPC) addition on growth and activity as well as on survival of mixed ABT-5 culture bacteria (Lactobacillus acidophilus, Bifidobacterium spp. and Streptococcus thermophilus) during 28 days of fermented whey cold storage (5 °C). Whey fermentation was observed at 37 °C with and without 1.5 and 3 % WPC addition. Whey fermentation with mixed ABT-5 bacterial cultu...

  14. Phospholipid Furan Fatty Acids and Ubiquinone-8: Lipid Biomarkers That May Protect Dehalococcoides Strains from Free Radicals

    OpenAIRE

    White, David C.; Geyer, Roland; Peacock, Aaron D.; Hedrick, David B.; Koenigsberg, Stephen S.; Sung, Youlboong; He, Jianzhong; Löffler, Frank E

    2005-01-01

    Dehalococcoides species have a highly restricted lifestyle and are only known to derive energy from reductive dehalogenation reactions. The lipid fraction of two Dehalococcoides isolates, strains BAV1 and FL2, and a tetrachloroethene-to-ethene-dechlorinating Dehalococcoides-containing consortium were analyzed for neutral lipids and phospholipid fatty acids. Unusual phospholipid modifications, including the replacement of unsaturated fatty acids with furan fatty acids, were detected in both De...

  15. Effect of methyl mercury induced free radical stress on nucleic acids and protein: Implications on cognitive and motor functions

    OpenAIRE

    Zahir, Farhana; Rizvi, Shameem J; Haq, Soghra K; Khan, Rizwan H.

    2006-01-01

    Mercury pollution and acute neurotoxicity of mercury is well known. The recent reports suggest the adverse effect of low dose mercury, though the available literature is still silent on its mechanism. This study was therefore undertaken to probe the effect of low dose methyl mercury induced heavy metal toxicity on free radical stress and its impact on behaviour of male albino rats. Male albino rats were exposed to 1 mg/kg body wt of methylmercury chloride for seven days, on day 8 they were te...

  16. Determination of protective properties of Bardejovske Kuple spa curative waters by rotational viscometry and ABTS assay

    OpenAIRE

    TOPOLSKA Dominika; VALACHOVA Katarina; HRABAROVA Eva; Rapta, Peter; BANASOVA Maria; JURNANEK Ivo; SOLTES Ladislav

    2014-01-01

    Mineral waters from Bardejovske Kupele spa are natural, strongly mineralized, with healing effects. They are classified as hydrocarbonic - containing chloride and sodium - carbonic, cold, hypotonic, with a relatively high boric acid content. Potential anti-oxidative effects of curative waters from Bardejovske Kupele were investigated against the hyaluronan (HA) degradation. High-molar-mass HA was exposed to the action of ascorbate and cupric ions, which initiate free-radical chain degradation...

  17. Enzyme inhibitory and radical scavenging effects of some antidiabetic plants of Turkey

    Directory of Open Access Journals (Sweden)

    Nilüfer Orhan

    2014-06-01

    Full Text Available Objective(s:Ethnopharmacological field surveys demonstrated that many plants, such as Gentiana olivieri, Helichrysum graveolens, Helichrysum plicatum ssp. plicatum, Juniperus oxycedrus ssp. oxycedrus, Juniperus  communis var. saxatilis, Viscum album (ssp. album, ssp. austriacum, are used as traditional medicine for diabetes in different regions of Anatolia. The present study was designed to evaluate the in vitro antidiabetic effects of some selected plants, tested in animal models recently. Materials and Methods: ?-glucosidase and ?-amylase enzyme inhibitory effects of the plant extracts were investigated and Acarbose was used as a reference drug. Additionally, radical scavenging capacities were determined using 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid ABTS radical cation scavenging assay and total phenolic content of the extracts were evaluated using Folin Ciocalteu method. Results: H. graveolens ethanol extract exhibited the highest inhibitory activity (55.7 % ± 2.2 on ?-amylase enzyme. Additionally, J. oxycedrus hydro-alcoholic leaf extract had potent ?-amylase inhibitory effect, while the hydro-alcoholic extract of J. communis fruit showed the highest ?-glucosidase inhibitory activity (IC50: 4.4 ?g/ml. Conclusion:Results indicated that, antidiabetic effect of hydro-alcoholic extracts of H. graveolens capitulums, J. communis fruit and J. oxycedrus leaf might arise from inhibition of digestive enzymes.

  18. Nitrogen Oxides in the Nocturnal Boundary Layer: Chemistry of Nitrous Acid (HONO) and the Nitrate Radical (N03)

    Energy Technology Data Exchange (ETDEWEB)

    Jochen Stutz

    2005-05-24

    Summary Chemical processes occurring at night in the lowest part of the urban atmosphere, the so called nocturnal boundary layer (NBL), can influence the composition of the atmosphere during the night as well as the following day. They may impact the budgets of some of the most important pollutants, such as ozone and nitrogen oxides, as well as influence size and composition of particular matter. Few studies have thus far concentrated on the nocturnal chemistry of the urban NBL, most likely due to the strong influence of vertical transport and mixing, which requires the measurement of trace gas profiles instead of simple point observations. Motivated by our lack of observations and understanding of nocturnal chemistry, the focus of this project was the study of the vertical distribution of trace gases and the altitude dependence of nocturnal chemistry under polluted conditions through field observations and modeling studies. The analysis of three field experiments (TEXAQS, Houston, 2000; Phoenix Sunrise Ozone Experiment, 2001; NAPOX, Boston, 2002), two of which were performed in this project, showed that ozone concentrations typically increase with height in the lowest 150m, while NO2 typically decreases. NO3, the dominant nocturnal radical species, showed much higher concentrations in the upper part of the NBL, and was often not present at the ground. With the help of a one-dimensional chemical transport model, developed in this project, we found that the interaction of ground emissions of NOx and hydrocarbons, together with their vertical transport, is responsible for the vertical profiles. The dominant chemical reactions influencing ozone, NO2 and NO3 are the reaction of ozone and NO3 with freshly emitted NO. Sensitivity studies with our model showed that the magnitude of the trace gas gradients depend both on the emission rates and the vertical stability of the NBL. Observations and model analysis clearly show that nocturnal chemistry in urban areas is altitude dependent. Measurements at one altitude, for example at the ground, where most air quality monitoring stations are located, are not representative for the rest of the NBL. Our model also revealed that radical chemistry is, in general, altitude dependent at night. We distinguish three regions: an unreactive, NO rich, ground layer; an upper, O3 and NO3 dominated layer, and a reactive mixing layer, where RO2 radicals are mixed from aloft with NO from the ground. In this reactive layer an active radical chemistry and elevated OH radical levels can be found. The downward transport of N2O5 and HO2NO2, followed by their thermal decay, was also identified as a radical source in this layer. Our observations also gave insight into the formation of HONO in the NBL. Based on our field experiments we were able to show that the NO2 to HONO conversion was relative humidity dependent. While this fact was well known, we found that it is most likely the uptake of HONO onto surfaces which is R.H. dependent, rather than the NO2 to HONO conversion. This finding led to the proposal of a new NO2 to HONO conversion mechanism, which is based on solid physical chemical principles. Noteworthy is also the observation of enhanced NO2 to HONO conversion during a dust storm event in Phoenix. The final activity in our project investigated the influence of the urban canopy, i.e. building walls and surfaces, on nocturnal chemistry. For the first time the surface area of a city was determined based on a Geographical Information System database of the city of Santa Monica. The surface to volume areas found in this study showed that, in the 2 lower part of the NBL, buildings provide a much larger surface area than the aerosol. In addition, buildings take up a considerable amount of the volume near the ground. The expansion of our model and sensitivity studies based on the Santa Monica data revealed that the surface area of buildings considerably influences HONO levels in urban areas. The volume reduction leads to a decrease of O3 and an increase of NO2 near the ground due to the stronger impact o

  19. Radical prostatectomy

    DEFF Research Database (Denmark)

    Fode, Mikkel; Sønksen, Jens; Jakobsen, Henrik

    2014-01-01

    OBJECTIVE: The aim of this study was to compare oncological and functional outcomes between robot-assisted laparoscopic radical prostatectomy (RALP) and retropubic radical prostatectomy (RRP) during the initial phase with RALP at a large university hospital. MATERIAL AND METHODS: Patient and tumour characteristics, surgeon, nerve sparing, surgical margins and blood loss were recorded prospectively in patients who underwent RRP or RALP between April 2008 and May 2012. Patients filled out the Dani...

  20. Influence of brewing method and acidity regulators on the antioxidant capacity of coffee brews.

    Science.gov (United States)

    Pérez-Martínez, Mónica; Caemmerer, Bettina; De Peña, M Paz; Cid, Concepción; Kroh, Lothar W

    2010-03-10

    The antioxidant capacity of coffee brews prepared with different coffeemakers (filter, plunger, mocha, and espresso) was measured by colorimetric (total phenolic compounds and ABTS) and electron spin resonance (ESR) spectroscopy techniques (Fremy's salt and TEMPO). The mocha coffeemaker had the highest yield in coffee antioxidant extraction per gram of ground roasted coffee, but espresso coffee was richest in terms of antioxidant intake (per milliliter of coffee brew) followed by mocha, plunger, and filter. Both Folin-Ciocalteu (total phenolic compounds) and ABTS assays reacted with standard solutions of chlorogenic acids (CGA) and melanoidins (MO-Ala and MO-Gly). However, Fremy's salt was mainly scavenged by chlorogenic acids, whereas the stabilized radical TEMPO was effectively scavenged by melanoidins, but not by chlorogenic acids. Thus, ESR spectroscopy allows distinguishing between phenolic and nonphenolic antioxidants. Moreover, the addition of pH-regulator agents to coffee, such as sodium carbonate (75 ppm) and bicarbonate (75 ppm), to extend its shelf life, slightly increases the pH, modifying the antioxidant capacity in those coffee brews with the highest capacity (mocha and espresso). PMID:20141144

  1. Phenolic acid content and radical scavenging activity of extracts from medlar (Mespilus germanica L.) fruit at different stages of ripening.

    Czech Academy of Sciences Publication Activity Database

    Grúz, Ji?í; Ayaz, F. A.; Torun, H.; Strnad, Miroslav

    2011-01-01

    Ro?. 124, ?. 1 (2011), s. 271-277. ISSN 0308-8146 R&D Projects: GA AV ?R KAN200380801 Institutional research plan: CEZ:AV0Z50380511 Keywords : Phenolic acid s * HPLC * Mass spectrometry * Fruit * Ripening Subject RIV: EF - Botanics Impact factor: 3.655, year: 2011

  2. Beyond prostaglandins - chemistry and biology of cyclic oxygenated metabolites formed by free-radical pathways from polyunsaturated fatty acids.

    Czech Academy of Sciences Publication Activity Database

    Jahn, Ullrich; Galano, J. M.; Durand, T.

    2008-01-01

    Ro?. 47, ?. 32 (2008), s. 5894-5955. ISSN 1433-7851 Institutional research plan: CEZ:AV0Z40550506 Keywords : biological activity * fatty acids * isoprostanes * oxidation * total synthesis Subject RIV: CC - Organic Chemistry Impact factor: 10.879, year: 2008

  3. Evaluation of in vitro antioxidant activity and free radical scavenging potential of variety of Tagetes erecta L. flowers growing in Bulgaria

    Directory of Open Access Journals (Sweden)

    Miglena Valyova

    2012-08-01

    Full Text Available Summary. Marigold (Tagetes erecta L. is well known for its antimicrobial, antiseptic, wound and ulcer healing, antiinflammatory, antioxidant and antiviral properties, and it has a long history of being used as an herbal remedy. T. erecta L. produces a variety of substances that possess pharmacological effects and antioxidant activity. The present study was therefore aimed to analyze the antioxidant activity of extracts and fractions of T. erecta L. flowers, cultivated in Bulgaria. Radical scavenging potential was determined using two different in vitro assays. 1, 1-diphenyl-2-picrylhydrazyl (DPPH and 2, 2’-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid (ABTS radicals. The ethyl acetate fraction of T. erecta L. ethanol extract was found to be the most effective in both assays, DPPH (IC50 4.3±0.4 ?g/ml and ABTS (0.8±0.2 TEAC. The greatest total phenolic content was detected in EtOAc fraction from EtOH extract (517.8 mg/g GAE. It was obtained high quantity of ascorbate and ascorbate/dehydroascorbate ratio more than 1. The quantity of glutathione reduced is low and glutathione reduced/glutathione oxidized ratio was lower than 1. A correlation between radical scavenging capacities of samples with total phenolic compound content was observed. The present study revealed that the EtOAc fraction effectively show the best ability to scavenge the free radicals. Industrial relevance. Herbal medicines have gained increasing attention worldwide for the treatment of chronic diseases because of their effectiveness and small side effects as compared to synthetic drugs.Recently, an attention has been directed toward the antioxidant phytochemicals which have proved as protective against cardiovascular diseases and cancer, associated with overproduction of reactive oxygen species. The present investigations focus has been to discover plant extracts and fractions from T. erecta useful to prevent chronic degenerative diseases, especially those mediated by free radicals damages. The great antioxidant activity indicates the potential of the extracts as a source of natural antioxidants or nutraceuticals with possible application to reduce oxidative stress with consequent health benefits. Keywords. Tagetes erecta L.; in vitro antioxidant activity; free radical scavenging potential; phenols; flavonoids; ascorbate, glutathione.

  4. Plasma thiobarbituric acid reactivity: reaction conditions and the role of iron, antioxidants and lipid peroxy radicals on the quantitation of plasma lipid peroxides

    Energy Technology Data Exchange (ETDEWEB)

    Wade, C.R.; van Rij, A.M.

    1988-01-01

    The effects of Fe/sup 3 +/, lipid peroxy radicals and the antioxidant butylated hydroxytoluene on the 2-thiobarbituric (TBA) acid quantitation of plasma lipid peroxides were investigated. Whole plasma and plasma fractions prepared by trichloroacetic acid (TCA) protein precipitation and lipid extraction, demonstrated markedly differing TBA reactivities in the presence or absence of added Fe/sup 3 +/. Examination of the spectral profiles of the TBA reacted whole plasma and TCA precipitated fractions demonstrated the presence of interfering compounds which gave rise to an artifactual increase in lipid peroxide concentrations. In contrast the TBA reacted lipid extracts had low levels of interfering compounds that could be removed by our previously described high pressure liquid chromatographic method. Further characterization of the TBA reactivity of the lipid extract showed that Fe/sup 3 +/ at an optimal concentration of 0.5 mM was necessary for the quantitative decomposition of the lipid peroxides to the TBA reactive product malondialdehyde (MDA). However the presence of Fe/sup 3 +/ resulted in further peroxidation of any unsaturated lipids present.

  5. Modeling nitrous acid and its impact on ozone and hydroxyl radical during the Texas Air Quality Study 2006

    OpenAIRE

    B. H. Czader; Rappenglück, B.; P. Percell; D. W. Byun; F. Ngan; Kim, S.

    2012-01-01

    Nitrous acid (HONO) mixing ratios for the Houston metropolitan area were simulated with the Community Multiscale Air Quality (CMAQ) model for an episode during the Texas Air Quality Study (TexAQS) II in August/September 2006 and compared to in-situ MC/IC (mist-chamber/ion chromatograph) and long path DOAS (Differential Optical Absorption Spectroscopy) measurements at three different altitudes. Several HONO sources were accounted for in simulations, such as gas phase formation, direct emission...

  6. Comparative evaluation of free radical scavenging activity of Boerhaavia diffusa root extracts (BDRE and determination of dose effectivity against radiation induced damages in Swiss albino mice

    Directory of Open Access Journals (Sweden)

    P Dhakar

    2012-12-01

    Full Text Available Summary: Purpose of the study was to evaluate free radical scavenging activity (FRSA of root extracts of Boerhaavia diffusa in different solvents and to examine its dose effectivity against radiation induced damages in Swiss albino mice. Scavenging activities of aqueous, ethanolic and hydroethanolic extracts of B. diffusa roots were evaluated by DPPH (2, 2-diphenyl-1 picryl hydrazyl, ABTS (2,2’-azino-bis-3-ethylbenzothiazoline-6-sulphonic acid and NO (nitric oxide assay to find the most effective extract and results were expressed as IC50. To find the most effective dose, hydroethanolic root extract (50:50 of B. diffusa was orally administered to Swiss albino mice at the dose of 250, 500 and 1000 mg/Kg.body.weight for 15 consecutive days prior to irradiation with 8 Gy gamma radiation. Results indicates that hydroethanolic extract exhibited the highest free radical scavenging activity in DPPH., ABTS.+ and NO. assays showing IC50 as 293.77, 43.62 and 32.58 µg/ml, respectively. Reduced symptoms of radiation sickness, decline in body weight and mortality were minimum when mice were pre-treated with hydroethanolic extract at the dose of 1000 mg/Kg.body.weight prior to irradiation with 8 Gy gamma radiation as compared to mice pre-treated with extract at  the dose of 250 and 500 mg/Kg.body.weight prior to irradiation with same dose of radiation. Thus, it was Concluded that certain phenolic constituents of B. diffusa roots like quercitin, caeffic acid, kempferol etc. and their derivatives act as antioxidant compounds confirming B. diffusa roots a potential source of antioxidant agent. Industrial Relevance: Having noticed with the importance of phytochemicals including flavonoids and phenolic acids as contributing factors to the antioxidant activity and common use of roots of Boerhaavia diffusa in majority of medicinal aspects can be responsible in curing oxidative stress related diseases in human beings. This study perhaps will be helpful in development of the effective drug for providing protection to biological systems against free radical induced damage. Keywords: Radioprotection, Boerrhavia diffusa, Free Radical Scavenging Activity, Dose Reduction Factor, Antioxidants.

  7. In Vitro and In Vivo Enhancement of Chemoradiation Using the Oral PARP Inhibitor ABT-888 in Colorectal Cancer Cells

    Energy Technology Data Exchange (ETDEWEB)

    Shelton, Joseph W., E-mail: jwshelt@emory.edu [Department of Radiation Oncology, Winship Cancer Institute, Emory University, Atlanta, Georgia (United States); Waxweiler, Timothy V.; Landry, Jerome; Gao, Huiying; Xu, Yanbo; Wang, Lanfang [Department of Radiation Oncology, Winship Cancer Institute, Emory University, Atlanta, Georgia (United States); El-Rayes, Bassel [Department of Hematology and Oncology, Winship Cancer Institute, Emory University, Atlanta, Georgia (United States); Shu, Hui-Kuo G. [Department of Radiation Oncology, Winship Cancer Institute, Emory University, Atlanta, Georgia (United States)

    2013-07-01

    Purpose: Poly(ADP-ribose) polymerase plays a critical role in the recognition and repair of DNA single-strand breaks and double-strand breaks (DSBs). ABT-888 is an orally available inhibitor of this enzyme. This study seeks to evaluate the use of ABT-888 combined with chemotherapy and radiation therapy (RT) in colorectal carcinoma models. Methods and Materials: RT clonogenic assays were performed on HCT116 and HT29 cells treated with 5-fluorouracil, irinotecan, or oxaliplatin with or without ABT. The surviving fraction at 2 Gy and dose-modifying factor at 10% survival were analyzed. Synergism was assessed by isobologram analysis for combination therapies. ?H2AX and neutral comet assays were performed to assess the effect of therapy on DSB formation/repair. In vivo assessments were made by use of HCT116 cells in a xenograft mouse model. Tumor growth delay was measured at a volume of 500 mm{sup 3}. Results: Both lines were radiosensitized by ABT alone, and ABT further increased chemotherapy dose-modifying factors to the 1.6 to 1.8 range. All combinations were synergistic (combination indices <0.9). ABT treatment significantly increased DSB after RT (?H2AX, 69% vs 43%; P=.017) and delayed repair. We found tumor growth delays of 7.22 days for RT; 11.90 days for RT and ABT; 13.5 days for oxaliplatin, RT, and ABT; 14.17 days for 5-fluorouracil, RT, and ABT; and 23.81 days for irinotecan, RT, and ABT. Conclusion: ABT-888 radiosensitizes at similar or higher levels compared with classic chemotherapies and acts synergistically with these chemotherapies to enhance RT effects. In vivo confirmation of these results indicates a potential role for combining its use with existing chemoradiation regimens.

  8. Determination of total antioxidant capacity of milk by CUPRAC and ABTS methods with separate characterisation of milk protein fractions.

    Science.gov (United States)

    Çekiç, Sema Demirci; Demir, Asl?; Ba?kan, Kevser Sözgen; Tütem, Esma; Apak, Re?at

    2015-05-01

    Most milk-applied antioxidant assays in literature are based on the isolation and quantification of individual antioxidative compounds, whereas total antioxidant capacity (TAC) gives a more holistic picture due to cooperative action of antioxidants. Recently, the cupric reducing antioxidant capacity (CUPRAC) method has been modified to measure the antioxidant capacities of thiol-containing proteins, where the classical ammonium acetate buffer - that may otherwise precipitate proteins- was replaced with concentrated urea buffer (able to expose embedded thiol groups of proteins to oxidative attack) adjusted to pH 7.0. Thus, antioxidant capacity of milk was investigated with two competing TAC assays, namely CUPRAC and ABTS (2,2'-azinobis(3-ethylbenzothiazoline-6-sulphonic acid))/persulphate, because only these assays were capable of evaluating protein contribution to the observed TAC value. As milk fat caused turbidity, experiments were carried out with skim milk or defatted milk samples. To determine TAC, modified CUPRAC method was applied to whole milk, separated and redissolved protein fractions, and the remaining liquid phase after necessary operations. Both TAC methods were investigated for their dilution sensitivity and antioxidant power assessment of separate milk fractions such as casein and whey. Proteins like ?-lactoglobulin and casein (but not simple thiols) exhibited enhanced CUPRAC reactivity with surfactant (SDS) addition. Addition of milk protein fractions to whole skim milk produced significant 'negative-biased' deviations (up to -26% relative standard error) from TAC absorbance additivity in the application of the ABTS method, as opposed to that of the CUPRAC method less affected by chemical deviations from Beer's law thereby producing much smaller deviations from additivity (i.e. the property of additivity is valid when the measured TAC of a mixture is equal to the sum of individual antioxidant capacities of its constituents). PMID:25731579

  9. The wheat cytochrome oxidase subunit II gene has an intron insert and three radical amino acid changes relative to maize

    OpenAIRE

    Bonen, Linda; Boer, Poppo H.; GRAY, MICHAEL W.

    1984-01-01

    We have determined the sequence of the wheat mitochondrial gene for cytochrome oxidase subunit II (COII) and find that its derived protein sequence differs from that of maize at only three amino acid positions. Unexpectedly, all three replacements are non-conservative ones. The wheat COII gene has a highly-conserved intron at the same position as in maize, but the wheat intron is 1.5 times longer because of an insert relative to its maize counterpart. Hybridization analysis of mitochondrial D...

  10. Stability studies of ascorbic acid 2-glucoside in cosmetic lotion using surface response methodology.

    Science.gov (United States)

    Huang, Wen-Ying; Lee, Pei-Chi; Huang, Ling-Kuei; Lu, Li-Ping; Liao, Wayne C

    2013-03-15

    Ascorbic acid 2-glucoside (AA-2G) has been widely used in cream and lotion types of cosmetic products. Thus, the degradation of AA-2G caused by the temperature change and pH variation was very critical for determining the bio-functionality of cosmetics. Response surface methodology (RSM) was introduced to study the influence of temperature and pH on the stability of AA-2G. The optimal condition of retaining AA-2G with the highest stability was determined to be 55.3°C and pH 6.4. The antioxidative activities of AA-2G including DPPH and ABTS free radical scavenging activities, metal chelating activity, and reducing ability were also determined. AA-2G was a good ascorbic acid derivative which could be used in cosmetic products as an active ingredient. PMID:23416010

  11. Estudio comparativo sobre la capacidad de atrapamiento del catiónradical ABTS+. Por los aceites esenciales de especies aromáticas con alto contenido de trans-ANETOL Y ESTRAGOL

    Directory of Open Access Journals (Sweden)

    Amner Muñoz

    2007-01-01

    Full Text Available Se determinó la composición química de aceites esenciales (AEs y extractos de seis especies aromáticas con alto contenido de trans-anetol y estragol (estragón de invierno, estragón, anís estrellado, anisillo, hinojo y sígueme morado, obtenidos por hidrodestilación asistida por radiación de microondas (MWHD y destilación-extracción simultánea con solvente (SDE. La separación e identificación de los compuestos se realizó por GC-MS en columna apolar DB-5MS, comparando sus espectros de masas con los de las bases de datos ADAMS, NIST02 y Wiley138 e índices de retención de kovàts. Para todos los AEs se evaluó su capacidad del atrapamiento del catión-radical ABTS+. (ácido 2,2? -azino-bis -(3-etiltiazolina-bencenosulfónico-6.

  12. Oxidation of Gas-Phase SO2 on the Surfaces of Acidic Microdroplets: Implications for Sulfate and Sulfate Radical Anion Formation in the Atmospheric Liquid Phase.

    Science.gov (United States)

    Hung, Hui-Ming; Hoffmann, Michael R

    2015-12-01

    The oxidation of SO2(g) on the interfacial layers of microdroplet surfaces was investigated using a spray-chamber reactor coupled to an electrospray ionization mass spectrometer. Four major ions, HSO3(-), SO3(•-), SO4(•-) and HSO4(-), were observed as the SO2(g)/N2(g) gas-mixture was passed through a suspended microdroplet flow, where the residence time in the dynamic reaction zone was limited to a few hundred microseconds. The relatively high signal intensities of SO3(•-), SO4(•-), and HSO4(-) compared to those of HSO3(-) as observed at pH oxygen suggests an efficient oxidation pathway via sulfite and sulfate radical anions on droplets possibly via the direct interfacial electron transfer from HSO3(-) to O2. The concentrations of HSO3(-) in the aqueous aerosol as a function of pH were controlled by the deprotonation of hydrated sulfur dioxide, SO2·H2O, which is also affected by the pH dependent uptake coefficient. When H2O2(g) was introduced into the spray chamber simultaneously with SO2(g), HSO3(-) is rapidly oxidized to form bisulfate in the pH range of 3 to 5. Conversion to sulfate was less at pH reactions. The rapid oxidation of SO2(g) on the acidic microdroplets was estimated as 1.5 × 10(6) [S(IV)] (M s(-1)) at pH ? 3. In the presence of acidic aerosols, this oxidation rate is approximately 2 orders of magnitude higher than the rate of oxidation with H2O2(g) at a typical atmospheric H2O2(g) concentration of 1 ppb. This finding highlights the relative importance of the acidic surfaces for SO2 oxidation in the atmosphere. Surface chemical reactions on aquated aerosol surfaces, as observed in this study, are overlooked in most atmospheric chemistry models. These reaction pathways may contribute to the rapid production of sulfate aerosols that is often observed in regions impacted by acidic haze aerosol such as Beijing and other megacities around the world. PMID:26270804

  13. Hydrogen transfer between sulfuric acid and hydroxyl radical in the gas phase: competition among hydrogen atom transfer, proton-coupled electron-transfer, and double proton transfer.

    Science.gov (United States)

    Anglada, Josep M; Olivella, Santiago; Solé, Albert

    2006-02-01

    In an attempt to assess the potential role of the hydroxyl radical in the atmospheric degradation of sulfuric acid, the hydrogen transfer between H2SO4 and HO* in the gas phase has been investigated by means of DFT and quantum-mechanical electronic-structure calculations, as well as classical transition state theory computations. The first step of the H2SO4 + HO* reaction is the barrierless formation of a prereactive hydrogen-bonded complex (Cr1) lying 8.1 kcal mol(-1) below the sum of the (298 K) enthalpies of the reactants. After forming Cr1, a single hydrogen transfer from H2SO4 to HO* and a degenerate double hydrogen-exchange between H2SO4 and HO* may occur. The single hydrogen transfer, yielding HSO4* and H2O, can take place through three different transition structures, the two lowest energy ones (TS1 and TS2) corresponding to a proton-coupled electron-transfer mechanism, whereas the higher energy one (TS3) is associated with a hydrogen atom transfer mechanism. The double hydrogen-exchange, affording products identical to reactants, takes place through a transition structure (TS4) involving a double proton-transfer mechanism and is predicted to be the dominant pathway. A rate constant of 1.50 x 10(-14) cm(3) molecule(-1) s(-1) at 298 K is obtained for the overall reaction H2SO4 + HO*. The single hydrogen transfer through TS1, TS2, and TS3 contributes to the overall rate constant at 298 K with a 43.4%. It is concluded that the single hydrogen transfer from H2SO4 to HO* yielding HSO4* and H2O might well be a significant sink for gaseous sulfuric acid in the atmosphere. PMID:16451034

  14. ANTIOXIDANT CAPACITY AND AMINO ACID PROFILES OF EGG TOFU

    Directory of Open Access Journals (Sweden)

    Maizura Murad

    2013-01-01

    Full Text Available Tofu contains high quality protein source and antioxidant which could reduce risk of cancer. This research aims to determine the effect of soymilk and egg ratios on the antioxidant capacity, daidzein and genistein content and amino acid profiles of egg tofu. Egg tofu was prepared using soymilk and fresh egg in ratios of 1:1, 2:1, 3:1 and 4:1. Glucono-Delta-Lactone (GDL was added in the egg tofu to act as a coagulating agent. Increased of soymilk at all ratios had significantly (p<0.05 increased in Ferric-Reducing Antioxidant Power (FRAP, daidzein and genistein content of egg tofu. Conversely, decreased in soymilk ratio had significantly (p<0.05 increased the radical scavenging activities of the 2,2-Azino-Bis 3-ethylbenzothiazoline-6-Sulfonic acid (ABTS and 2,2-Diphenyl-2-Picrylhydrazyl (DPPH in egg tofu. Increased of soymilk ratio up to 3:1 caused decreased in amino acid methionine (met and cystein (cys significantly (p<0.05. A significant (p<0.01 and a positive correlation was observed between Total Phenolic Content (TPC and FRAP (r = 0.93. However, there was a negative (p<0.01 correlation between TPC and DPPH (r = -0.83. The antioxidant capacity of egg tofu in DPPH assay showed a positive and significant (p<0.01 correlation with cysteine, methionine and tryptophan with r value of 0.92, 0.93 and 0.96 respectively. Higher content of egg in egg tofu had contributed to the increased of antioxidant capacity as indicated in DPPH assay and ABTS assay as well as amino acid methionine and cysteine.

  15. In vitro antioxidant properties, free radicals scavenging activities of extracts and polyphenol composition of a non-timber forest product used as spice: Monodora myristica

    Scientific Electronic Library Online (English)

    Bruno Moukette, Moukette; Constant Anatole, Pieme; Jacques Romain, Njimou; Cabral Prosper Nya, Biapa; Bravi, Marco; Jeanne Yonkeu, Ngogang.

    Full Text Available BACKGROUND: Excessive production of free radicals causes direct damage to biological molecules such as DNA, proteins, lipids, carbohydrates leading to tumor development and progression. Natural antioxidant molecules from phytochemicals of plant origin may directly inhibit either their production or [...] limit their propagation or destroy them to protect the system. In the present study, Monodora myristica a non-timber forest product consumed in Cameroon as spice was screened for its free radical scavenging properties, antioxidant and enzymes protective activities. Its phenolic compound profile was also realized by HPLC. RESULTS: This study demonstrated that M. myristica has scavenging properties against DPPH',OH',NO', and ABTS'radicals which vary in a dose depending manner. It also showed an antioxidant potential that was comparable with that of Butylated Hydroxytoluene (BHT) and vitamin C used as standard. The aqueous ethanol extract of M. myristica barks (AEH); showed a significantly higher content in polyphenolic compounds (21.44 ±0.24 mg caffeic acid/g dried extract) and flavonoid (5.69 ± 0.07 quercetin equivalent mg/g of dried weight) as compared to the other studied extracts. The HPLC analysis of the barks and leaves revealed the presence of several polyphenols. The acids (3,4-OH-benzoic, caffeic, gallic, O- and P- coumaric, syringic, vanillic), alcohols (tyrosol and OH-tyrosol), theobromine, quercetin, rutin, catechine and apigenin were the identified and quantified polyphenols. All the tested extracts demonstrated a high protective potential on the superoxide dismutase (SOD), catalase and peroxidase activities. CONCLUSION: Finally, the different extracts from M. myristica and specifically the aqueous ethanol extract reveal several properties such as higher free radical scavenging properties, significant antioxidant capacities and protective potential effects on liver enzymes.

  16. Understanding sensitivity to BH3 mimetics: ABT-737 as a case study to foresee the complexities of personalized medicine

    Directory of Open Access Journals (Sweden)

    Stamelos Vasileios A

    2012-08-01

    Full Text Available Abstract BH3 mimetics such as ABT-737 and navitoclax bind to the BCL-2 family of proteins and induce apoptosis through the intrinsic apoptosis pathway. There is considerable variability in the sensitivity of different cells to these drugs. Understanding the molecular basis of this variability will help to determine which patients will benefit from these drugs. Furthermore, this understanding aids in the design of rational strategies to increase the sensitivity of cells which are otherwise resistant to BH3 mimetics. We discuss how the expression of BCL-2 family proteins regulates the sensitivity to ABT-737. One of these, MCL-1, has been widely described as contributing to resistance to ABT-737 which might suggest a poor response in patients with cancers that express levels of MCL-1. In some cases, resistance to ABT-737 conferred by MCL-1 is overcome by the expression of pro-apoptotic proteins that bind to apoptosis inhibitors such as MCL-1. However, the distribution of the pro-apoptotic proteins amongst the various apoptosis inhibitors also influences sensitivity to ABT-737. Furthermore, the expression of both pro- and anti-apoptotic proteins can change dynamically in response to exposure to ABT-737. Thus, there is significant complexity associated with predicting response to ABT-737. This provides a paradigm for the multiplicity of intricate factors that determine drug sensitivity which must be considered for the full implementation of personalized medicine.

  17. The effects of ABT-491 administration on visual evoked potentials in rat model of hypoxic ischemic brain injury - Original Article

    Directory of Open Access Journals (Sweden)

    Tolgay Ergeno?lu

    2010-12-01

    Full Text Available Aim: In the present study, we aimed to investigate the effects of ABT-491 on visual evoked potentials (VEP in rat model of hypoxic ischemic brain injury (HIBI. Material and Method: Fifty-seven male Wistar newborn rats were used in this study. Animals were divided into three groups randomly. HIBI was formed on postnatal seventh day according to modified Levine-Rice model in 1st (n=18 and 2nd (n=20 groups. Third group (n=19 served as sham group. After HIBI, ABT-491 was applied intraperitoneally to rats in the 1st group (ABT group and saline was administered to the rats in the 2nd group (saline group. On postnatal 16th weeks, VEPs were recorded from Ag-AgCl disc electrode placed on the occipital region. Results: The latencies of P3 wave were shorter in the ABT group than the saline group (p<0.05. Peak-to-peak amplitudes of P2-N2 and N2-P3 were smaller in the ABT and saline groups compared to the sham group (for all pairwise comparisons p<0.001.Conclusions:It was concluded that HIBI caused a decrement in amplitudes of VEP responses and this change could not be ameliorated with ABT-491. However, shortening in latencies of P3 wave could be ameliorated with ABT-491 treatment after HIBI was formed. (Turk Arch Ped 2010; 45: 319-23

  18. Radical-scavenging capacity of phenol fractions in the brown seaweed Ascophyllum nodosum: an electrochemical approach.

    Science.gov (United States)

    Blanc, Nathalie; Hauchard, Didier; Audibert, Laetitia; Gall, Erwan Ar

    2011-04-15

    In this article, the radical-scavenging capacity of phenol fractions extracted from the brown seaweed Ascophyllum nodosum was assessed using in parallel colorimetric methods (ABTS and DPPH) and electrochemistry (cyclic voltammetry). Results obtained by the three methods correlated in the case of global fractions, whereas only ABTS and DPPH correlated when activities were expressed on a phenol basis. The successive fractions separated by both their average molecular size and their polarity exhibited activities largely dependent on their phenol content, suggesting that phlorotannins are the main anti-oxidant molecules in hydro-alcoholic extracts of A. nodosum. In addition, phenol fractions of relative low molecular weight were clearly more active than others. This work opens new opportunities to better evaluate the radical-scavenging potential of phenol pools in algae using both bi-parametric fractionating and electrochemistry. PMID:21376981

  19. In vitro antioxidant assay of medium chain fatty acid rich rice bran oil in comparison to native rice bran oil.

    Science.gov (United States)

    Sengupta, Avery; Ghosh, Mahua; Bhattacharyya, D K

    2015-08-01

    The study aimed to evaluate the in vitro antioxidant activity of medium chain fatty acid (MCFA) rich-rice bran oils in comparison with native rice bran oil. Different in vitro methods were used to evaluate the free radical scavenging activity, metal chelation activity, reducing acitivity, ABTS radical scavenging activity, thiobarbituric acid (TBA) value and so on at different concentrations of the oils such as 10-100 ?g/mL. Inhibition of lipid peroxidation was evaluated measuring thiobarbituric acid responsive substance (TBARS) and conjugated diene formation. All the oils showed potent antioxidant activity at 100 ?g/mL concentration. TBARS formation and conjugated diene formation was lower with MCFA rich oils i.e. the inhibition of lipid peroxidation was more in MCFA rich oils than original rice bran oil. Caprylic acid rich rice bran oil showed maximum antioxidant activity in comparison to capric- and lauric acid rich rice bran oils. Overall the MCFA rich rice bran oils showed to be more potent antioxidant than rice bran oil due to their lower unsaturated fatty acid content. PMID:26243941

  20. Increased lymphocyte apoptosis in mouse models of colitis upon ABT-737 treatment is dependent upon BIM expression.

    Science.gov (United States)

    Lutz, C; Mozaffari, M; Tosevski, V; Caj, M; Cippà, P; McRae, B L; Graff, C L; Rogler, G; Fried, M; Hausmann, M

    2015-08-01

    Exaggerated activation of lymphocytes contributes to the pathogenesis of inflammatory bowel disease (IBD). Medical therapies are linked to the BCL-2 family-mediated apoptosis. Imbalance in BCL-2 family proteins may cause failure in therapeutic responses. We investigated the role of BCL-2 inhibitor ABT-737 for lymphocyte apoptosis in mice under inflammatory conditions. B.6129P2-interleukin (IL)-10(tm1Cgn) /J (IL-10(-/-) ) weighing 25-30 g with ongoing colitis were used. Fifty mg/kg/day ABT-737 was injected intraperitoneally (i.p.). Haematological analyses were performed with an ADVIA 2120 flow cytometer and mass cytometry with a CyTOF 2. Following i.p. administration, ABT-737 was detected in both spontaneous and acute colitis in peripheral blood (PBL) and colon tissue. Treatment led to lymphopenia. CD4(+) CD44(+) CD62L(+) central memory and CD8(+) , CD44(+) CD62L(-) central memory T cells were decreased in PBL upon ABT-737 compared to vehicle-receiving controls. Increased apoptosis upon ABT-737 was determined in blood lymphocytes, splenocytes and Peyer's patches and was accompanied by a decrease in TNF and IL-1B. ABT-737 positively altered the colonic mucosa and ameliorated inflammation, as shown by colonoscopy, histology and colon length. A decreased BIM/BCL-2 ratio or absence of BIM in both Bim(-) (/) (-) and Il10(-) (/) (-) × Bim(-) (/) (-) impeded the protective effect of ABT-737. The BIM/BCL-2 ratio decreased with age and during the course of treatment. Thus, long-term treatment resulted in adapted TNF levels and macroscopic mucosal damage. ABT-737 was efficacious in diminishing lymphocytes and ameliorating colitis in a BIM-dependent manner. Regulation of inappropriate survival of lymphocytes by ABT-737 may provide a therapeutic strategy in IBD. PMID:25845418

  1. Cupric ion reducing antioxidant capacity assay for antioxidants in human serum and for hydroxyl radical scavengers.

    Science.gov (United States)

    Apak, Re?at; Güçlü, Kubilay; Ozyürek, Mustafa; Bekta?o?lu, Burcu; Bener, Mustafa

    2010-01-01

    Tests measuring the combined antioxidant effect of the nonenzymatic defenses in biological fluids may be useful in providing an index of the organism's capability to counteract reactive species known as pro-oxidants, resist oxidative damage, and combat oxidative stress-related diseases. The selected chromogenic redox reagent for the assay of human serum should be easily accessible, stable, selective, and respond to all types of biologically important antioxidants such as ascorbic acid, alpha-tocopherol, beta-carotene, reduced glutathione (GSH), uric acid, and bilirubin, regardless of chemical type or hydrophilicity. Our recently developed cupric reducing antioxidant capacity (CUPRAC) spectrophotometric method for a number of polyphenols and flavonoids using the copper(II)-neocuproine reagent in ammonium acetate buffer is now applied to a complete series of plasma antioxidants for the assay of total antioxidant capacity of serum, and the resulting absorbance at 450 nm is recorded either directly (e.g., for ascorbic acid, alpha-tocopherol, and glutathione) or after incubation at 50 degrees C for 20 min (e.g., for uric acid, bilirubin, and albumin), quantitation being made by means of a calibration curve. The lipophilic antioxidants, alpha-tocopherol and beta-carotene, are assayed in dichloromethane. Lipophilic antioxidants of serum are extracted with n-hexane from an ethanolic solution of serum subjected to centrifugation. Hydrophilic antioxidants of serum are assayed in the centrifugate after perchloric acid precipitation of proteins. The CUPRAC molar absorptivities, linear ranges, and TEAC (trolox equivalent antioxidant capacity) coefficients of the serum antioxidants are established, and the results are evaluated in comparison with the findings of the ABTS/TEAC reference method. The intra- and inter-assay coefficients of variation (CVs) are 0.7 and 1.5%, respectively, for serum. The CUPRAC assay proved to be efficient for glutathione and thiol-type antioxidants, for which the FRAP (ferric reducing antioxidant potency) test is basically nonresponsive. The additivity of absorbances of all the tested antioxidants confirmed that antioxidants in the CUPRAC test do not chemically interact among each other so as to cause an intensification or quenching of the theoretically expected absorbance, and that a total antioxidant capacity (TAC) assay of serum is possible. As a distinct advantage over other electron-transfer based assays (e.g., Folin, FRAP, ABTS, DPPH), CUPRAC is superior in regard to its realistic pH close to the physiological pH, favorable redox potential, accessibility and stability of reagents, and applicability to lipophilic antioxidants as well as hydrophilic ones. The CUPRAC procedure can also assay hydroxyl radicals, being the most reactive oxygen species (ROS). As a more convenient, efficient, and less costly alternative to HPLC/electrochemical detection techniques and to the nonspecific, low-yield TBARS test, we use p-aminobenzoate, 2,4- and 3,5-dimethoxybenzoate probes for detecting hydroxyl radicals generated from an equivalent mixture of [Fe(II)+EDTA] with hydrogen peroxide. The produced hydroxyl radicals attack both the probe and the water-soluble antioxidants in 37 degrees C-incubated solutions for 2 h. The CUPRAC absorbance of the ethylacetate extract due to the reduction of Cu(II)-neocuproine reagent by the hydroxylated probe decreases in the presence of (.)OH scavengers, the difference being proportional to the scavenging ability of the tested compound. The developed method is less lengthy, more specific, and of a higher yield than the classical TBARS assay. PMID:20072920

  2. Strong Inhibition of O-Atom Transfer Reactivity for Mn(IV)(O)(?-Radical-Cation)(Lewis Acid) versus Mn(V)(O) Porphyrinoid Complexes.

    Science.gov (United States)

    Zaragoza, Jan Paulo T; Baglia, Regina A; Siegler, Maxime A; Goldberg, David P

    2015-05-27

    The oxygen atom transfer (OAT) reactivity of two valence tautomers of a Mn(V)(O) porphyrinoid complex was compared. The OAT kinetics of Mn(V)(O)(TBP8Cz) (TBP8Cz = octakis(p-tert-butylphenyl)corrolazinato(3-)) reacting with a series of triarylphosphine (PAr3) substrates were monitored by stopped-flow UV-vis spectroscopy, and revealed second-order rate constants ranging from 16(1) to 1.43(6) × 10(4) M(-1) s(-1). Characterization of the OAT transition state analogues Mn(III)(OPPh3)(TBP8Cz) and Mn(III)(OP(o-tolyl)3)(TBP8Cz) was carried out by single-crystal X-ray diffraction (XRD). A valence tautomer of the closed-shell Mn(V)(O)(TBP8Cz) can be stabilized by the addition of Lewis and Brønsted acids, resulting in the open-shell Mn(IV)(O)(TBP8Cz(•+)):LA (LA = Zn(II), B(C6F5)3, H(+)) complexes. These Mn(IV)(O)(?-radical-cation) derivatives exhibit dramatically inhibited rates of OAT with the PAr3 substrates (k = 8.5(2) × 10(-3) - 8.7 M(-1) s(-1)), contrasting the previously observed rate increase of H-atom transfer (HAT) for Mn(IV)(O)(TBP8Cz(•+)):LA with phenols. A Hammett analysis showed that the OAT reactivity for Mn(IV)(O)(TBP8Cz(•+)):LA is influenced by the Lewis acid strength. Spectral redox titration of Mn(IV)(O)(TBP8Cz(•+)):Zn(II) gives Ered = 0.69 V vs SCE, which is nearly +700 mV above its valence tautomer Mn(V)(O)(TBP8Cz) (Ered = -0.05 V). These data suggest that the two-electron electrophilicity of the Mn(O) valence tautomers dominate OAT reactivity and do not follow the trend in one-electron redox potentials, which appear to dominate HAT reactivity. This study provides new fundamental insights regarding the relative OAT and HAT reactivity of valence tautomers such as M(V)(O)(porph) versus M(IV)(O)(porph(•+)) (M = Mn or Fe) found in heme enzymes. PMID:25964988

  3. Reaction between protein radicals and other biomolecules

    DEFF Research Database (Denmark)

    Østdal, Henrik; Davies, Michael Jonathan

    2002-01-01

    The present study investigates the reactivity of bovine serum albumin (BSA) radicals towards different biomolecules (urate, linoleic acid, and a polypeptide, poly(Glu-Ala-Tyr)). The BSA radical was formed at room temperature through a direct protein-to-protein radical transfer from H(2)O(2)-activated immobilized horseradish peroxidase (im-HRP). Subsequently, each of the three different biomolecules was separately added to the BSA radicals, after removal of im-HRP by centrifugation. Electron spin resonance (ESR) spectroscopy showed that all three biomolecules quenched the BSA radicals. Subsequent analysis showed a decrease in the concentration of urate upon reaction with the BSA radical, while the BSA radical in the presence of poly(Glu-Ala-Tyr) resulted in increased formation of the characteristic protein oxidation product, dityrosine. Reaction between the BSA radical and a linoleic acid oil-in-water emulsion resulted in additional formation of lipid hydroperoxides and conjugated dienes. The results clearly show that protein radicals have to be considered as dynamic species during oxidative processes in biological systems and that protein radicals should not be considered as end-products, but rather as reactive intermediates during oxidative processes in biological systems hereby supporting recent data.

  4. A phase I study of ABT-510 plus bevacizumab in advanced solid tumors

    International Nuclear Information System (INIS)

    Targeting multiple regulators of tumor angiogenesis have the potential to improve treatment efficacy. Bevacizumab is a monoclonal antibody directed against vascular endothelial growth factor and ABT-510 is a synthetic analog of thrombospondin, an endogenous angiogenesis inhibitor. Dual inhibition may result in additional benefit. We evaluated the safety, tolerability, and efficacy of the combination of bevacizumab plus ABT-510 in patients with refractory solid tumors. We also explored the effects of these agents on plasma-based biomarkers and wound angiogenesis. Thirty-four evaluable subjects were enrolled and received study drug. Therapy was well tolerated; minimal treatment-related grade 3/4 toxicity was observed. One patient treated at dose level 1 had a partial response and five other patients treated at the recommended phase II dose had prolonged stable disease for more than 1 year. Biomarker evaluation revealed increased levels of D-dimer, von Willebrand factor, placental growth factor, and stromal-derived factor 1 in response to treatment with the combination of bevacizumab and ABT-510. Data suggest that continued evaluation of combination antiangiogenesis therapies may be clinically useful

  5. Celecoxib-induced apoptosis is enhanced by ABT-737 and by inhibition of autophagy in human colorectal cancer cells

    OpenAIRE

    Huang, Shengbing; Sinicrope, Frank A

    2010-01-01

    Apoptosis and autophagy have been shown to be negatively regulated by prosurvival Bcl-2 proteins. We determined whether the anticancer agent celecoxib, alone or combined with a small molecule Bcl-2/Bcl-xL antagonist (ABT-737), can induce autophagy in colon cancer cells. Furthermore, we determined whether inhibition of autophagy can drive colon cancer cells into apoptosis. Celecoxib was shown to induce apoptosis that was attenuated by ectopic Bcl-2 or Bax knockout. ABT-737 synergistically enha...

  6. Chemical Constituents with Free-Radical-Scavenging Activities from the Stem of Microcos paniculata

    OpenAIRE

    Yu Chen; Xiang-Ming Liu; Tong Zheng; Zhi-Nan Mei; Guang-Zhong Yang; Su Chen; Hua Fan

    2010-01-01

    The free-radical-scavenging activities of various solvent extracts of Microcos paniculata were evaluated through in vitro model systems, such as 1,1-diphenyl-2-picrylhydrazyl (DPPH), 2,2'-azino-bis-(3-ethylbenzothiazoline-6-sulfonate) (ABTS) and Co (II) EDTA-induced luminol chemiluminescence by flow injection. In all three of these systems the ethyl acetate (EtOAc) extract showed the highest free-radical-scavenging activity compared with the other three (n-BuOH, water and petroleum ether) ext...

  7. Cafestol overcomes ABT-737 resistance in Mcl-1-overexpressed renal carcinoma Caki cells through downregulation of Mcl-1 expression and upregulation of Bim expression.

    Science.gov (United States)

    Woo, S M; Min, K-J; Seo, B R; Nam, J-O; Choi, K S; Yoo, Y H; Kwon, T K

    2014-01-01

    Although ABT-737, a small-molecule Bcl-2/Bcl-xL inhibitor, has recently emerged as a novel cancer therapeutic agent, ABT-737-induced apoptosis is often blocked in several types of cancer cells with elevated expression of Mcl-1. Cafestol, one of the major compounds in coffee beans, has been reported to have anti-carcinogenic activity and tumor cell growth-inhibitory activity, and we examined whether cafestol could overcome resistance against ABT-737 in Mcl-1-overexpressed human renal carcinoma Caki cells. ABT-737 alone had no effect on apoptosis, but cafestol markedly enhanced ABT-737-mediated apoptosis in Mcl-1-overexpressed Caki cells, human glioma U251MG cells, and human breast carcinoma MDA-MB231 cells. By contrast, co-treatment with ABT-737 and cafestol did not induce apoptosis in normal human skin fibroblast. Furthermore, combined treatment with cafestol and ABT-737 markedly reduced tumor growth compared with either drug alone in xenograft models. We found that cafestol inhibited Mcl-1 protein expression, which is important for ABT-737 resistance, through promotion of protein degradation. Moreover, cafestol increased Bim expression, and siRNA-mediated suppression of Bim expression reduced the apoptosis induced by cafestol plus ABT-737. Taken together, cafestol may be effectively used to enhance ABT-737 sensitivity in cancer therapy via downregulation of Mcl-1 expression and upregulation of Bim expression. PMID:25375379

  8. In vitro antioxidant potential and deoxyribonucleic acid protecting activity of CNB-001, a novel pyrazole derivative of curcumin

    Directory of Open Access Journals (Sweden)

    Richard L Jayaraj

    2014-01-01

    Full Text Available Background: Free radicals are underpinned to initiate cascade of toxic events leading to oxidative stress and resultant cell death in many neurodegenerative disorders. Now-a-days antioxidants have become mandatory in the treatment of various diseases apart from the drug?s modes of action. CNB-001, a novel hybrid molecule synthesized by combining curcumin and cyclohexyl bisphenol A is known to possess various biological activities, but the antioxidative property of the compound has not yet been elucidated. Aim: The present study is aimed to analyze various free radicals scavenging by employing in vitro antioxidant assays and to evaluate the deoxyribonucleic acid (DNA protecting the ability of CNB-001 against hydroxyl radicals. Materials and methods: The in vitro antioxidant potential of CNB-001 was evaluated by analyzing its ability to scavenge DPPH, ABTS, nitric oxide, superoxide, hydrogen peroxide, superoxide anion, hydroxyl, hydrogen peroxide radicals and reducing power using spectroscopic method. The DNA protecting activity of CNB-001 was also evaluated on pUC19 plasmid DNA subjected to hydroxyl radicals using standard agarose gel electrophoresis. Results: From the assays, it was observed that CNB-001 scavenged free radicals effectively in a dose dependent manner. CNB-001 scavenged 2,2-diphenyl-1-picrylhydrazyl (IC50 = 44.99 ?g/ml, 2,2-azinobis (3-ethylbenzothiazoline-6-sulfonic acid (IC50 = 17.99 ?g/ml, nitric oxide (IC50 = 1.36 ?g/ml, superoxide radical (IC50 = 77.17 ?g/ml, hydrogen peroxide (IC50 = 492.7 ?g/ml, superoxide (IC50 = 36.92 ?g/ml and hydroxyl (IC50 = 456.5 ?g/ml radicals effectively and the reducing power was found to be 11.53 ?g/ml. CNB-001 showed considerable protecting activity against plasmid DNA (pUC19 strand scission by ·OH at dose dependent manner. Conclusion: Results from these assays concluded that CNB-001 has a good antioxidant potential by reducing reactive oxygen and reactive nitrogen radicals and it showed significant protecting activity against DNA scission by hydroxyl radicals. Hence, CNB-001 can be further developed as potential drug for free radical induced neurodegenerative disorders.

  9. Hydrophobic benzyl amines as supports for liquid-phase C-terminal amidated peptide synthesis: application to the preparation of ABT-510.

    Science.gov (United States)

    Matsumoto, Emiko; Fujita, Yuko; Okada, Yohei; Kauppinen, Esko I; Kamiya, Hidehiro; Chiba, Kazuhiro

    2015-09-01

    C-terminal amidation is one of the most common modification of peptides and frequently found in bioactive peptides. However, the C-terminal modification must be creative, because current chemical synthetic techniques of peptides are dominated by the use of C-terminal protecting supports. Therefore, it must be carried out after the removal of such supports, complicating reaction work-up and product isolation. In this context, hydrophobic benzyl amines were successfully added to the growing toolbox of soluble tag-assisted liquid-phase peptide synthesis as supports, leading to the total synthesis of ABT-510 (2). Although an ethyl amide-forming type was used in the present work, different types of hydrophobic benzyl amines could also be simply designed and prepared through versatile reductive aminations in one step. The standard acidic treatment used in the final deprotection step for peptide synthesis gave the desired C-terminal secondary amidated peptide with no epimerization. PMID:26200065

  10. Antioxidant activities and radical scavenging activities of flavonoids studied by the electrochemical methods and ESR technique based on the novel paramagnetic properties of poly(aniline-co-5-aminosalicylic acid)

    International Nuclear Information System (INIS)

    Graphical abstract: ESR spectra of the PAASA/RGO/graphite electrodes: (1) in the buffer solution consisting of 0.20 M phosphate and methanol (80: 20, v/v), (2) in the buffer solutions containing 150 ?M of (+)-catechin. -- Abstract: Four kinds of flavonoid, viz. flavanone naringenin, Flavone apigenin, flavonol kaempferol, and flavanol (+)-catechin, are used to investigate their antioxidant and radical scavenging activitis in the water-methanol solution of pH 6.3, using the electrochemical methods and electron spin resonance (ESR) technique. Poly(aniline-co-5-aminosalicylic acid) (PAASA) is first used as a radical source that was polymerized on a reduced graphene oxide (RGO)/glassy carbon (GC) disk or on the RGO/graphite fiber electrode. The assessment of the antioxidant activities is performed using both cyclic voltammetry and the open circuit potential measurement. On the basis of results from both electrochemical mathods, the order of the antioxidant actitvities of flavonoids is as follows: (+)-catechin > kaempferol > apigenin > naringenin However, the difference in the antioxidant activities between naringenin and apigenin is very small. On the basis of the ESR signal intensities of PAASA, the order of the radical scavenging activities of flavonoids is in good agreement with that of the above antioxdant activities.Three oxidation peaks on the cyclic voltammograms of (+)-catechin are first detected, which gives us a deep insight into the oxidation mechanism of (+)-catechin

  11. Exploiting the Synergy between Carboplatin and ABT-737 in the Treatment of Ovarian Carcinomas

    OpenAIRE

    Jain, Harsh Vardhan; Richardson, Alan; Meyer-Hermann, Michael; Helen M. Byrne

    2014-01-01

    Platinum drug-resistance in ovarian cancers mediated by anti-apoptotic proteins such as Bcl-xL is a major factor contributing to the chemotherapeutic resistance of recurrent disease. Consequently, concurrent inhibition of Bcl-xL in combination with chemotherapy may improve treatment outcomes for patients. Here, we develop a mathematical model to investigate the potential of combination therapy with ABT-737, a small molecule inhibitor of Bcl-xL, and carboplatin, a platinum-based drug, on a sim...

  12. A novel poly(ADP-ribose) polymerase inhibitor, ABT-888, radiosensitizes malignant human cell lines under hypoxia

    International Nuclear Information System (INIS)

    The chemo- and radioresponse of tumor cells can be determined by genetic factors (e.g., those that modify cell cycle arrest, DNA damage repair or cell death) and microenvironmental factors, such as hypoxia. Poly(ADP-ribose) polymerase (PARP) is a nuclear enzyme that rapidly recognizes and binds to DNA breaks to facilitate DNA strand break repair. Pre-clinical data suggest that PARP inhibitors (PARPi) may potentiate the effects of radiotherapy and chemotherapy. However, it is unclear as to whether PARPi are effective against hypoxic cells. We therefore tested the role for a novel PARPi, ABT-888, as a radiosensitizing agent under hypoxic conditions. Using human prostate (DU-145, 22RV1) and non-small cell lung (H1299) cancer cell lines, we observed that ABT-888 inhibited both recombinant PARP activity and intracellular PARP activity (86% to 92% decrease in all 3 cells lines following 2.5 ?M treatment). ABT-888 was toxic to both oxic and hypoxic cells. When ABT-888 was combined with ionizing radiation (IR), clonogenic radiation survival was decreased by 40-50% under oxic conditions. Under acute hypoxia, ABT-888 radiosensitized malignant cells to a level similar to oxic radiosensitivity. To our knowledge, this is the first study to demonstrate that inhibition of PARP activity can sensitize hypoxic cancer cells and the combination of IR-PARPi has the potential to improve the therapeutic ratio of radiotherapy

  13. Anticancer compound ABT-263 accelerates apoptosis in virus-infected cells and imbalances cytokine production and lowers survival rates of infected mice

    OpenAIRE

    Kakkola, L; Denisova, O V; Tynell, J; Viiliäinen, J; Ysenbaert, T; Matos, R C; Nagaraj, A; Öhman, T; Kuivanen, S; Paavilainen, H; Feng, L; Yadav, B; Julkunen, I; Vapalahti, O.; Hukkanen, V

    2013-01-01

    ABT-263 and its structural analogues ABT-199 and ABT-737 inhibit B-cell lymphoma 2 (Bcl-2), BCL2L1 long isoform (Bcl-xL) and BCL2L2 (Bcl-w) proteins and promote cancer cell death. Here, we show that at non-cytotoxic concentrations, these small molecules accelerate the deaths of non-cancerous cells infected with influenza A virus (IAV) or other viruses. In particular, we demonstrate that ABT-263 altered Bcl-xL interactions with Bcl-2 antagonist of cell death (Bad), Bcl-2-associated X protein (...

  14. Free radical activity in young adult cigarette smokers.

    OpenAIRE

    Leonard, M.B.; Lawton, K; Watson, I. D.; MacFarlane, I.

    1995-01-01

    Cigarette smoke is capable of generating free radicals. In this study markers of free radical activity (thiobarbituric acid reactivity, superoxide dismutase and glutathione peroxidase) were measured in young adult smoking and non-smoking volunteers. No significant differences were found in any of the free radical markers between the two groups. The number of leucocytes was elevated and a positive correlation was found between the number of leucocytes and thiobarbituric acid reactivity in the ...

  15. Emergence of oxyl radicals as selective oxidants.

    Science.gov (United States)

    Ramasarma, T

    2012-10-01

    Hydroxyl radicals (HO*) are derived in Fenton reaction with ferrous salt and H2O2 in acid medium, and at neutral pH, metal-oxyl radicals (M-O*) predominate. Evidence is accumulating that M-O* radicals are also active in oxidation reactions, in addition to metal-oxo (M=O) now shown in many publications. Reactivity of these radicals gives selective oxidized products useful in cellular activities, in contrast to purported indiscriminate cell damage by hydroxyl radicals. Reactions with vanadium compounds, such as diperoxovanadate, peroxo-bridged mixed valency divanadate, vanadium-oxyl radical, tetravalent vanadyl and decavanadate illustrates selective gain in oxidative capacity of oxo- and oxyl- species. Occurrence of ESR signals typical of hydroxyl radicals is demonstrated in cell homogenates and tissue perfusates treated with spin trap agents. It is known for a long time lipid peroxides are formed in tissue microsomal systems exclusively in presence of salts of iron, among many metals tested. Oxygen and a reducing agent, ascorbate (non-enzymic) or NADPH (enzymic) are required to produce 'ferryl', the chelated Fe=O active form (possibly Fe-O* and Fe-O-O-Fe ?) for the crucial step of H-atom abstraction. Yet literature is replete with unsupported affirmations that hydroxyl radicals initiate lipid peroxidation, an unexplained fixation of mindset. The best-known *OH generator, a mixture of ferrous salt and H2O2, does not promote lipid peroxidation, nor do the many hydroxyl radical quenching agents stop it. The availability of oxo and oxyl-radical forms with transition metals, and also with non metals, P, S, N and V, calls for expansion of vision beyond superoxide and hydroxyl radicals and explore functions of multiple oxygen radicals for their biological relevance. PMID:23259316

  16. Reactions of carbonate radical with cobalt(II) aminopolycarboxylates

    International Nuclear Information System (INIS)

    Reactions of carbonate (CO3-radical) and bicarbonate (HCO3radical) radicals generated by photolysis of a carbonate or bicarbonate solution at pH 11.2 and 8.5, respectively, with Co(II) complexes of iminodiacetic acid (IDA) and ethylenediaminetetraacetic acid (EDTA) have been studied. The rate constants for the reactions were in the order of 106-107 dm3mol-1s-1. From the time-resolved spectroscopy of the products formed after reaction of CO3-radical or HCO3radical, it is observed that CO3-radical or HCO3radical oxidize the metal center to its higher oxidation state. (author) 26 refs.; 2 figs.; 1 tab

  17. Contemporary Radical Prostatectomy

    OpenAIRE

    Leon Sun; Qiang Fu; Judd W. Moul

    2011-01-01

    Purpose. Patients diagnosed with clinically localized prostate cancer have more surgical treatment options than in the past. This paper focuses on the procedures' oncological or functional outcomes and perioperative morbidities of radical retropubic prostatectomy, radical perineal prostatectomy, and robotic-assisted laparoscopic radical prostatectomy. Materials and Methods. A MEDLINE/PubMed search of the literature on radical prostatectomy and other new management options was performed. Resul...

  18. Reactions of melatonin with radicals in deoxygenated aqueous solution

    International Nuclear Information System (INIS)

    Reactions of melatonin (N-acetyl-5-methoxytryptamine) with radiolytically generated radicals were studied. Reaction of melatonin with OH radicals is diffusion-controlled (k=1.2 x 1010 dm3 mol-1 x s-1), the main (but not the only one) intermediate being the indolyl-type radical, while the rate constant for the reaction with hydrated electrons is k=4.3 x 108 dm3 x mol-1 x s-1. Melatonin is capable of scavenging tert-butanol radicals, while its reactivity towards polymer radicals of poly(acrylic acid) and poly(vinyl pyrrolidone) is very low. (author)

  19. In Vitro Antioxidant Activities, Free Radical Scavenging Capacity, and Tyrosinase Inhibitory of Flavonoid Compounds and Ferulic Acid from Spiranthes sinensis (Pers.) Ames

    OpenAIRE

    Chung Pin Liang; Chia Hao Chang; Chien Cheng Liang; Kuei Yu Hung; Chang Wei Hsieh

    2014-01-01

    In this study, ultrasound-assisted extraction (UAE) and other methods of extracting flavonoid compounds and ferulic acid (FA) from S. sinensis were investigated. Five different extraction methods, including water extraction (W), water extraction using UAE (W+U), 75% ethanol extraction (E), 75% ethanol extraction using UAE (E+U), and supercritical CO2 extraction (SFE) were applied in the extraction of bioactive compounds (flavonoids and ferulic acid) in order to compare their efficiency. The h...

  20. Radical theory of rings

    CERN Document Server

    Gardner, JW

    2003-01-01

    Radical Theory of Rings distills the most noteworthy present-day theoretical topics, gives a unified account of the classical structure theorems for rings, and deepens understanding of key aspects of ring theory via ring and radical constructions. Assimilating radical theory's evolution in the decades since the last major work on rings and radicals was published, the authors deal with some distinctive features of the radical theory of nonassociative rings, associative rings with involution, and near-rings. Written in clear algebraic terms by globally acknowledged authorities, the presentation

  1. Rational discovery and development of a mitochondria-targeted antioxidant based on cinnamic acid scaffold.

    Science.gov (United States)

    Teixeira, José; Soares, Pedro; Benfeito, Sofia; Gaspar, Alexandra; Garrido, Jorge; Murphy, Michael P; Borges, Fernanda

    2012-05-01

    A novel mitochondria-targeted antioxidant (TPP-OH) was synthesized by attaching the natural hydrophilic antioxidant caffeic acid to an aliphatic lipophilic carbon chain containing a triphenylphosphonium (TPP) cation. This compound has similar antioxidant activity to caffeic acid as demonstrated by measurement of DPPH/ABTS radical quenching and redox potentials, but is significantly more hydrophobic than its precursor as indicated by the relative partition coefficients. The antioxidant activity of both compounds was intrinsic related to the ortho-catechol system, as the methoxylation of the phenolic functions, namely in TPP-OCH(3) and dimethoxycinnamic acid, gave compounds with negligible antioxidant action. The incorporation of the lipophilic TPP cation to form TTP-OH and TPP-OCH(3) allowed the cinnamic derivatives to accumulate within mitochondria in a process driven by the membrane potential. However, only TPP-OH was an effective antioxidant: TPP-OH protected cells against H(2)O(2) and linoleic acid hydroperoxide-induced oxidative stress. As mitochondrial oxidative damage is associated with a number of clinical disorders, TPP-OH may be a useful lead that could be added to the family of mitochondria-targeted antioxidants that can decrease mitochondrial oxidative damage. PMID:22292941

  2. Oxidation of SO2 by stabilized Criegee intermediate (sCI radicals as a crucial source for atmospheric sulfuric acid concentrations

    Directory of Open Access Journals (Sweden)

    M. Boy

    2013-04-01

    Full Text Available The effect of increased reaction rates of stabilized Criegee intermediates (sCIs with SO2 to produce sulfuric acid is investigated using data from two different locations, SMEAR II, Hyytiälä, Finland, and Hohenpeissenberg, Germany. Results from MALTE, a zero-dimensional model, show that using previous values for the rate coefficients of sCI + SO2, the model underestimates gas phase H2SO4 by up to a factor of two when compared to measurements. Using the rate coefficients recently calculated by Mauldin et al. (2012 increases sulfuric acid by 30–40%. Increasing the rate coefficient for formaldehyde oxide (CH2OO with SO2 according to the values recommended by Welz et al. (2012 increases the H2SO4 yield by 3–6%. Taken together, these increases lead to the conclusion that, depending on their concentrations, the reaction of stabilized Criegee intermediates with SO2 could contribute as much as 33–46% to atmospheric sulfuric acid gas phase concentrations at ground level. Using the SMEAR II data, results from SOSA, a one-dimensional model, show that the contribution from sCI reactions to sulfuric acid production is most important in the canopy, where the concentrations of organic compounds are the highest, but can have significant effects on sulfuric acid concentrations up to 100 m. The recent findings that the reaction of sCI + SO2 is much faster than previously thought together with these results show that the inclusion of this new oxidation mechanism could be crucial in regional as well as global models.

  3. Free radical scavenging activity of papaya juice

    Energy Technology Data Exchange (ETDEWEB)

    Webman, E.J.; Mower, H.F.; Edlin, Gordon

    1989-03-01

    Papaya juice is an efficient scavenger of highly reactive hydroxyl radicals (OH radical) formed during /sup 60/Co irradiation of water. The OH anion radicals were detected by the electron spin resonance (ESR) technique of spin trapping using DMPO (5,5-dimethyl-1-pyrroline-N-oxide) or by a colorimetric assay in which salicylate is converted into polyhydroxybenzoic acids. Papaya juice is also able to quench the ESR signal of a stable free radical (TEMPOL) and the ESR signal of the DMPO-OH adduct. The active substance(s) in papaya juice are heat-stable, dialyzable, and soluble in water but not in lipid solvents. The active agents do not appear to be ascorbate, tocopherol, or carotenoids.

  4. Free radical scavenging activity of papaya juice

    International Nuclear Information System (INIS)

    Papaya juice is an efficient scavenger of highly reactive hydroxyl radicals (OH radical) formed during 60Co irradiation of water. The OH anion radicals were detected by the electron spin resonance (ESR) technique of spin trapping using DMPO (5,5-dimethyl-1-pyrroline-N-oxide) or by a colorimetric assay in which salicylate is converted into polyhydroxybenzoic acids. Papaya juice is also able to quench the ESR signal of a stable free radical (TEMPOL) and the ESR signal of the DMPO-OH adduct. The active substance(s) in papaya juice are heat-stable, dialyzable, and soluble in water but not in lipid solvents. The active agents do not appear to be ascorbate, tocopherol, or carotenoids. (author)

  5. Radical Perineal Prostatectomy

    Directory of Open Access Journals (Sweden)

    Cemal Gökta?

    2015-12-01

    Full Text Available Prostate cancer is the most common malignancy and the second leading cause of cancer death in men. Complete surgical removal of the prostate is the most commonly used treatment option for patients with localized prostate cancer. Surgical treatment of localized prostate cancer includes radical retropubic prostatectomy, radical perineal prostatectomy and robotic/ laparoscopic radical prostatectomy. Since lympadenectomy from the same incision is not possible in radical retropubic prostatectomy, this approach is less preferable. On the other hand, when radical perineal prostatectomy in well selected cases is compared with radical retropubic prostatectomy in terms of many operational or functional criteria, similar results were obtained. In this paper, we aimed to report our experiences with this uncommon surgical approach.

  6. In Vitro Activity of ABT-773 against Legionella pneumophila, Its Pharmacokinetics in Guinea Pigs, and Its Use to Treat Guinea Pigs with L. pneumophila Pneumonia

    OpenAIRE

    Edelstein, Paul H; F. Higa; Edelstein, Martha A. C.

    2001-01-01

    The activity of ABT-773 was studied against extracellular and intracellular Legionella pneumophila and for the treatment of guinea pigs with L. pneumophila pneumonia. The ABT-773 MIC at which 50% of isolates are inhibited (MIC50) for 20 different Legionella sp. strains was 0.016 ?g/ml, whereas the MIC50s of clarithromycin and erythromycin were 0.032 and 0.125 ?g/ml, respectively. ABT-773 (1 ?g/ml) was bactericidal for two L. pneumophila strains grown in guinea pig alveolar macrophages. In con...

  7. Effect of free radical spin trap N-tert-butyl-alpha-phenylnitrone (PBN) on seizures induced in immature rats by homocysteic acid.

    Czech Academy of Sciences Publication Activity Database

    Folbergrová, Jaroslava; Druga, Rastislav; Otáhal, Jakub; Haugvicová, Renata; Mareš, Pavel; Kubová, Hana

    2006-01-01

    Ro?. 201, ?. 1 (2006), s. 105-119. ISSN 0014-4886 R&D Projects: GA ?R(CZ) GA309/05/2015; GA ?R(CZ) GA309/02/1238 Institutional research plan: CEZ:AV0Z50110509; CEZ:AV0Z50200510 Keywords : DL-homocysteic acid induced seizures * neuronal damage * protection Subject RIV: ED - Physiology Impact factor: 4.156, year: 2006

  8. Comparison of In Vitro Activities of ABT-773 and Telithromycin against Macrolide-Susceptible and -Resistant Streptococci and Staphylococci

    OpenAIRE

    Shortridge, Virginia D.; Zhong, Ping; Cao, ZhenSheng; Beyer, Jill M.; Almer, Laurel S.; Ramer, Nancy C.; Doktor, Stella Z.; Flamm, Robert K.

    2002-01-01

    The activity of a new ketolide, ABT-773, was compared to the activity of the ketolide telithromycin (HMR-3647) against over 600 gram-positive clinical isolates, including 356 Streptococcus pneumoniae, 167 Staphylococcus aureus, and 136 Streptococcus pyogenes isolates. Macrolide-susceptible isolates as well as macrolide-resistant isolates with ribosomal methylase (Erm), macrolide efflux (Mef), and ribosomal mutations were tested using the NCCLS reference broth microdilution method. Both compou...

  9. Cistectomía radical robótica / Robotic radical cystectomy

    Scientific Electronic Library Online (English)

    Burak, Turna; Monish, Aron; Georges-Pascal, Haber; Inderbir S., Gill; Jihad H., Kaouk.

    2007-05-01

    Full Text Available Objetivos: En la última década hemos visto un tremendo crecimiento en la implantacion y desarrollo de los robots quirúrgicos. Popularizados por la prostatectomía radical, las técnicas robóticas están siendo, en la actualidad, muy aplicadas en la cistectomía radical. Trataremos aquí de revisar el des [...] arrollo y estado actual de la cistectomía radical robótica (CRR) en la práctica contemporánea de la urología. Métodos: Se ha revisado toda la literatura publicada, entre 1995 y 2007, en la base de datos de la Biblioteca Nacional de Medicina (MEDLINE) utilizando las palabras clave: robótica, asistido por robot, laparoscópica y cistectomía. Desde el primer trabajo en 2003, se han encontrado 9 originales publicados. Se valoraron con respecto a la técnica, ventajas y desventajas perioperatorias y resultados oncológicos. Describimos asimismo nuestra experiencia inicial, aún no publicada. Resultados: En este momento todos los artículos publicados sobre la CRR se basan en un número pequeño de pacientes con seguimientos a corto plazo. No obstante, demuestran la viabilidad de la CRR con resultados perioperatorios esperanzadores. Comparada con la cistectomía radical abierta (CRA), la CRR parece estar asociada con menor pérdida de sangre, estancia hospitalaria y necesidades analgésicas. Estas ventajas se encuentran asimismo en la cistectomía radical laparoscópica (CRL) y son una función del abordaje mínimamente invasivo. El tiempo quirúrgico es mayor, de forma considerable cuando el tiempo intestinal se realiza de manera intracorpórea. Conclusiones: La cistectomía radical robótica está en evolución. La viabilidad técnica ha sido demostrada. Los resultados perioperatorios iniciales son prometedores. Los resultados oncológicos esperan identificar el papel de la misma en el manejo del cáncer de vejiga. Se necesitan ensayos prospectivos y aleatorizados comparando la CRA con la CRR y la CRL. Abstract in english Objectives: The last decade has seen tremendous growth of surgical robotics. Popularized for radical prostatectomy, robotic techniques are now increasingly being applied to radical cystectomy. Herein, we review the development and current status of robotic radical cystectomy (RRC) in contemporary ur [...] ological practice. Methods: Between 1995 and 2007 published literature was reviewed using the National Library of Medicine database and the following key words: robotic, robot-assisted, laparoscopic and cystectomy. Since the first report in 2003, nine published original reports were identified. These were evaluated with regards to the technique, advantages and disadvantages, perioperative and oncological outcomes. Our initial experience, as yet unpublished, is also described. Results: At this writing, all published papers on RRC are based on small number of patients with short-term follow-up. Nevertheless, they have demonstrated the technical feasibility of RRC with encouraging perioperative outcomes. Compared to open radical cystectomy (ORC), RRC appears to be associated with decreased blood loss, hospital stay and analgesic requirement. These advantages are also found with laparoscopic radical cystectomy (LRC) and are a function of the minimally invasive approach. The operating time is longer, markedly so when the bowel work is performed intracorporeally. Conclusions: RRC is in evolution. Technical feasibility has been demonstrated. Initial perioperative outcomes are encouraging. Oncological outcomes are awaited to identify the role of RRC in the management of bladder cancer. Multi-center prospective randomized trials comparing ORC with RRC and LRC are necessary.

  10. Quantificação de compostos fenólicos e ácido ascórbico em frutos e polpas congeladas de acerola, caju, goiaba e morango / Quantification of phenolic compounds and ascorbic acid in fruits and frozen pulp of acerola, cashew, strawberry and guava

    Scientific Electronic Library Online (English)

    Juliana Mesquita, Freire; Celeste Maria Patto de, Abreu; Denise Alvarenga, Rocha; Angelita Duarte, Corrêa; Natália Rodrigues, Marques.

    2013-12-01

    Full Text Available O crescente interesse da população pela promoção da saúde vem despertando a atenção dos consumidores por alimentos ricos em antioxidantes, combinado com a praticidade do consumo de sucos de frutos processados. O presente trabalho objetivou quantificar e avaliar a capacidade antioxidante de compostos [...] fenólicos e ácido ascórbico em frutas in natura e polpas congeladas. As frutas in natura e polpas congeladas obtidas na região de Lavras - MG foram submetidas à quantificação de compostos fenólicos e ácido ascórbico e os respectivos extratos acetônico-etanólico e acetônico-metanólico. Foram determinadas suas atividades antioxidantes pelos métodos radicalares DPPH e ABTS. O extrato acetônico-metanólico foi mais efetivo para extrair os compostos antioxidantes das amostras. Apenas as polpas congeladas de acerola apresentaram uma redução do teor de compostos fenólicos em relação ao fruto. Para o teor de ácido ascórbico, houve uma redução nas polpas congeladas de acerola e goiaba. As amostras de acerola apresentaram os maiores teores de compostos fenólicos, ácido ascórbico e atividade antioxidante em relação aos demais frutos analisados. Abstract in english The growing public interest in health- promotion, has called the attention of consumers for foods rich in antioxidants, combined with the practicality of the consumption of processed fruit juices. Therefore, this study aimed to quantify and evaluate the antioxidant capacity of phenolic compounds and [...] ascorbic acid in fruits "in natura" and frozen pulps. The fruits "in natura" and frozen pulps from region of Lavras-MG, underwent quantification of phenolic compounds, ascorbic acid and the corresponding extracts acetonic-ethanolic and acetonic-methanolic. Their antioxidant activities were evaluated by DPPH and ABTS radical methods. The extract acetonic-methanolic was more effective to extract the antioxidant compounds from samples. Only frozen acerola pulps showed lower content of phenolic compounds in relation to fruit. For ascorbic acid, there was a reduction in the frozen pulp of acerola and guava. Acerola samples showed higher content of phenolic compounds, ascorbic acid and antioxidant activity compared to other fruits analyzed.

  11. Antimicrobial, free radical scavenging activities and catalytic oxidation of benzyl alcohol by nano-silver synthesized from the leaf extract of Aristolochia indica L.: a promenade towards sustainability

    Science.gov (United States)

    Shanmugam, C.; Sivasubramanian, G.; Parthasarathi, Bera; Baskaran, K.; Balachander, R.; Parameswaran, V. R.

    2015-07-01

    Silver nanoparticles (Ag-NPs) were synthesized from aqueous silver nitrate through a simple route using the leaf extract of Aristolochia indica L. (LAIL) which acted as a reducing as well as capping agent. X-ray diffraction confirmed that the synthesized silver particles have a face centred cubic structure. EDS predicted the presence of elemental silver. The SEM images showed the synthesis of spherically mono-dispersed particles, with nano dimensions accounted by the TEM images. Infra-red spectrum adopted to the different organic functionalities present at the surface of the particles. TGA indicated an overall 11 % weight loss up to 1000 °C, suggesting desorption of biomolecules from the surface. X-ray photoelectron spectroscopy (XPS) analysis revealed the presence of metallic silver nanoparticles. The prepared material was utilized as catalyst in the oxidation of benzyl alcohol with molecular oxygen as the oxidant in methanol, under ambient conditions of temperature and pressure. Also Ag-NPs showed good to moderate anti-microbial activity employing the Agar disc diffusion method against various strains using Ciprofloxacin and Fluconazole as standard. Free radical scavenging activity of the nanoparticles were observed by modified 1,1-diphynyl-2-picrylhydrazyl, DPPH and 2,2-azinobis(3-ethylbenzothiazoline-6-sulfonic acid), ABTS in vitro assays. The work presented here demonstrates the adaptability of the synthesized Ag-NPs in participating as a disinfectant agent, free radical scavenger and an effective oxidation catalyst. The basic premise of attaining sustainability through the green synthesis of smart multifaceted materials has been consciously addressed.

  12. Upregulating Noxa by ER Stress, Celastrol Exerts Synergistic Anti-Cancer Activity in Combination with ABT-737 in Human Hepatocellular Carcinoma Cells

    OpenAIRE

    Zhu, Hong; Yang, Wei; He, Ling-juan; Ding, Wan-jing; Zheng, Lin; Liao, Si-Da; HUANG, PING; Lu, Wei; He, Qiao-jun; Yang, Bo

    2012-01-01

    The human hepatocellular carcinoma (HCC) represents biologically aggressive and chemo-resistant cancers. Owing to the low affinity with the apoptotic factor Mcl-1, the BH3 mimetic drug ABT-737 failed to exert potent cancer-killing activities in variety of cancer models including HCC. The current study demonstrated that combining ABT-737 and Celastrol synergistically suppressed HCC cell proliferation, and induced apoptosis which was accompanied with the activation of caspase cascade and releas...

  13. In Vitro Activities of a New Ketolide, ABT-773, Alone and in Combination with Amoxicillin, Metronidazole, or Tetracycline against Helicobacter pylori

    OpenAIRE

    Pendland, Susan L.; Prause, Jennifer L.; Neuhauser, Melinda M.; Boyea, Nicole; Hackleman, Jodi M.; Danziger, Larry H.

    2000-01-01

    The in vitro activity of ABT-773, a new ketolide, was compared with those of clarithromycin, amoxicillin, metronidazole, and tetracycline against 15 strains of Helicobacter pylori. The MIC of ABT-773 at which 90% of isolates were inhibited was 0.25 ?g/ml, which was 3 dilutions higher than that of the most active agent, clarithromycin. Synergy and antagonism were not seen with any combinations. Additive activity was seen with tetracycline, metronidazole, and amoxicillin in 100, 60, and 40% of ...

  14. Potent and selective small-molecule MCL-1 inhibitors demonstrate on-target cancer cell killing activity as single agents and in combination with ABT-263 (navitoclax)

    Science.gov (United States)

    Leverson, J D; Zhang, H; Chen, J; Tahir, S K; Phillips, D C; Xue, J; Nimmer, P; Jin, S; Smith, M; Xiao, Y; Kovar, P; Tanaka, A; Bruncko, M; Sheppard, G S; Wang, L; Gierke, S; Kategaya, L; Anderson, D J; Wong, C; Eastham-Anderson, J; Ludlam, M J C; Sampath, D; Fairbrother, W J; Wertz, I; Rosenberg, S H; Tse, C; Elmore, S W; Souers, A J

    2015-01-01

    The anti-apoptotic protein MCL-1 is a key regulator of cancer cell survival and a known resistance factor for small-molecule BCL-2 family inhibitors such as ABT-263 (navitoclax), making it an attractive therapeutic target. However, directly inhibiting this target requires the disruption of high-affinity protein–protein interactions, and therefore designing small molecules potent enough to inhibit MCL-1 in cells has proven extremely challenging. Here, we describe a series of indole-2-carboxylic acids, exemplified by the compound A-1210477, that bind to MCL-1 selectively and with sufficient affinity to disrupt MCL-1–BIM complexes in living cells. A-1210477 induces the hallmarks of intrinsic apoptosis and demonstrates single agent killing of multiple myeloma and non-small cell lung cancer cell lines demonstrated to be MCL-1 dependent by BH3 profiling or siRNA rescue experiments. As predicted, A-1210477 synergizes with the BCL-2/BCL-XL inhibitor navitoclax to kill a variety of cancer cell lines. This work represents the first description of small-molecule MCL-1 inhibitors with sufficient potency to induce clear on-target cellular activity. It also demonstrates the utility of these molecules as chemical tools for dissecting the basic biology of MCL-1 and the promise of small-molecule MCL-1 inhibitors as potential therapeutics for the treatment of cancer. PMID:25590800

  15. Potent and selective small-molecule MCL-1 inhibitors demonstrate on-target cancer cell killing activity as single agents and in combination with ABT-263 (navitoclax).

    Science.gov (United States)

    Leverson, J D; Zhang, H; Chen, J; Tahir, S K; Phillips, D C; Xue, J; Nimmer, P; Jin, S; Smith, M; Xiao, Y; Kovar, P; Tanaka, A; Bruncko, M; Sheppard, G S; Wang, L; Gierke, S; Kategaya, L; Anderson, D J; Wong, C; Eastham-Anderson, J; Ludlam, M J C; Sampath, D; Fairbrother, W J; Wertz, I; Rosenberg, S H; Tse, C; Elmore, S W; Souers, A J

    2015-01-01

    The anti-apoptotic protein MCL-1 is a key regulator of cancer cell survival and a known resistance factor for small-molecule BCL-2 family inhibitors such as ABT-263 (navitoclax), making it an attractive therapeutic target. However, directly inhibiting this target requires the disruption of high-affinity protein-protein interactions, and therefore designing small molecules potent enough to inhibit MCL-1 in cells has proven extremely challenging. Here, we describe a series of indole-2-carboxylic acids, exemplified by the compound A-1210477, that bind to MCL-1 selectively and with sufficient affinity to disrupt MCL-1-BIM complexes in living cells. A-1210477 induces the hallmarks of intrinsic apoptosis and demonstrates single agent killing of multiple myeloma and non-small cell lung cancer cell lines demonstrated to be MCL-1 dependent by BH3 profiling or siRNA rescue experiments. As predicted, A-1210477 synergizes with the BCL-2/BCL-XL inhibitor navitoclax to kill a variety of cancer cell lines. This work represents the first description of small-molecule MCL-1 inhibitors with sufficient potency to induce clear on-target cellular activity. It also demonstrates the utility of these molecules as chemical tools for dissecting the basic biology of MCL-1 and the promise of small-molecule MCL-1 inhibitors as potential therapeutics for the treatment of cancer. PMID:25590800

  16. ABT-737 reverses the acquired radioresistance of breast cancer cells by targeting Bcl-2 and Bcl-xL

    Directory of Open Access Journals (Sweden)

    Li Ji-Yu

    2012-12-01

    Full Text Available Abstract Background Acquired radioresistance of cancer cells remains a fundamental barrier to attaining the maximal efficacy of radiotherapy for the treatment of breast cancer. Anti-apoptotic proteins, such as Bcl-2 and Bcl-xL, play an important role in the radioresistance of cancer cells. In the present study, we aimed to determine if ABT-737, a BH3-only mimic, could reverse the acquired radioresistance of the breast cancer cell line MDA-MB-231R by targeting Bcl-2 and Bcl-xL. Methods The radiosensitivity of MDA-MB-231 and MDA-MB-231R cells was compared using colony formation assays. Reverse-transcription PCR and western blot were performed to detect the expression of Bcl-2 and Bcl-xL in the cancer cell lines. Annexin V flow cytometric analysis and caspase-3 colorimetric assay were used to evaluate apoptosis of the cancer cells. Cell viability was measured using the Cell Counting Kit-8. The animals used in this study were 4 to 6-week-old athymic female BALB/c nu/nu mice. Results The MDA-MB-231R cells were more radioresistant than the MDA-MB-231 cells, and Bcl-2 and Bcl-xL were overexpressed in the MDA-MB-231R cells. While ABT-737 was able to restore the radiosensitivity of the MDA-MB-231R cells in vitro and in vivo experiment, it was not able to enhance the radiosensitivity of the MDA-MB-231 cells. In addition, ABT-737 increased radiation-induced apoptosis in the MDA-MB-231R cells. Bcl-2 and Bcl-xL were down regulated in the MDA-MB-231R cells following treatment with ABT-737. Conclusions Targeting of the anti-apoptotic proteins Bcl-2 and Bcl-xL with ABT-737 may reverse the acquired radioresistance of MDA-MB-231R cells in vitro and in vivo. These findings suggest an attractive strategy for overcoming the acquired radioresistance of breast cancer cells.

  17. Chemotherapeutic drugs sensitize human renal cell carcinoma cells to ABT-737 by a mechanism involving the Noxa-dependent inactivation of Mcl-1 or A1

    Directory of Open Access Journals (Sweden)

    Zantl Niko

    2010-06-01

    Full Text Available Abstract Background Human renal cell carcinoma (RCC is very resistant to chemotherapy. ABT-737 is a novel inhibitor of anti-apoptotic proteins of the Bcl-2 family that has shown promise in various preclinical tumour models. Results We here report a strong over-additive pro-apoptotic effect of ABT-737 and etoposide, vinblastine or paclitaxel but not 5-fluorouracil in cell lines from human RCC. ABT-737 showed very little activity as a single agent but killed RCC cells potently when anti-apoptotic Mcl-1 or, unexpectedly, A1 was targeted by RNAi. This potent augmentation required endogenous Noxa protein since RNAi directed against Noxa but not against Bim or Puma reduced apoptosis induction by the combination of ABT-737 and etoposide or vinblastine. At the level of mitochondria, etoposide-treatment had a similar sensitizing activity and allowed for ABT-737-induced release of cytochrome c. Conclusions Chemotherapeutic drugs can overcome protection afforded by Mcl-1 and A1 through endogenous Noxa protein in RCC cells, and the combination of such drugs with ABT-737 may be a promising strategy in RCC. Strikingly, A1 emerged in RCC cell lines as a protein of similar importance as the well-established Mcl-1 in protection against apoptosis in these cells.

  18. Prostatectomia radical laparoscópica / Radical laparoscopic prostatectomy

    Scientific Electronic Library Online (English)

    OCTAVIO A, CASTILLO C; IVAR, VIDAL-MORA; RAFAEL, SÁNCHEZ-SALAS.

    2011-04-01

    Full Text Available La Prostatectomia radical laparoscópica (PRL) se ha convertido en una técnica atractiva para el tratamiento quirúrgico del cáncer de próstata localizado. Si bien, los resultados actuales son inicialmente comparables a la prostatectomia radical abierta, es importante mencionar que la tendencia quirúr [...] gica en cáncer de próstata, se ha modificado a pesar de que no hay estudios que confirmen la superioridad del método endoscópico y hoy, el estándar dorado sigue siendo la prostatectomia radical abierta. Dos rutas de acceso quirúrgico pueden ser utilizadas para la realización de PRL, la vía extraperitoneal y la transperitoneal. Un menor sangrado y menor tasa de transfusión, así como, tiempo de hospitalización y recuperación más cortos, son ventajas incuestionables para los procedimientos laparoscópicos. Los resultados oncológicos y funcionales de la prostatectomia laparoscópica son hoy en día comparables, pero en ningún caso mejores que la técnica retropúbica abierta estándar. Recientemente, Hu y colaboradores, en base a una revisión de cerca de 3.000 pacientes tratados en los Estados Unidos, plantean la posibilidad de que los pacientes tratados con prostatectomia laparoscópica (pura o asistida por robot), pudiesen tener mayor riesgo de recurrencia de la enfermedad. Esta es una posición discutible, ya que el análisis, a pesar de ser extenso es limitado para establecer conclusiones finales en el tema. Es importante recordar que la PRL sigue siendo una intervención técnicamente difícil y debiera ser realizada en centros seleccionados con equipos experimentados. La prostatectomía laparoscópica asistida por Robot, facilita el procedimiento y en suma, pareciera mejorar los resultados oncológicos y funcionales. La PRL es hoy en día una alternativa válida a la prostatectomía retropúbica tradicional, con ciertas ventajas adicionales. Abstract in english Radical laparosocpic prostatectomy (RLP) is an attractive therapeutic modality for localized prostate cancer. The results obtained with this technique are similar to those obtained with open radical prostatectomy, which continues to be the gold standard for the treatment of prostate cancer. The surg [...] ical access for RLP can be extra-peritoneal or trans-peritoneal. The advantages of laparoscopy are lower bleeding rates, less need for transfusion and shorter recuperation time and hospital stay. The oncological results of RLP are similar, but in any case better, that those obtained with open retropubic radical prostatectomy. Recent reports raised the concern that laparoscopic prostatectomy could have higher rates of relapse of cancer. However this opinion is questionable. RLP is a difficult technique and should be performed by experienced teams. Robot assistance facilitates the procedure and could improve functional and oncological results. Therefore RLP is nowadays an alternative to traditional retropubic prostatectomy.

  19. Radical chemistry of artemisinin

    Energy Technology Data Exchange (ETDEWEB)

    Denisov, Evgenii T; Solodova, S L; Denisova, Taisa G [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region (Russian Federation)

    2010-12-29

    The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

  20. Free-radical reactions of glycerolipids and sphingolipids

    Science.gov (United States)

    Yurkova, I. L.

    2012-02-01

    Free-radical reactions of glycero- and sphingolipids occurring in their polar moiety (fragmentation) and in their hydrophobic residue (peroxidation) under the action of reactive oxygen species are considered. The main attention is focused on free-radical fragmentation; its mechanism and regularities are discussed. Lipid peroxidation has been shown to modify the residues of polyunsaturated fatty acids, while the free-radical fragmentation results in the cleavage of ester, O-glycosidic and amide bonds in lipid molecules to give glycerophosphatides, ceramides and fatty acid amides functioning as secondary messengers in biosystems. The bibliography includes 132 references.

  1. Free radical scavenging activity of leaves of Alocasia indica (Linn

    Directory of Open Access Journals (Sweden)

    Mulla W

    2009-01-01

    Full Text Available The free radical scavenging potential of the plant Alocasia indica (Linn. was studied by using different antioxidant models of screening like scavenging of 1,1-diphenyl-2-picryl hydrazyl radical, nitric oxide radical, superoxide anion radical, hydroxyl radical, iron chelating activity, total antioxidant capacity, non-enzymatic glycosylation of haemoglobin, rapid screening for antioxidant compounds by thin layer chromatography. The hydroalcoholic extract at 1000 ?g/ml showed maximum scavenging of superoxide radical (87.17 by riboflavin-NBT-system, followed by scavenging of stable radical 1,1-diphenyl-2-picryl hydrazyl radical (83.48%, nitric oxide radical (74.09% hydroxyl radical (60.96% at the same concentration. However the extract showed only moderate activity by iron chelation (68.26%. That could be due to higher phenolic content in the extract. This finding suggests that hydro alcoholic extract of A. indica possess potent in vitro antioxidant activity as compared to the standard ascorbic acid. The results justify the therapeutic applications of the plant in the indigenous system of medicine, augmenting its therapeutic value.

  2. Violent Radicalization in Europe

    DEFF Research Database (Denmark)

    Dalgaard-Nielsen, Anja

    2010-01-01

    When, why, and how do people living in a democracy become radicalized to the point of being willing to use or directly support the use of terrorist violence against Fellow citizens? This question has been at the center of academic and public debate over the past years as terrorist attacks and foiled plots inspired by militant Islamism have grabbed European and American headlines. This article identifies and discusses empirical studies of radicalization and points to the strengths as well as the ...

  3. Violent Radicalization in Europe

    DEFF Research Database (Denmark)

    Dalgaard-Nielsen, Anja

    2010-01-01

    When, why, and how do people living in a democracy become radicalized to the point of being willing to use or directly support the use of terrorist violence against fellow citizens? This question has been at the center of academic and public debate over the past years as terrorist attacks and foiled plots inspired by militant Islamism have grabbed European and American headlines. This article identifies and discusses empirical studies of radicalization and points to the strengths as well as the ...

  4. Homegrown religious radicalization

    DEFF Research Database (Denmark)

    Khawaja, Iram

    2015-01-01

    It has been reported that a growing number of youngsters from Western Europe are engaging in conflicts motivated by religious and political conflicts in the Middle East. This paper aims at exploring the reasons behind this seemingly religious radicalization from the point of view of the youngsters and their families. Existing literature and ways of thinking about the social psychological process of radicalization will be reviewed, such as social identity theory and transformative learning theory...

  5. Laparoscopic radical prostatectomy

    OpenAIRE

    Lipke Michael; Sundaram Chandru

    2005-01-01

    Millions of men are diagnosed annually with prostate cancer worldwide. With the advent of PSA screening, there has been a shift in the detection of early prostate cancer, and there are increased numbers of men with asymptomatic, organ confined disease. Laparoscopic radical prostatectomy is the latest, well accepted treatment that patients can select. We review the surgical technique, and oncologic and functional outcomes of the most current, large series of laparoscopic radical prostatectomy ...

  6. Sources, sinks, and mechanisms of hydroxyl radical (•OH) photoproduction and consumption in authentic acidic continental cloud waters from Whiteface Mountain, New York: The role of the Fe(r) (r = II, III) photochemical cycle

    Science.gov (United States)

    Arakaki, Takemitsu; Faust, Bruce C.

    1998-02-01

    Hydroxyl radical (•OH) photoproduction in 25 authentic acidic (pH = 2.9-4.4) continental cloud waters from Whiteface Mountain, New York was quantified by phenol formed from the •OH-mediated oxidation of benzene (1.2 mM) that was added as an •OH scavenger. Based on the effect of added bisulfite (HSO3-/HOSO2-), an HOOH sink, the •OH photoproduction in these samples was apportioned into two categories: HOOH-dependent sources (dominant), and HOOH-independent sources (minor). On average only a small percentage (median = 9.4%, mean±standard deviation = 16±12%) of the HOOH-dependent •OH source is due to direct photolysis (313 nm) of HOOH. Nearly all of the HOOH-dependent •OH source is accounted for by an iron(II)-HOOH photo-Fenton reaction mechanism (Fe(II) + HOOH ? Fe(III) + •OH + OH-) that is initiated by photoreduction of Fe(III) to Fe(II) in the presence of HOOH. A photostationary state is established, involving rapid photolysis of Fe(III) to form Fe(II), and rapid reoxidation of Fe(II) to Fe(III). Consequently, a new term is introduced, Fe(r) (r = II, III), to represent the family of labile Fe(III) and Fe(II) species whose rapid photoredox cycling drives the Fenton production of •OH. The Fe(r) photochemical cycle, which drives the aqueous phase photoformation of •OH, is analogous to the classical NOx photochemical cycle, which drives the gas phase formation of O3 and thus •OH. Based on the cloud waters studied here, the iron(II)-HOOH photo-Fenton reaction is a significant source of •OH to acidic continental cloud waters in comparison to gas-to-drop partitioning processes. Filtering (0.5 ?m Teflon) cloud water samples had little effect on the •OH photoformation kinetics. Measured lifetimes of aqueous •OH ranged from 2.4 to 10.6 ?s in these cloud waters, and decreased with increasing concentration of dissolved organic carbon. In acidic atmospheric water drops, the principal aqueous sinks for •OH will be reactions with dissolved organic compounds, bisulfite, and Cl-. Given such short chemical reaction lifetimes, little of the aqueous phase photoformed •OH is likely to escape to the gas phase.

  7. Anticancer compound ABT-263 accelerates apoptosis in virus-infected cells and imbalances cytokine production and lowers survival rates of infected mice.

    Science.gov (United States)

    Kakkola, L; Denisova, O V; Tynell, J; Viiliäinen, J; Ysenbaert, T; Matos, R C; Nagaraj, A; Ohman, T; Kuivanen, S; Paavilainen, H; Feng, L; Yadav, B; Julkunen, I; Vapalahti, O; Hukkanen, V; Stenman, J; Aittokallio, T; Verschuren, E W; Ojala, P M; Nyman, T; Saelens, X; Dzeyk, K; Kainov, D E

    2013-01-01

    ABT-263 and its structural analogues ABT-199 and ABT-737 inhibit B-cell lymphoma 2 (Bcl-2), BCL2L1 long isoform (Bcl-xL) and BCL2L2 (Bcl-w) proteins and promote cancer cell death. Here, we show that at non-cytotoxic concentrations, these small molecules accelerate the deaths of non-cancerous cells infected with influenza A virus (IAV) or other viruses. In particular, we demonstrate that ABT-263 altered Bcl-xL interactions with Bcl-2 antagonist of cell death (Bad), Bcl-2-associated X protein (Bax), uveal autoantigen with coiled-coil domains and ankyrin repeats protein (UACA). ABT-263 thereby activated the caspase-9-mediated mitochondria-initiated apoptosis pathway, which, together with the IAV-initiated caspase-8-mediated apoptosis pathway, triggered the deaths of IAV-infected cells. Our results also indicate that Bcl-xL, Bcl-2 and Bcl-w interact with pattern recognition receptors (PRRs) that sense virus constituents to regulate cellular apoptosis. Importantly, premature killing of IAV-infected cells by ABT-263 attenuated the production of key pro-inflammatory and antiviral cytokines. The imbalance in cytokine production was also observed in ABT-263-treated IAV-infected mice, which resulted in an inability of the immune system to clear the virus and eventually lowered the survival rates of infected animals. Thus, the results suggest that the chemical inhibition of Bcl-xL, Bcl-2 and Bcl-w could potentially be hazardous for cancer patients with viral infections. PMID:23887633

  8. Setting the stage for electron transfer: Molecular basis of ABTS-binding to four laccases from Trametes versicolor at variable pH and protein oxidation state

    DEFF Research Database (Denmark)

    Christensen, Niels Johan; Kepp, Kasper Planeta

    2014-01-01

    Laccases are multi-copper oxidases having exquisite oxidation power, high stability, and multiple industrial applications. Although Km varies ?1000-fold across laccases, the molecular basis of substrate binding is poorly understood. Furthermore, laccase isoenzymes vary substantially in stability and activity for unknown reasons, and are thus useful probes of stability-function trade-offs relevant to protein engineering. We report here the first systematic comparison of ABTS-binding to different proteins, i.e. the four isoforms of Trametes versicolor, using a combination of sequence clustering, density functional theory calculations, homology modeling, and multiple induced-fit docking protocols at variable pH-dependent protonation states and T1-copper oxidation state. Clustering analysis provided a systematic overview of laccases across Trametes and revealed distinct isoenzyme classes (A–J) with the four T. versicolor isoforms belonging to separate classes. The T1 oxidation state had minor effect on ABTS binding, whereas the protonation state of Asp206 was important, consistent with site-directed mutagenesis studies. The absence of active poses for the ?-isoform agrees with its large Km, whereas the ?-isoform with the smallest Km also had most active poses with protonated Asp206 corresponding to its pHopt?2. Protonated Asp can bind to ABTS to form strong, active conformations partially explaining the low pHopt of fungal laccases toward ABTS. We identified several laccase properties optimal for ABTS binding. Notably, very high (R2?0.99) correlation was observed between logKm (ABTS) and binding-pocket charge due to sites 157, 161, 269, 271, and 333, i.e. laccases optimal for ABTS turnover have positively charged anchor points in their pockets. Our work also demonstrates how activity-constraints can markedly improve docking to reduce inactive false positives.

  9. The Thrombospondin-1 Mimetic ABT-510 Increases the Uptake and Effectiveness of Cisplatin and Paclitaxel in a Mouse Model of Epithelial Ovarian Cancer

    Directory of Open Access Journals (Sweden)

    Nicole E. Campbell

    2010-03-01

    Full Text Available Epithelial ovarian cancer (EOC comprises approximately 90% of ovarian cancers and arises from the surface epithelium. Typical treatment of EOC involves cytoreductive surgery combined with chemotherapy. More recent therapies have targeted the tumor vasculature using antiangiogenic compounds such as thrombospondin-1 (TSP-1. TSP-1 mimetic peptides such as ABT-510 have been created and have been in various clinical trials. We have previously shown that ABT-510 reduces abnormal vasculature associated with tumor tissue and increases the presence of mature blood vessels. It has been hypothesized that treatment with antiangiogenic compounds would allow increased delivery of cytotoxic agents and enhance treatment. In this study, we evaluated the potential role of ABT-510 and various chemotherapeutics (cisplatin and paclitaxel on tumor progression, angiogenesis, and the benefits of combinational treatments on tissue uptake and perfusion using an orthotopic syngeneic mouse model of EOC. Animals were treated with ABT-510 (100 mg/kg per day alone or in combination with cisplatin (2 mg/kg per 3 days or paclitaxel (10 mg/kg per 2 days at 60 days after tumor induction. Radiolabeled and fluorescently labeled paclitaxel demonstrated a significant increase in tumor uptake after ABT-510 treatment. Combined treatment with ABT-510 and cisplatin or paclitaxel resulted in a significant increase in tumor cell and tumor endothelial cell apoptosis and a resultant decrease in ovarian tumor size. Combined treatment also regressed secondary lesions and eliminated the presence of abdominal ascites. The results from this study show that through vessel normalization, ABT-510 increases uptake of chemotherapy drugs and can induce regression of advanced ovarian cancer.

  10. Radical scavenging activities of Tyr-, Trp-, Cys- and Met-Gly and their protective effects against AAPH-induced oxidative damage in human erythrocytes.

    Science.gov (United States)

    Zheng, Lin; Dong, Hongzhu; Su, Guowan; Zhao, Qiangzhong; Zhao, Mouming

    2016-04-15

    Radical scavenging activities of Tyr-, Trp-, Cys- and Met-Gly and their protective effects against AAPH-induced oxidative damage in erythrocytes were evaluated in this study. This damage includes hemolysis, oxidation of hemoglobin, formation of MDA and the depletion of glutathione (GSH) and catalase (CAT). Results showed that Tyr- and Trp-Gly could quench the radicals effectively in ABTS and ORAC assays with TE (Trolox equivalent) values of more than 1.0?mol TE/?mol, followed by Cys- and Met-Gly. All these dipeptides could protect erythrocytes against AAPH-induced hemolysis in a dose-dependent manner. They could also significantly (pTyr-Gly>Met-Gly>Cys-Gly, which were consistent with their peroxyl radical scavenging activities. It suggested that these dipeptides might protect erythrocytes against AAPH-induced oxidative damage, mainly by acting as the direct radical scavengers. PMID:26617020

  11. Antioxidant capacity and radical scavenging effect of polyphenol rich Mallotus philippenensis fruit extract on human erythrocytes: an in vitro study.

    Science.gov (United States)

    Gangwar, Mayank; Gautam, Manish Kumar; Sharma, Amit Kumar; Tripathi, Yamini B; Goel, R K; Nath, Gopal

    2014-01-01

    Mallotus philippinensis is an important source of molecules with strong antioxidant activity widely used medicinal plant. Previous studies have highlighted their anticestodal, antibacterial, wound healing activities, and so forth. So, present investigation was designed to evaluate the total antioxidant activity and radical scavenging effect of 50% ethanol fruit glandular hair extract (MPE) and its role on Human Erythrocytes. MPE was tested for phytochemical test followed by its HPLC analysis. Standard antioxidant assays like DPPH, ABTS, hydroxyl, superoxide radical, nitric oxide, and lipid peroxidation assay were determined along with total phenolic and flavonoids content. Results showed that MPE contains the presence of various phytochemicals, with high total phenolic and flavonoid content. HPLC analysis showed the presence of rottlerin, a polyphenolic compound in a very rich quantity. MPE exhibits significant strong scavenging activity on DPPH and ABTS assay. Reducing power showed dose dependent increase in concentration absorption compared to standard, Quercetin. Superoxide, hydroxyl radical, lipid peroxidation, nitric oxide assay showed a comparable scavenging activity compared to its standard. Our finding further provides evidence that Mallotus fruit extract is a potential natural source of antioxidants which have a protective role on human Erythrocytes exhibiting minimum hemolytic activity and this justified its uses in folklore medicines. PMID:25525615

  12. ABT-737 reverses the acquired radioresistance of breast cancer cells by targeting Bcl-2 and Bcl-xL

    OpenAIRE

    Li Ji-Yu; Li Yu-Yang; Jin Wei; Yang Qing; Shao Zhi-Ming; Tian Xing-Song

    2012-01-01

    Abstract Background Acquired radioresistance of cancer cells remains a fundamental barrier to attaining the maximal efficacy of radiotherapy for the treatment of breast cancer. Anti-apoptotic proteins, such as Bcl-2 and Bcl-xL, play an important role in the radioresistance of cancer cells. In the present study, we aimed to determine if ABT-737, a BH3-only mimic, could reverse the acquired radioresistance of the breast cancer cell line MDA-MB-231R by targeting Bcl-2 and Bcl-xL. Methods The rad...

  13. (S)-3-methyl-5-(1-methyl-2-pyrrolidinyl) isoxazole (ABT 418): a novel cholinergic ligand with cognition-enhancing and anxiolytic activities: I. In vitro characterization.

    Science.gov (United States)

    Arneric, S P; Sullivan, J P; Briggs, C A; Donnelly-Roberts, D; Anderson, D J; Raszkiewicz, J L; Hughes, M L; Cadman, E D; Adams, P; Garvey, D S

    1994-07-01

    A diversity of nicotinic acetylcholine receptor (nAChR) subtypes has been identified in mammalian brain using recombinant DNA technology. Alterations in the activity of these acetylcholinegated ion channels have been implicated in a number of central nervous system disorders including Alzheimer's disease (AD). The potential therapeutic usefulness of (-)-nicotine [(S)-3-(1-methyl-2-pyrrolidinyl) pyridine], the prototypic agonist at nAChRs, is severely limited by side effects that are the result of activation of both cholinergic and noncholinergic pathways in the central and peripheral nervous systems. This study sought to determine the in vitro selectivity of (S)-3-methyl-5-(1methyl-2-pyrrolidinyl)isoxazole (ABT 418), a novel analog of (-)-nicotine in which the pyridine ring was replaced with an isoxazole bioisotere, to activate nAChRs. ABT 418 was a potent inhibitor of [3H]-cytisine binding to nAChR in rat brain (Ki = 3 nM) but was inactive (Ki > 10,000 nM) in 37 other receptor/neurotransmitter-uptake/enzyme/transduction system binding assays, including those for alpha-bungarotoxin, muscarinic and 5-hydroxytryptamine3 receptors. In PC12 cells, patch-clamp studies indicated that ABT 418 was an agonist with an EC50 value of 209 microM, a potency to activate cholinergic channel currents some 4-fold less than that of (-)-nicotine (52 microM). Channel current responses elicited by ABT 418 were prevented by the cholinergic channel blocker, mecamylamine. ABT 418 was also approximately 10-fold less potent (EC50 value = 380 nM) than (-)-nicotine (40 nM) in increasing [3H]-dopamine release from rat striatal slices, an effect that was blocked by the nAChR antagonist, dihydro-beta-erythroidine (10 microM).2+ In contrast, ABT 418 appeared equipotent with (-)-nicotine in enhancing 86Rb+ flux from mouse thalamic synaptosomes. ABT 418 demonstrated an in vitro pharmacological profile of cholinergic channel activation that was robust at some nAChR, but not others. The reasons for this are unclear. However, a nAChR subtype selectivity may account for the in vitro potency differences of ABT 418 on various neurotransmitter systems, and the substantial separation between the cognitive enhancement/anxiolytic benefits, and the reduced central nervous system side-effect liabilities seen in vivo. ABT 418 represents the first neuronal nAChR ligand that differentiates the toxicities/liabilities and other negative aspects normally associated with liabilities and other negative aspects normally associated with (-)-nicotine from the potential pharmacological benefits of selective cholinergic channel activation. PMID:7518514

  14. Antioxidant activity and free radical scavenging capacity of phenolic extracts from Helicteres isora L. and Ceiba pentandra L.

    OpenAIRE

    Loganayaki, Nataraj; Siddhuraju, Perumal; Manian, Sellamuthu

    2011-01-01

    In the present study, antioxidant activities of the phenolic extracts from H. isora fruits and C. pentandra seeds were investigated by employing established in vitro systems, which included reducing power, OH?, DPPH?, ABTS?+, linoleic acid emulsion, metal chelation and antihemolytic activity. The extracts of C. pentandra contained relatively higher levels of total phenolics and flavonoids than those of H. isora. All the extracts showed dose dependent reducing power activity and moreover, they...

  15. The Corrole Radical.

    Science.gov (United States)

    Schweyen, Peter; Brandhorst, Kai; Wicht, Richard; Wolfram, Benedikt; Bröring, Martin

    2015-07-01

    The reaction of 5,10,15-trimesitylcorrole (H3 cor) with tungsten hexachloride and tungsten hexacarbonyl resulted in the unexpected formation of the 3,17-dichloro-5,10,15-trimesitylcorrole radical (H2 cor*) as an air-stable product. X-ray crystallography proved the planarization of the corrole radical structure, which was rationalized by the reduced steric hindrance of two versus three hydrogen atoms inside the N4 cavity. Although the aromaticity was lost, no specific changes in C-C or C-N bond distances could be observed. The regioselectivity of the two-fold chlorination is the result of the nucleophilic attack of chloride ions to an oxidized corrole macrocycle, and is supported by DFT results. The corrole radical acts as a dianionic ligand and allows the insertion of the divalent zinc(II) cation, which usually does not form neutral corrole complexes. PMID:26074281

  16. Anesthesia for radical prostatectomy

    Directory of Open Access Journals (Sweden)

    Hadži-?oki? J.

    2005-01-01

    Full Text Available Radical prostatectomy is one of most common treatment options currently recommended for clinically localized prostate cancer. Evaluation of intraoperative and postoperative complications is important in evaluation of relative morbidity of this treatment option. Furthermore, investigation of complications of surgical treatment in correlation with not only surgical technique, but comorbidity, ASA stage and anesthetic technique enables improvements in complete perioperative treatment and decrease of incidence of complications resulting from the procedure. Improvement of anesthetic techniques and use of new anesthetic agents contributes to better outcome of surgical treatment. For radical surgery, combined epidural analgesia and general anesthesia reduces postoperative complications and mortality. Benefits can be conferred most likely by altered coagulation activation in surgery, increased blood flow, reduction of operative stress response. Modalities for reduction of intraoperative blood loss during radical prostatectomy are normovolemic haemodilution, preoperative donation of blood for autologus transfusion and use of erythropoietin for increasing red cell mass.

  17. Laparoscopic radical prostatectomy

    Directory of Open Access Journals (Sweden)

    Lipke Michael

    2005-01-01

    Full Text Available Millions of men are diagnosed annually with prostate cancer worldwide. With the advent of PSA screening, there has been a shift in the detection of early prostate cancer, and there are increased numbers of men with asymptomatic, organ confined disease. Laparoscopic radical prostatectomy is the latest, well accepted treatment that patients can select. We review the surgical technique, and oncologic and functional outcomes of the most current, large series of laparoscopic radical prostatectomy published in English. Positive margin rates range from 2.1-6.9% for pT2a, 9.9-20.6% for pT2b, 24.5-42.3% for pT3a, and 22.6-54.5% for pT3b. Potency rates after bilateral nerve sparing laparoscopic radical prostatectomy range from 47.1 to 67%. Continence rates at 12 months range from 83.6 to 92%.

  18. Reaction of hydroxyl radicals with 1-bromo-n-iodoalkanes in aqueous solution: 2c-3e bonded radical cations

    International Nuclear Information System (INIS)

    The transient optical absorption bands (?max=310, 350 nm) formed on reaction of OH radicals with 1-bromo-4-iodobutane (pH=6) are assigned to OH-adduct. In acidic solutions (pH=3.0), the OH adduct is converted to a transient band with ?max=440 nm. This band is assigned to intramolecular radical cation formed on p-orbital overlap of oxidized iodine with bromine. In 1-bromo-3-iodopropane, the hydroxyl radicals react to form absorption band with ?max=400 nm and a small shoulder in 310-330 nm region. In acidic solutions, the absorption of 310-330 nm band decreases and that of 400 nm band increases. The transient band at 400 nm is assigned to intramolecular radical cation. A fraction of OH radical is able to react by electron transfer mechanism at neutral pH. The fraction of OH radical forming OH-adduct at neutral pH decreases and is converted to radical cation in acidic pH. (author). 4 refs

  19. Free radical scavenging abilities of polypeptide from Chlamys farreri

    Science.gov (United States)

    Han, Zhiwu; Chu, Xiao; Liu, Chengjuan; Wang, Yuejun; Mi, Sun; Wang, Chunbo

    2006-09-01

    We investigated the radical scavenging effect and antioxidation property of polypeptide extracted from Chlamys farreri (PCF) in vitro using chemiluminescence and electron spin resonance (ESR) methods. We examined the scavenging effects of PCF on superoxide anions (O{2/-}), hydroxyl radicals (OH·), peroxynitrite (ONOO-) and the inhibiting capacity of PCF on peroxidation of linoleic acid. Our experiment suggested that PCF could scavenge oxygen free radicals including superoxide anions (O{2/-}) (IC50=0.3 mg/ml), hydroxyl radicals (OH·) (IC50=0.2 ?g/ml) generated from the reaction systems and effectively inhibit the oxidative activity of ONOO- (IC50=0.2 mg/ml). At 1.25 mg/ml of PCF, the inhibition ratio on lipid peroxidation of linoleic acid was 43%. The scavenging effect of PCF on O{2/-}, OH· and ONOO- free radicals were stronger than those of vitamin C but less on lipid peroxidation of linoleic acid. Thus PCF could scavenge free radicals and inhibit the peroxidation of linoleic acid in vitro. It is an antioxidant from marine products and potential for industrial production in future.

  20. Oxidation of aromatic amines and diamines by OH radicals. Formation and ionization constants of amine cation radicals in water

    International Nuclear Information System (INIS)

    The one-electron oxidation by hydroxyl radicals of aromatic amines and diamines in water was studied using the fast-reaction technique of pulse radiolysis and kinetic absorption spectrophotometry. The following compounds were examined: N,N,N1,N1- tetramethyl-p-phenylenediamine (TMPD), p-phenylenediamine (PD), N,N-dimethyl-p-phenylenediamene (DMPD), N,N,N1,N1-tetramethylbenzidine (TMB), and diphenylamine (DPA). The main initial reaction of the OH radicals is suggested to be an addition to these compounds to give absorption spectra which absorb strongly in the visible and uv regions. These OH radical adducts decay by first-order kinetics and have lifetimes of approximately 5-50 ?sec, dependent on the pH, buffer concentration, and the nature of the aromatic amines and diamines. They decay to give species with somewhat similar absorption spectra and extinction coefficients, which are very long lived in the absence of oxygen. The latter species are assigned to the cation radicals TMPD.+, PD.+, DMPD.+, TMB.+, and DPA.+. The OH radical adducts and the cation radicals have acid-base properties. The pK/sub a/ values of the cation radicals TMPDH.2+, PDH.2+, DMPDH.2+, TMBH.2+, and DPAH.2+ were found to be 5.3, 5.9, 6.1, 5.1, and 4.2, respectively. The results indicate that these aromatic amines and diamines can be oxidized by free radicals to yield the corresponding cation radicals. (U.S.)

  1. Synthesis of novel well-defined poly(vinyl acetate)-b-poly(acrylonitrile) and derivatized water-soluble poly(vinyl alcohol)-b-poly(acrylic acid) block copolymers by cobalt-mediated radical polymerization

    OpenAIRE

    Debuigne, A.; Warnant, J; Jerome, R.; I. K. Voets; Keizer, A (Arie) de; Cohen Stuart, M.A.; Detrembleur, C

    2008-01-01

    Poly(vinyl acetate)¿Co(acac)2 macroinitiators, prepared by cobalt-mediated radical polymerization of vinyl acetate (VAc), were used to synthesize well-defined poly(vinyl acetate)-b-poly(acrylonitrile) (PVAc-b-PAN) block copolymers. Different solvents and temperatures were tested for the polymerization of the acrylonitrile segment by cobalt-mediated radical polymerization (CMRP), and copolymers with low polydispersity were obtained provided that dimethylformamide was used as solvent at 0 °C. T...

  2. Pomegranate seed oil: Effect on 3-nitropropionic acid-induced neurotoxicity in PC12 cells and elucidation of unsaturated fatty acids composition.

    Science.gov (United States)

    Al-Sabahi, Bushra N; Fatope, Majek O; Essa, Musthafa Mohamed; Subash, Selvaraju; Al-Busafi, Saleh N; Al-Kusaibi, Fatma S N; Manivasagam, Thamilarasan

    2014-09-19

    Background Seed oils are used as cosmetics or topical treatment for wounds, allergy, dandruff, and other purposes. Natural antioxidants from plants were recently reported to delay the onset or progress of various neurodegenerative conditions. Over one thousand cultivars of Punica granatum (Punicaceae) are known and some are traditionally used to treat various ailments. Aim The effect of pomegranate oil on 3-nitropropionic acid- (3-NP) induced cytotoxicity in rat pheochromocytoma (PC12) neuronal cells was analyzed in this study. Furthermore, the analysis of unsaturated fatty acid composition of the seed oil of pomegranate by gas chromatography-electron impact mass spectrometry (GC-MS) was done. Results GC-MS study showed the presence of 6,9-octadecadiynoic acid (C18:2(6,9)) as a major component (60%) as 4,4-dimethyloxazoline derivative. The total extractable oil with light petroleum ether by Soxhlet from the dry seed of P. granatum was 4-6%. The oil analyzed for 48.90 ±?1.50 mg gallic acid equivalents/g of oil, and demonstrated radical-scavenging-linked antioxidant activities in various in vitro assays like the DPPH (2,2-diphenyl-l-picrylhydrazyl, % IP = 35.2 ± 0.9%), ABTS (2,2'-azino-bis-3-ethylene benzothiozoline-6-sulfonic acid, % IP 2.2 ± 0.1%), and ?-carotene bleaching assay (% IP = 26 ± 3%), respectively, which could be due the possible role of one methylene interrupted diynoic acid system for its radical-scavenging/antioxidant properties of oil. The oil also reduced lipid peroxidation, suppressed reactive oxygen species, extracellular nitric oxide, lactate/pyruvate ratio, and lactase dehydrogenase generated by 3-NP- (100 mM) induced neurotoxicity in PC12 cells, and enhanced the levels of enzymatic and non-enzymatic antioxidants at 40 ?g of gallic acid equivalents. Conclusion The protective effect of pomegranate seed oil might be due to the ability of an oil to neutralize ROS or enhance the expression of antioxidant gene. PMID:25238165

  3. Radically enhanced molecular recognition

    KAUST Repository

    Trabolsi, Ali

    2009-12-17

    The tendency for viologen radical cations to dimerize has been harnessed to establish a recognition motif based on their ability to form extremely strong inclusion complexes with cyclobis(paraquat-p-phenylene) in its diradical dicationic redox state. This previously unreported complex involving three bipyridinium cation radicals increases the versatility of host-guest chemistry, extending its practice beyond the traditional reliance on neutral and charged guests and hosts. In particular, transporting the concept of radical dimerization into the field of mechanically interlocked molecules introduces a higher level of control within molecular switches and machines. Herein, we report that bistable and tristable [2]rotaxanes can be switched by altering electrochemical potentials. In a tristable [2]rotaxane composed of a cyclobis(paraquat-p-phenylene) ring and a dumbbell with tetrathiafulvalene, dioxynaphthalene and bipyridinium recognition sites, the position of the ring can be switched. On oxidation, it moves from the tetrathiafulvalene to the dioxynaphthalene, and on reduction, to the bipyridinium radical cation, provided the ring is also reduced simultaneously to the diradical dication. © 2010 Macmillan Publishers Limited. All rights reserved.

  4. Counter radicalization development assistance

    OpenAIRE

    van Hippel, Karin

    2006-01-01

    The paper reviews current research and practice and recommends strategies for development agencies working in the Arab and Muslim world. It builds on the basic assumption that the realization of the Millennium Development Goals will be vital to reduce support for terrorism in the long term. Within this overall framework, emphasis is placed on particular programs that could be specifically applied to counter radicalization.

  5. Guest Editorial: Processes of radicalization and de-radicalization

    OpenAIRE

    Donatella Della Porta; Gary LaFree

    2012-01-01

    The study of radicalization and de-radicalization, understood as processes leading towards the increased or decreased use of political violence, is central to the question of how political violence emerges, how it can be prevented, and how it can be contained. The focus section of this issue of the International Journal of Conflict and Violence addresses radicalization and de-radicalization, seeking to develop a more comprehensive understanding of the processes, dynamics, and mechanisms invol...

  6. Impacts of an unknown daytime nitrous acid source on its daytime concentration and budget, as well as those of hydroxyl, hydroperoxyl, and organic peroxy radicals, in the coastal regions of China

    Directory of Open Access Journals (Sweden)

    Y. Tang

    2015-01-01

    Full Text Available Many field experiments have found high nitrous acid (HONO mixing ratios in both urban and rural areas during daytime, but these high daytime HONO mixing ratios cannot be explained well by gas-phase production, suggesting that an unknown daytime HONO source (Punknown could exist. The formula Punknown ≈ 19.60 × NO2 × J(NO2 was obtained using observed data from 13 field experiments across the globe. The additional HONO sources (i.e. the Punknown, HONO emissions, and nighttime hydrolysis conversion of nitrogen dioxide (NO2 on aerosols were coupled into the WRF-Chem model (Weather Research and Forecasting model coupled with Chemistry to assess the Punknown impacts on the concentrations and budgets of HONO and peroxy (hydroxyl, hydroperoxyl, and organic peroxy radicals (ROx (= OH + HO2 + RO2 in the coastal regions of China. Results indicated that the additional HONO sources produced a significant improvement in HONO and OH simulations, particularly in the daytime. Elevated daytime-mean Punknown values were found in the coastal regions of China, with a maximum of 2.5 ppb h?1 in the Beijing–Tianjin–Hebei region. The Punknown produced a 60–250% increase of OH, HO2 and RO2 near the ground in the major cities of the coastal regions of China, and a 5–48% increase of OH, HO2 and RO2 in the daytime meridional-mean mixing ratios within 1000 m above the ground. When the additional HONO sources were included, the photolysis of HONO was dominated in the OH production rate in Beijing, Shanghai and Guangzhou before 10:00 LST with a maximum of 10.01 [7.26 due to the Punknown] ppb h?1 in Beijing, whereas the reaction of HO2 + NO (nitric oxide was dominated after 10:00 LST with a maximum of 9.38 [7.23] ppb h?1 in Beijing. The whole ROx cycle was accelerated by the additional HONO sources, especially the Punknown. The OH production rate was enhanced by 0.67 [0.64] to 4.32 [3.86] ppb h?1 via the reaction of HO2 + NO, and by 0.85 [0.69] to 4.11 [3.61] ppb h?1 via the photolysis of HONO, and the OH loss rate was enhanced by 0.58 [0.55] to 2.03 [1.92] ppb h?1 via the reaction of OH + NO2 and by 0.31 [0.28] to 1.78 [1.64] ppb h?1 via the reaction of OH + CO (carbon monoxide in Beijing, Shanghai and Guangzhou. Similarly, the additional HONO sources produced an increase of 0.31 [0.28] to 1.78 [1.64] ppb h?1 via the reaction of OH + CO and 0.10 [0.09] to 0.63 [0.59] ppb h?1 via the reaction of CH3O2 (methylperoxy radical + NO in the HO2 production rate, and 0.67 [0.61] to 4.32 [4.27] ppb h?1 via the reaction of HO2 + NO in the HO2 loss rate in Beijing, Shanghai and Guangzhou. The above results suggest that the Punknown considerably enhanced the ROx concentrations and accelerated ROx cycles in the coastal regions of China, and could produce significant increases in concentrations of inorganic aerosols and secondary organic aerosols and further aggravate haze events in these regions.

  7. Impacts of an unknown daytime nitrous acid source on its daytime concentration and budget, as well as those of hydroxyl, hydroperoxyl, and organic peroxy radicals, in the coastal regions of China

    Science.gov (United States)

    Tang, Y.; An, J.; Wang, F.; Li, Y.; Qu, Y.; Chen, Y.; Lin, J.

    2015-01-01

    Many field experiments have found high nitrous acid (HONO) mixing ratios in both urban and rural areas during daytime, but these high daytime HONO mixing ratios cannot be explained well by gas-phase production, suggesting that an unknown daytime HONO source (Punknown) could exist. The formula Punknown ? 19.60 × NO2 × J(NO2) was obtained using observed data from 13 field experiments across the globe. The additional HONO sources (i.e. the Punknown, HONO emissions, and nighttime hydrolysis conversion of nitrogen dioxide (NO2) on aerosols) were coupled into the WRF-Chem model (Weather Research and Forecasting model coupled with Chemistry) to assess the Punknown impacts on the concentrations and budgets of HONO and peroxy (hydroxyl, hydroperoxyl, and organic peroxy) radicals (ROx) (= OH + HO2 + RO2) in the coastal regions of China. Results indicated that the additional HONO sources produced a significant improvement in HONO and OH simulations, particularly in the daytime. Elevated daytime-mean Punknown values were found in the coastal regions of China, with a maximum of 2.5 ppb h-1 in the Beijing-Tianjin-Hebei region. The Punknown produced a 60-250% increase of OH, HO2 and RO2 near the ground in the major cities of the coastal regions of China, and a 5-48% increase of OH, HO2 and RO2 in the daytime meridional-mean mixing ratios within 1000 m above the ground. When the additional HONO sources were included, the photolysis of HONO was dominated in the OH production rate in Beijing, Shanghai and Guangzhou before 10:00 LST with a maximum of 10.01 [7.26 due to the Punknown] ppb h-1 in Beijing, whereas the reaction of HO2 + NO (nitric oxide) was dominated after 10:00 LST with a maximum of 9.38 [7.23] ppb h-1 in Beijing. The whole ROx cycle was accelerated by the additional HONO sources, especially the Punknown. The OH production rate was enhanced by 0.67 [0.64] to 4.32 [3.86] ppb h-1 via the reaction of HO2 + NO, and by 0.85 [0.69] to 4.11 [3.61] ppb h-1 via the photolysis of HONO, and the OH loss rate was enhanced by 0.58 [0.55] to 2.03 [1.92] ppb h-1 via the reaction of OH + NO2 and by 0.31 [0.28] to 1.78 [1.64] ppb h-1 via the reaction of OH + CO (carbon monoxide) in Beijing, Shanghai and Guangzhou. Similarly, the additional HONO sources produced an increase of 0.31 [0.28] to 1.78 [1.64] ppb h-1 via the reaction of OH + CO and 0.10 [0.09] to 0.63 [0.59] ppb h-1 via the reaction of CH3O2 (methylperoxy radical) + NO in the HO2 production rate, and 0.67 [0.61] to 4.32 [4.27] ppb h-1 via the reaction of HO2 + NO in the HO2 loss rate in Beijing, Shanghai and Guangzhou. The above results suggest that the Punknown considerably enhanced the ROx concentrations and accelerated ROx cycles in the coastal regions of China, and could produce significant increases in concentrations of inorganic aerosols and secondary organic aerosols and further aggravate haze events in these regions.

  8. Changes in free-radical scavenging ability of kombucha tea during fermentation.

    Science.gov (United States)

    Jayabalan, R; Subathradevi, P; Marimuthu, S; Sathishkumar, M; Swaminathan, K

    2008-07-01

    Kombucha tea is a fermented tea beverage produced by fermenting sugared black tea with tea fungus (kombucha). Free-radical scavenging abilities of kombucha tea prepared from green tea (GTK), black tea (BTK) and tea waste material (TWK) along with pH, phenolic compounds and reducing power were investigated during fermentation period. Phenolic compounds, scavenging activity on DPPH radical, superoxide radical (xanthine-xanthine oxidase system) and inhibitory activity against hydroxyl radical mediated linoleic acid oxidation (ammonium thiocyanate assay) were increased during fermentation period, whereas pH, reducing power, hydroxyl radical scavenging ability (ascorbic acid-iron EDTA) and anti-lipid peroxidation ability (thiobarbituric assay) were decreased. From the present study, it is obvious that there might be some chances of structural modification of components in tea due to enzymes liberated by bacteria and yeast during kombucha fermentation which results in better scavenging performance on nitrogen and superoxide radicals, and poor scavenging performance on hydroxyl radicals. PMID:26054285

  9. Hydroxyl Radical and Its Scavengers in Health and Disease

    OpenAIRE

    Boguslaw Lipinski

    2011-01-01

    It is generally believed that diseases caused by oxidative stress should be treated with antioxidants. However, clinical trials with such antioxidants as ascorbic acid and vitamin E, failed to produce the expected beneficial results. On the other hand, important biomolecules can be modified by the introduction of oxygen atoms by means of non-oxidative hydroxyl radicals. In addition, hydroxyl radicals can reduce disulfide bonds in proteins, specifically fibrinogen, resulting in their unfoldin...

  10. New free radical scavenging neolignans from fruits of Piper attenuatum

    Science.gov (United States)

    Reddy, S. Divya; Siva, Bandi; Poornima, B.; Kumar, D. Anand; Tiwari, Ashok K.; Ramesh, U.; Babu, K. Suresh

    2015-01-01

    Objective: The aim was to study and identify free radicals scavenging and antihyperglycemic principles in fruit of Piper attenuatum. Materials and Methods: Bioassay guided identification of extracts possessing potent free radical scavenging activity, and isolation of compounds was done. Chloroform extract of P. attenuatum possessing potent radical scavenging activity was also evaluated for antihyperglycemic activity following oral glucose tolerance test in rats. Results: Nine neolignans namely, denudatin B (1), iso-4’, 5’-dimethoxy-3, 4-methylenedioxy-2’-oxo-?3’,5’,8’-8.1’-lignan (2), lancifolin D (3), denudatin A (4), wallichinin (5), piperenone (6), lancifolin C (7), 2-oxo-piperol B (8), piperkadsin A (9) and a crotepoxide (10) was identified in Chloroform extract of P. attenuatum. Neolignans (1-9) displayed potent 2, 2’-azino-bis (3-ethylbenzothiazoline-6-sulphonic acid) radical and piperkadsin A (9) also displayed 1, 1-diphenyl-2-picrylhydrazyl radical scavenging activity. Analysis of structure-activity relationship revealed that presence of furan ring and methoxy groups is an important criterion to influence 2, 2’-azino-bis (3-ethylbenzothiazoline-6-sulphonic acid) radical scavenging potentials. Chloroform extract of P. attenuatum fruit could not display antihyperglycemic activity following oral glucose tolerance test in rats. Conclusion: Neolignans present in P. attenuatum fruits are potent free radical scavengers and this is the first report identifying these compounds and activities in this fruit. PMID:25829760

  11. Yield determination of radical OH with therapeutic ion beam

    International Nuclear Information System (INIS)

    Solution of Coumarin-3-carboxylic acid (CCA) has been applied to yield measurement of radical OH in water radiolysis with carbon ion beams. Production yield of a fluorescent probe, 7OH-CCA, which is a stable product produced after scavenging reaction for radical OH by CCA, was determined by using HPLC connected to a fluorometer. By using this chemical system, radical OH yields near the Bragg peak have been measured. Contribution of fragmentations, which are known to be significant near the Bragg peak of high-energy heavy ions, is also discussed by conducting fragmentation simulation with deterministic, semi-empirical and one-dimensional code named HIBRAC. (author)

  12. Structure and lyoluminescent reactions of free radicals of irradiated lactose

    International Nuclear Information System (INIS)

    To determine mechanisms of processes, resulting in lyoluminescence the structure of fren radicals in ?-irradiated lactose was investigated by the method of electron paramagnetic resonance. Analysis of dependences of different radical content in irradiated crystals and lyoluminescent characteristics of these samples on the period of their storing enabled to confirm suggested earlier luminescence mechanism with lambdasub(max)=630 nm of irradiated carbon-hydrate in neutral and acid media. The possibility of controlling the content of different types of radicals in samples by lyoluminescent method was shown

  13. Fenoles totales y capacidad antioxidante estimada con los ensayos DPPH/ABTS en rosas en soluciones preservantes / Total phenols and antioxidant capacity estimated with DPPH/ABTS assays in roses on preservative solutions

    Scientific Electronic Library Online (English)

    Nadia, Zenil Lugo; Ma. Teresa, Colinas León; Cecilio, Bautista Bañuelos; Tito Roque, Vázquez Rojas; Héctor, Lozoya Saldaña; Ma.Teresa, Martínez Damián.

    2014-09-01

    Full Text Available Tallos de rosa 'Freedom' se evaluaron en dos soluciones preservantes: 8-citrato de hidroxiquinoleina (HQC) y Chrysal CLEAR Professional 2® T-bag (CHRYSAL) en un pulso de 24 h a temperatura ambiente (24 ± 2 °C, 75 % HR) y agua como testigo. Se utilizó un diseño completamente al azar con cuatro repeti [...] ciones, la unidad experimental fue un tallo floral. Se evaluó la vida de florero, el contenido de fenoles totales con el método colorimétrico de Folin-Ciocalteauy la capacidad antioxidante total (caT) con los ensayos DPPH y ABTS tanto en hoja como en pétalo. Se realizó el ANOVA y correlaciones simples entre la caT y el contenido de fenoles, y entre ambos ensayos. Los resultados muestran que las soluciones preservantes promueven un aumento en la caT y contenido de fenoles totales en hoja, pero no en pétalo. Las hojas de los tallos florales tratados con CHRYSAL presentaron los mayores contenidos de fenoles totales y caT, mientras que el testigo los menores. La vida media de florero fue de: 13, 11 y 9 días para los tratados con CHRYSAL, HQC y el testigo, respectivamente. El contenido de fenoles totales presentó una estrecha relación positiva (?? 0.01) con la caT: 0.87 y 0.85 medida con el ABTS y 0.92 y 0.85 con el DPPH en hoja y pétalo respectivamente y también ambos métodos se correlacionaron entre sí positiva y significativamente (r= 0.91) en hoja y (r= 0.93) en pétalo. Abstract in english Rose stems 'Freedom' were evaluated in two preservative solutions: 8-hydroxyquinoline citrate (HQC) and Chrysal CLEAR® Professional 2 T-bag (CHRYSAL) in a pulse of 24 h at room temperature (24 ± 2 °C, 75% HR) and water as control. A completely randomized design with four replications was used; the e [...] xperimental unit was a flower stem. Vase life, total phenolic content with the colorimetric method Folin-Ciocalteauy, total antioxidant capacity (caT) with DPPH and ABTS assays in both leaf and petal was evaluated. ANOVA and simple correlations between caT and content of phenols and between both assays was made. The results show that preservative solutions promote an increase in caT and total phenolic content in leaf, but not in petal. The leaves of the flowering stems treated with CHRYSAL had the highest contents of total phenols and caT, while control the lowest. The average vase life was 13, 11 and 9 days for those treated with CHRYSAL, HQC and control, respectively. The total phenolic content showed a strong positive relation (? ?0.01) with caT: 0.87 and 0.85 measured with ABTS and 0.92 and 0.85 with DPPH in leaf and petal respectively and also both methods were correlated positively and significantly with each other (r= 0.91) in leaf and (r= 0.93) in petal.

  14. Atropisomerism of the Asn ? Radicals Revealed by Ramachandran Surface Topology

    DEFF Research Database (Denmark)

    Gerlei, Klára Z.; Jákli, Imre

    2013-01-01

    C radicals are typically trigonal planar and thus achiral, regardless of whether they originate from a chiral or an achiral C-atom (e.g., C-H + (•)OH ? C• + H2O). Oxidative stress could initiate radical formation in proteins when, for example, the H-atom is abstracted from the C?-carbon of an amino acid residue. Electronic structure calculations show that such a radical remains achiral when formed from the achiral Gly, or the chiral but small Ala residues. However, when longer side-chain containing proteogenic amino acid residues are studied (e.g., Asn), they provide radicals of axis chirality, which in turn leads to atropisomerism observed for the first time for peptides. The two enantiomeric extended backbone structures, •?L and •?D, interconvert via a pair of enantiotopic reaction paths, monitored on a 4D Ramachandran surface, with two distinct transition states of very different Gibbs-free energies: 37.4 and 67.7 kJ/mol, respectively. This discovery requires the reassessment of our understanding on radical formation and their conformational and stereochemical behavior. Furthermore, the atropisomerism of proteogenic amino acid residues should affect our understanding on radicals in biological systems and, thus, reframes the role of the D-residues as markers of molecular aging.

  15. In vitro free radical scavenging activity of platinum nanoparticles

    International Nuclear Information System (INIS)

    A polyacrylic acid (PAA)-protected platinum nanoparticle species (PAA-Pt) was prepared by alcohol reduction of hexachloroplatinate. The PAA-Pt nanoparticles were well dispersed and homogeneous in size with an average diameter of 2.0 ± 0.4 nm (n = 200). We used electron spin resonance to quantify the residual peroxyl radical AOO. generated from 2,2-azobis (2-aminopropane) dihydrochloride (AAPH) by thermal decomposition in the presence of O2 and a spectrophotometric method to quantify the residual 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical. PAA-Pt scavenged these two radicals in a dose-dependent manner. Platinum was the functional component. PAA-Pt reduced the rate of oxygen consumption required for linoleic acid peroxidation initiated by AOO. generated from AAPH, indicating inhibition of the propagation of linolate peroxidation. A thiobarbituric acid test also revealed dose-dependent inhibition of the linolate peroxidation by PAA-Pt. Fifty micromolar platinum, as PAA-Pt, completely quenched 250 ?M DPPH radical for 5 min. Even when twice diluted in half, the PAA-Pt still quenched 100% of the 250 ?M DPPH radical. The scavenging activity of PAA-Pt is durable. These observations suggest that PAA-Pt is an efficient scavenger of free radicals.

  16. In vitro free radical scavenging activity of platinum nanoparticles

    Science.gov (United States)

    Watanabe, Aki; Kajita, Masashi; Kim, Juewon; Kanayama, Atsuhiro; Takahashi, Kyoko; Mashino, Tadahiko; Miyamoto, Yusei

    2009-11-01

    A polyacrylic acid (PAA)-protected platinum nanoparticle species (PAA-Pt) was prepared by alcohol reduction of hexachloroplatinate. The PAA-Pt nanoparticles were well dispersed and homogeneous in size with an average diameter of 2.0 ± 0.4 nm (n = 200). We used electron spin resonance to quantify the residual peroxyl radical (\\mathrm {AOO}^{\\bullet } ) generated from 2,2-azobis (2-aminopropane) dihydrochloride (AAPH) by thermal decomposition in the presence of O2 and a spectrophotometric method to quantify the residual 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical. PAA-Pt scavenged these two radicals in a dose-dependent manner. Platinum was the functional component. PAA-Pt reduced the rate of oxygen consumption required for linoleic acid peroxidation initiated by \\mathrm {AOO}^{\\bullet } generated from AAPH, indicating inhibition of the propagation of linolate peroxidation. A thiobarbituric acid test also revealed dose-dependent inhibition of the linolate peroxidation by PAA-Pt. Fifty micromolar platinum, as PAA-Pt, completely quenched 250 µM DPPH radical for 5 min. Even when twice diluted in half, the PAA-Pt still quenched 100% of the 250 µM DPPH radical. The scavenging activity of PAA-Pt is durable. These observations suggest that PAA-Pt is an efficient scavenger of free radicals.

  17. In vitro free radical scavenging activity of platinum nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Aki; Kajita, Masashi; Kim, Juewon; Kanayama, Atsuhiro; Miyamoto, Yusei [Department of Integrated Biosciences, Graduate School of Frontier Sciences, University of Tokyo, Bioscience Building 402, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8562 (Japan); Takahashi, Kyoko; Mashino, Tadahiko, E-mail: yusei74@k.u-tokyo.ac.j [Department of Pharmaceutical Sciences, Faculty of Pharmacy, Keio University, 1-5-30 Shibakoen, Minato, Tokyo 105-8512 (Japan)

    2009-11-11

    A polyacrylic acid (PAA)-protected platinum nanoparticle species (PAA-Pt) was prepared by alcohol reduction of hexachloroplatinate. The PAA-Pt nanoparticles were well dispersed and homogeneous in size with an average diameter of 2.0 {+-} 0.4 nm (n = 200). We used electron spin resonance to quantify the residual peroxyl radical AOO. generated from 2,2-azobis (2-aminopropane) dihydrochloride (AAPH) by thermal decomposition in the presence of O{sub 2} and a spectrophotometric method to quantify the residual 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical. PAA-Pt scavenged these two radicals in a dose-dependent manner. Platinum was the functional component. PAA-Pt reduced the rate of oxygen consumption required for linoleic acid peroxidation initiated by AOO. generated from AAPH, indicating inhibition of the propagation of linolate peroxidation. A thiobarbituric acid test also revealed dose-dependent inhibition of the linolate peroxidation by PAA-Pt. Fifty micromolar platinum, as PAA-Pt, completely quenched 250 {mu}M DPPH radical for 5 min. Even when twice diluted in half, the PAA-Pt still quenched 100% of the 250 {mu}M DPPH radical. The scavenging activity of PAA-Pt is durable. These observations suggest that PAA-Pt is an efficient scavenger of free radicals.

  18. Toward Radicalizing Community Service Learning

    Science.gov (United States)

    Sheffield, Eric C.

    2015-01-01

    This article advocates a radicalized theoretical construction of community service learning. To accomplish this radicalization, I initially take up a discussion of traditional understandings of CSL rooted in pragmatic/progressive thought. I then suggest that this traditional structural foundation can be radicalized by incorporating Deborah…

  19. Phenolic antioxidant scavenging of myosin radicals generated by hypervalent myoglobin.

    Science.gov (United States)

    Jongberg, Sisse; Lund, Marianne N; Østdal, Henrik; Skibsted, Leif H

    2012-12-01

    The scavenging activity of extracts of green tea (GTE), white grape (WGE), and rosemary (RE), all plant material with high phenolic content, and of the phenolic compounds 4-methylcatechol (4-MC), (+)-catechin, and carnosic acid toward long-lived myosin radicals generated by reaction with H2O2-activated myoglobin at room temperature (pH 7.5, I=1.0) was investigated by freeze-quench ESR spectroscopy. Myosin radicals were generated by incubating 16 ?M myosin, 800 ?M metmyoglobin, and 800 ?M H2O2 for 10 min, and the phenolic extracts were subsequently added (1% (w/w) phenolic compounds relative to myosin). GTE was able to scavenge myosin radicals and reduce the radical intensity by 65%. Furthermore, a low concentration of 4-MC (33 ?M) was found to increase the radical concentration when added to the myosin radicals, whereas a higher concentration of 4-MC and catechin (330 ?M) was found to scavenge myosin radicals and reduce the overall radical concentration by ?65%. PMID:23163579

  20. Resonant cavity spectroscopy of radical species

    Science.gov (United States)

    Ritchie, Grant

    2015-04-01

    Photo-oxidation in the troposphere is highly complex, being initiated by short lived radical species, in the daytime dominated by the hydroxyl radical, OH, with contributions from Cl atoms, and at night by either NO3 radicals or ozone. Chemical oxidation cycles, which couple OH, HO2 and peroxy (RO2) radical species, remove primary emitted trace species which are harmful to humans or to the wider environment. However, many of the secondary products produced by atmospheric photo-oxidation are also directly harmful, for example O3, NO2, acidic and multifunctional species, many of which are of low volatility and are able to partition effectively to the condensed phase, creating secondary organic aerosol (SOA), which contributes a significant fraction of tropospheric aerosol, with associated impacts on climate and human health. The accuracy of atmospheric models to predict these impacts necessarily requires accurate knowledge of the chemical oxidative cycling. Two of the simplest intermediates are the hydroperoxy radical, HO2, and the smallest and dominant organic peroxy radical, CH3O2, formed directly by the reactions of OH with CO/O2 and CH4/O2, respectively, and indirectly following the oxidation of larger VOCs. OH, HO2 and RO2 (collectively known as ROx) are rapidly cycled, being at the centre of tropospheric oxidation, and hence are some of the best targets for models to compare with field data. The reaction of HO2 and RO2 with NO constitutes the only tropospheric in-situ source of O3. Despite their importance, neither HO2 nor CH3O2 is measured directly in the atmosphere. HO2 is only measured indirectly following its conversion to OH and CH3O2 is not measured at all. Typically only the sum of RO2 radicals is measured, making no distinction between different organic peroxy radicals. This contribution will detail recent studies using (i) optical feedback cavity enhanced absorption spectroscopy with both quantum and inter-band cascade lasers in the mid-IR, and (ii) near-IR diode laser based noise immune cavity enhanced heterodyne molecular spectroscopy as potential methods for the direct detection of HO2 and CH3O2 at atmospheric levels.

  1. Cytoplasmic superoxide radical

    Science.gov (United States)

    Murakami, Kazuma; Shimizu, Takahiko

    2012-01-01

    Soluble amyloid ? (A?) oligomers cause memory loss and synaptic dysfunction in Alzheimer disease (AD). Despite intensive studies on A? assembly in vitro and in vivo, the localization and cellular mechanism of A? oligomerization are not fully understood. Previously, we demonstrated that cytoplasmic superoxide radicals contribute to drusen deposition, a hallmark of age-related macular degeneration as well as other geriatric diseases (fatty liver, skin thinning, and osteoporosis). Using a transgenic mouse model of AD, we recently clarified the role of cytoplasmic oxidative stress in cognitive impairment and oligomer formation. Moreover, we also found that these phenomena were associated with neuroinflammation, tau phosphorylation, and synaptic loss. Notably, studies using human brains support the involvement of cytoplasmic superoxide radicals in AD pathology. In this addendum to Murakami et al. (JBC 2011), we discuss and comment on intracellular A? oligomer formation and the possible therapeutic effects of intracellular redox state modulators. PMID:22896786

  2. Salvage robotic radical prostatectomy

    OpenAIRE

    Kaffenberger, Samuel D.; Smith, Joseph A.

    2014-01-01

    Failure of non-surgical primary treatment for localized prostate cancer is a common occurrence, with rates of disease recurrence ranging from 20% to 60%. In a large proportion of patients, disease recurrence is clinically localized and therefore potentially curable. Unfortunately, due to the complex and potentially morbid nature of salvage treatment, radical salvage surgery is uncommonly performed. In an attempt to decrease the morbidity of salvage therapy without sacrificing oncologic effica...

  3. Gangs, Terrorism, and Radicalization

    OpenAIRE

    Scott Decker; David Pyrooz

    2011-01-01

    What can street gangs tell us about radicalization and extremist groups? At first glance, these two groups seem to push the boundaries of comparison. In this article, we examine the important similarities and differences across criminal, deviant, and extremist groups. Drawing from research on street gangs, this article explores issues such as levels of explanation,organizational structure, group process, and the increasingly important role of technology and the Internet in the context of radi...

  4. Probability and radical behaviorism

    OpenAIRE

    Espinosa, James M.

    1992-01-01

    The concept of probability appears to be very important in the radical behaviorism of Skinner. Yet, it seems that this probability has not been accurately defined and is still ambiguous. I give a strict, relative frequency interpretation of probability and its applicability to the data from the science of behavior as supplied by cumulative records. Two examples of stochastic processes are given that may model the data from cumulative records that result under conditions of continuous reinforc...

  5. DEMOCRACIA RADICAL Y CIUDADANÍA

    OpenAIRE

    Pedro Pablo Serna

    2008-01-01

    En el presente texto se presentan dos miradas con respecto a la democracia y su relación con el pensamiento liberal, mostrando de manera específica las características principales de la democracia radical y la manera como ésta puede realizar un adecuado encuentro entre lo individual y lo social, sin afectar las garantías mínimas que se le deben dar a todos los individuos para la realización de su propia concepción de bien. Debe propiciar también unas condiciones adecuadas de participación y c...

  6. Women and radicalization

    OpenAIRE

    Badran, Margot

    2006-01-01

    The paper focuses on women and radicalization within the context of Muslim societies (majority, minority, and half Muslim) societies and groups, mainly in Asia and Africa. The basic argument advanced in this paper is that Islamic feminism with its gender-egalitarian discourse and practices has a major role to play in the empowerment of Muslim women—and of men and society as a whole—and should be brought to bear in devising policy, strategy, and tools.

  7. The Reaction of Acetyl Peroxy Radical with Aldehyde: Impact on the OH Radical Model Simulation

    Science.gov (United States)

    Huang, D.; Chen, Z.

    2014-12-01

    Understanding the budget of OH (hydroxyl radical) is very important for investigating the atmospheric oxidation capacity, aerosol formation and climate change. Recent studies indicate that there may be a great gap between the modeled and measured OH concentrations in some rural forest areas. This gap may result from our incomplete knowledge about the oxidation mechanism of volatile organic compounds (VOCs). Here, we suggest that acetyl peroxy radical (CH3C(O)OO•), the OH-initiated oxidation intermediate of most VOCs, can take the H-atom from the aldehyde group to form corresponding peroxy carboxylic acids. This reaction has not been concerned in the atmosphere. The acetyl peroxy radical may share the "oxidation responsibility" of OH, and help saving OH from being consumed by aldehyde. Using a box model coupled with the isoprene-OH reaction mechanism selected from MCM v3.2, we get OH saving ratio (SROH) when we compare the modeled OH levels in the presence and absence of the reaction of acetyl peroxy radical with aldehyde. We find that SROH is not a constant but a function of OH production rate, reaction time, isoprene concentration and the ratio of aldehyde to isoprene. It is expected that CH3C(O)OO• radical, a non-OH oxidant, plays an important role in maintaining the oxidation capacity of the troposphere.

  8. Evidence for radical-oxidation of plasma proteins in humans

    Energy Technology Data Exchange (ETDEWEB)

    Wang, D.; Davies, M.; Dean, R. [Heart Research Institute, Camperdown, NSW (Australia); Fu, S.; Taurins, A.; Sullivans, D. [Royal Prince Alfred Hospital, Camperdown, NSW (Australia). Department of Biochemistry; Muench, G. [Biozentrum der University of Wuerzberg, (Germany)

    1998-12-31

    Oxidation of proteins by radicals has been implicated in many pathological processes. The hydroxyl radical is known to generate protein-bound hydroxylated derivatives of amino acids, for example hydroxyvaline (from Val), hydroxyleucine (from Leu), o-tyrosine (from Phe), and DOPA (from Tyr). In this study, we have investigated the occurrence of these oxidised amino acids in human plasma proteins from both normal subjects and dialysis patients. By employing previously established HPLC methods [Fu et al. Biochemical Journal, 330, 233-239, 1998], we have found that oxidised amino acids exist in normal human plasma proteins (n=32). The level of these oxidised amino acids is not correlated to age. Similar levels of oxidised amino acids are found in the plasma proteins of the dialysis patients (n=6), but a more detailed survey is underway. The relative abundance of the oxidised amino acids is similar to that resulting from oxidation of BSA by hydroxy radicals or Fenton systems [Fu et al. Biochemical Journal, 333, 519-525, 1998]. The results suggest that metal-ion catalysed oxyl-radical chemistry may be a key contributor to the oxidative damage in plasma proteins in vivo in humans

  9. Evidence for radical-oxidation of plasma proteins in humans

    International Nuclear Information System (INIS)

    Oxidation of proteins by radicals has been implicated in many pathological processes. The hydroxyl radical is known to generate protein-bound hydroxylated derivatives of amino acids, for example hydroxyvaline (from Val), hydroxyleucine (from Leu), o-tyrosine (from Phe), and DOPA (from Tyr). In this study, we have investigated the occurrence of these oxidised amino acids in human plasma proteins from both normal subjects and dialysis patients. By employing previously established HPLC methods [Fu et al. Biochemical Journal, 330, 233-239, 1998], we have found that oxidised amino acids exist in normal human plasma proteins (n=32). The level of these oxidised amino acids is not correlated to age. Similar levels of oxidised amino acids are found in the plasma proteins of the dialysis patients (n=6), but a more detailed survey is underway. The relative abundance of the oxidised amino acids is similar to that resulting from oxidation of BSA by hydroxy radicals or Fenton systems [Fu et al. Biochemical Journal, 333, 519-525, 1998]. The results suggest that metal-ion catalysed oxyl-radical chemistry may be a key contributor to the oxidative damage in plasma proteins in vivo in humans

  10. The revealing of the absorption band of phenol cation-radical

    International Nuclear Information System (INIS)

    The photolysis and radiolysis of phenol in polar solutions resulted in the appearance of the bands typical of a solvated electron and phenoxy radical in the absorption spectra. At the same time no bands which could be attributed to phenol cation-radical were found. To find the region of the phenol cation-radical absorption the 77 K and room temperature absorption spectra of phenol photolysis products in a boric acid glass (1x10-3 M) have been investigated, where cation-radicals were known to be effectively stabilized. The room-temperature photolysis resulted in the appearance of the features in absorption spectrum typical of phenoxy radical in the region of 410 nm, while the 77 K photolysis lead to the formation of a photolysis with somewhat another spectrum. After refreezing the sample photolyzed at 77 K, its absorption spectrum changed to coincide completely with the phenoxy radical spectrum. Such absorption spectrum behaviour can be accounted for the phenol cation-radical formation in the glassy boric acid by the 77 K photolysis and its subsequent conversion to phenoxy radical with proton splitting by refreezing. This phenol cation-radical absorption band is situated in the region of 440-450 nm for this matrix. A similar absorption spectrum was observed by the phenol radiolysis in butyl chloride and by the anisole photolysis in orthophosphoric acid at 77 K, the facts confirming the validity of the assignment of this band to the cation-radical. (author)

  11. Sorafenib Sensitizes Glioma Cells to the BH3 Mimetic ABT-737 by Targeting MCL1 in a STAT3-Dependent Manner

    Directory of Open Access Journals (Sweden)

    Irina Kiprianova

    2015-07-01

    Full Text Available The oncogenic transcription factor signal transducer and activator of transcription 3 (STAT3 is overactivated in malignant glioma and plays a key role in promoting cell survival, thereby increasing the acquired apoptosis resistance of these tumors. Here we investigated the STAT3/myeloid cell leukemia 1 (MCL1 signaling pathway as a target to overcome the resistance of glioma cells to the Bcl-2-inhibiting synthetic BH3 mimetic ABT-737. Stable lentiviral knockdown of MCL1 sensitized LN229 and U87 glioma cells to apoptotic cell death induced by single-agent treatment with ABT-737 which was associated with an early activation of DEVDase activity, cytochrome c release, and nuclear apoptosis. Similar sensitizing effects were observed when ABT-737 treatment was combined with the multikinase inhibitor sorafenib which effectively suppressed levels of phosphorylated STAT3 and MCL1 in MCL1-proficient LN229 and U87 glioma cells. In analogous fashion, these synergistic effects were observed when we combined ABT-737 with the STAT3 inhibitor WP-1066. Lentiviral knockdown of the activating transcription factor 5 combined with subsequent quantitative polymerase chain reaction analysis revealed that sorafenib-dependent suppression of MCL1 occurred at the transcriptional level but did not depend on activating transcription factor 5 which previously had been proposed to be essential for MCL1-dependent glioma cell survival. In contrast, the constitutively active STAT3 mutant STAT3-C was able to significantly enhance MCL1 levels under sorafenib treatment to retain cell survival. Collectively, these data demonstrate that sorafenib targets MCL1 in a STAT3-dependent manner, thereby sensitizing glioma cells to treatment with ABT-737. They also suggest that targeting STAT3 in combination with inducers of the intrinsic pathway of apoptosis may be a promising novel strategy for the treatment of malignant glioma.

  12. Sorafenib Sensitizes Glioma Cells to the BH3 Mimetic ABT-737 by Targeting MCL1 in a STAT3-Dependent Manner12

    Science.gov (United States)

    Kiprianova, Irina; Remy, Janina; Milosch, Nelli; Mohrenz, Isabelle V.; Seifert, Volker; Aigner, Achim; Kögel, Donat

    2015-01-01

    The oncogenic transcription factor signal transducer and activator of transcription 3 (STAT3) is overactivated in malignant glioma and plays a key role in promoting cell survival, thereby increasing the acquired apoptosis resistance of these tumors. Here we investigated the STAT3/myeloid cell leukemia 1 (MCL1) signaling pathway as a target to overcome the resistance of glioma cells to the Bcl-2-inhibiting synthetic BH3 mimetic ABT-737. Stable lentiviral knockdown of MCL1 sensitized LN229 and U87 glioma cells to apoptotic cell death induced by single-agent treatment with ABT-737 which was associated with an early activation of DEVDase activity, cytochrome c release, and nuclear apoptosis. Similar sensitizing effects were observed when ABT-737 treatment was combined with the multikinase inhibitor sorafenib which effectively suppressed levels of phosphorylated STAT3 and MCL1 in MCL1-proficient LN229 and U87 glioma cells. In analogous fashion, these synergistic effects were observed when we combined ABT-737 with the STAT3 inhibitor WP-1066. Lentiviral knockdown of the activating transcription factor 5 combined with subsequent quantitative polymerase chain reaction analysis revealed that sorafenib-dependent suppression of MCL1 occurred at the transcriptional level but did not depend on activating transcription factor 5 which previously had been proposed to be essential for MCL1-dependent glioma cell survival. In contrast, the constitutively active STAT3 mutant STAT3-C was able to significantly enhance MCL1 levels under sorafenib treatment to retain cell survival. Collectively, these data demonstrate that sorafenib targets MCL1 in a STAT3-dependent manner, thereby sensitizing glioma cells to treatment with ABT-737. They also suggest that targeting STAT3 in combination with inducers of the intrinsic pathway of apoptosis may be a promising novel strategy for the treatment of malignant glioma. PMID:26297434

  13. MCL-1 and BCL-xL-dependent resistance to the BCL-2 inhibitor ABT-199 can be overcome by preventing PI3K/AKT/mTOR activation in lymphoid malignancies

    Science.gov (United States)

    Choudhary, G S; Al-harbi, S; Mazumder, S; Hill, B T; Smith, M R; Bodo, J; Hsi, E D; Almasan, A

    2015-01-01

    Overexpression of anti-apoptotic BCL-2 family members is a hallmark of many lymphoid malignancies, including chronic lymphocytic leukemia (CLL) and non-Hodgkin lymphoma (NHL) that can be targeted with small molecule inhibitors. ABT-199 is a rationally designed BCL-2 homology (BH)-3 mimetic that specifically binds to BCL-2, but not to MCL-1 and BCL-xL. Although the thrombocytopenia that occurs with navitoclax treatment has not been a problem with ABT-199, clinical trials in CLL could benefit by lowering the ABT-199 concentration through targeting other survival pathways. In this study, we investigated the mechanisms of resistance that develops to ABT-199 therapy by generating ABT-199-resistant (ABT199-R) cell lines via chronic exposure of NHL cell lines to ABT-199. Acquired resistance resulted in substantial AKT activation and upregulation of MCL-1 and BCL-xL levels that sequestered BIM. ABT199-R cells exhibited increased MCL-1 stability and failed to activate BAX in response to ABT-199. The ABT-199 acquired and inherent resistant cells were sensitized to treatment with ABT-199 by inhibitors of the PI3K, AKT, and mTOR pathways, NVP-BEZ235 and GS-1101. NVP-BEZ235, a dual inhibitor of p-AKT and mTOR, reduced MCL-1 levels causing BIM release from MCL-1 and BCL-xL, thus leading to cell death by BAX activation. The PI3K? inhibitor GS-1101 (idelalisib) downregulated MCL-1 and sensitized ABT199-R cells through AKT-mediated BAX activation. A genetic approach, through siRNA-mediated down-regulation of AKT, MCL-1, and BCL-xL, significantly decreased cell survival, demonstrating the importance of these cell survival factors for ABT-199 resistance. Our findings suggest a novel mechanism that modulates the expression and activity of pro-survival proteins to confer treatment resistance that could be exploited by a rational combination therapeutic regimen that could be effective for treating lymphoid malignancies. PMID:25590803

  14. Free radical-scavenging capacity, antioxidant activity and phenolic content of Pouzolzia zeylanica

    Directory of Open Access Journals (Sweden)

    PEIYUAN LI

    2011-05-01

    Full Text Available Pouzolzia zeylanica was extracted with different solvents (acetone, ethyl acetate and petroleum ether, using different protocols (cold-extraction and Soxhlet extraction. To evaluate the antiradical and antioxidant abilities of the extracts, four in vitro test systems were employed, i.e., DPPH, ABTS and hydroxyl radical scavenging assays and a reducing power assay. All extracts exhibited outstanding antioxidant activities that were superior to that of butylated hydroxytoluene. The ethyl acetate extracts exhibited the most significant antioxidant activities, and cold-extraction under stirring seemed to be the more efficacious method for acquiring the predominant antioxidants. Furthermore, the antioxidant activities and total phenolic (TP content of different extracts followed the same order, i.e., there is a good correlation between antioxidant activities and TP content. The results showed that these extracts, especially the ethyl acetate extracts, could be considered as natural antioxidants and may be useful for curing diseases arising from oxidative deterioration.

  15. Ellagic acid derivatives, ellagitannins, proanthocyanidins and other phenolics, vitamin C and antioxidant capacity of two powder products from camu-camu fruit (Myrciaria dubia).

    Science.gov (United States)

    Fracassetti, Daniela; Costa, Carlos; Moulay, Leila; Tomás-Barberán, Francisco A

    2013-08-15

    The aims of this study were the evaluation of polyphenols and vitamin C content, and antioxidant capacity of dehydrated pulp powder and the dried flour obtained from the skin and seeds residue remaining after pulp preparation from camu-camu (Myrciaria dudia). Fifty-three different phenolics were characterised by HPLC-DAD-ESI-MS-MS and UPLC-HR-QTOF-MS-MS. The phenolic content of camu-camu flour was higher than that of the pulp powder (4007.95 mg/100 g vs. 48.54 mg/100 g). In both products the flavonol myricetin and conjugates, ellagic acid and conjugates and ellagitannins were detected. Cyanidin 3-glucoside, and quercetin and its glycosides were only found in the pulp powder, while proanthocyanidins were only present in the flour (3.5 g/100 g, mean degree of polymerisation 3). The vitamin C content was lower in pulp powder (3.5%) than in the flour (9.1%). The radical-scavenging capacity of both powders was determined by the DPPH, ABTS and ORAC assays, and was higher for camu-camu flour as could be expected for its higher phenolics and vitamin C content. Comparative analyses with fresh camu-camu berries indicate that some transformations occur during processing. Analysis of fresh berries showed that ellagic acid derivatives and ellagitannins were mainly present in the seeds, while proanthocyanidins were present both in the seeds and skin. PMID:23561148

  16. Synthesis, molecular modeling and biological evaluation of novel 2-allyl amino 4-methyl sulfanyl butyric acid as ?-amylase and ?-glucosidase inhibitor

    Science.gov (United States)

    Balan, Kannan; Perumal, Perumal; Sundarabaalaji, Narayanan; Palvannan, Thayumanavan

    2015-02-01

    In the present study 2-allyl amino 4-methyl sulfanyl butyric acid (AMSB) was synthesized in good yield. AMSB was characterized by Fourier transforms infrared spectroscopy (FTIR), Nuclear magnetic resonance (NMR) (1H and 13C) and Liquid chromatography mass spectrometry (LCMS). The radical scavenging activity and reducing power assay of AMSB was assessed using 1-1-diphenyl 2-picryl hydrazyl (DPPH), 2,2?-azino-bis (3-ethyl benzothiazoline-6-sulfonic acid) (ABTS) and ferric ion reducing antioxidant power assay (FRAP) and was found to be 44.1, 34.71 and 41.7 ?g/ml respectively. The compound showed effective inhibition against ?-amylase and ?-glucosidase. AMSB was identified to be a reversible mixed noncompetitive inhibitor of ?-amylase and ?-glucosidase. The molecular docking study was carried out to evaluate the specific groove binding properties and affords valuable information of AMSB binding mode in the active site of ?-glucosidase the study may lead to the which leads to the rational design of new class of antidiabetic drugs targeting ?-glucosidase based on AMSB in near future.

  17. [Radical prostatectomy - pro laparoscopic].

    Science.gov (United States)

    Do, H M; Holze, S; Qazi, H; Dietel, A; Häfner, T; Liatsikos, E; Stolzenburg, J-U

    2012-05-01

    Recent publications have failed to demonstrate significant differences in perioperative oncological and functional outcomes between laparoscopic radical prostatectomy (LRPE) and R-LRPE. Reports suggesting better functional results, in particular better potency rates for R-LRPE, are rare. However, to date no large prospective, randomized, multicenter studies have compared the two methods. With an experienced operator both methods produce comparably good results. The monopoly of the intuitive system with extremely high cost of purchase and maintenance are the major disadvantages of R-LRPE. PMID:22526174

  18. Characteristics of the OH radical scavenging activity of tea catechins

    International Nuclear Information System (INIS)

    Reaction rate constants of (-)-epigallocatechin gallate (EGCG) and (+)-catechin with the hydroxyl radical (·OH) were measured using the rapid flow ESR method. The rate constant of EGCG was larger twice than that of the pyrogallol or gallic acid, they are the model compounds of the B ring of EGCG. It was explained by the quantum-chemical calculation of the bond dissociation energy (BDE) of the phenolic hydroxyl group (?-OH) and the spin densities of EGCG radical. The energy of the EGCG radical was lowered by the hydrogen bonding between the radical part on the B ring and the hydroxyl group on the gallate group, leading to the lowering of BDE. Linear relationship between the relative activation energy and BDE of all the polyphenols measured was observed (Evans-Polanyi equation), showing that the reaction with ·OH occurs in the same manner. (author)

  19. Bursectomy at radical gastrectomy.

    Science.gov (United States)

    Kayaalp, Cuneyt

    2015-10-27

    Radical gastrectomy with extended lymph node dissection and prophylactic resection of the omentum, peritoneum over the posterior lesser sac, pancreas and/or spleen was advocated at the beginning of the 1960s in Japan. In time, prophylactic routine resections of the pancreas and/or spleen were abandoned because of the high incidence of postoperative complications. However, omentectomy and bursectomy continued to be standard parts of traditional radical gastrectomy. The bursa omentalis was thought to be a natural barrier against invasion of cancer cells into the posterior part of the stomach. The theoretical rationale for bursectomy was to reduce the risk of peritoneal recurrences by eliminating the peritoneum over the lesser sac, which might include free cancer cells or micrometastases. Over time, the indication for bursectomy was gradually reduced to only patients with posterior gastric wall tumors penetrating the serosa. Despite its theoretical advantages, its benefit for recurrence or survival has not been proven yet. The possible reasons for this inconsistency are discussed in this review. In conclusion, the value of bursectomy in the treatment of gastric cancer is still under debate and large-scale randomized studies are necessary. Until clear evidence of patient benefit is obtained, its routine use cannot be recommended. PMID:26523213

  20. Model studies in cytochrome P-450-mediated toxicity of halogenated compounds: radical processes involving iron porphyrins.

    OpenAIRE

    Brault, D

    1985-01-01

    Haloalkane toxicity originates from attack on biological targets by reactive intermediates derived from haloalkane metabolism by a hemoprotein, cytochrome P-450. Carbon-centered radicals and their peroxyl derivatives are most likely involved. The reactions of iron porphyrin--a model for cytochrome P-450--with various carbon-centered and peroxyl radicals generated by pulse radiolysis are examined. Competition between iron porphyrin and unsaturated fatty acids for attack by peroxyl radicals is ...

  1. Antioxidant and Free Radical Scavenging Properties of Twelve Traditionally Used Indian Medicinal Plants

    OpenAIRE

    AQIL, Farrukh; Ahmad, Iqbal; MEHMOOD, Zafar

    2006-01-01

    The methanolic crude extracts of 12 traditionally used Indian medicinal plants were screened for their antioxidant and free radical scavenging properties using a-tocopherol and butylated hydroxy toluene (BHT) as standard antioxidants. Antioxidant activity was measured by ferric thiocyanate (FTC) assay and compared with the thiobarbituric acid (TBA) method. Free radical scavenging activity was evaluated using diphenyl picryl hydrazyl (DPPH) radicals. The overall antioxidant activity of Lawsoni...

  2. Screening of Various Botanical Extracts for Antioxidant Activity Using DPPH Free Radical Method

    OpenAIRE

    Waqas, Muhammad Khurram; Saqib, Najam-us; Rashid, Saeed-ur; Shah, Pervaiz Akhtar; Akhtar, Naveed; Murtaza, Ghulam

    2013-01-01

    Aiming at the exploration of herbal use by society, crude extracts of the seeds of some commonly used medicinal plants (Vitis vinifera, Tamarindus indica and Glycin max) were screened for their free radical scavenging properties using ascorbic acid as standard antioxidant. Free radical scavenging activity was evaluated using 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical. The overall antioxidant activity of grape seeds (Vitis vinifera) was the strongest, followed in descending order by soy...

  3. Antimutagenic and free radical scavenger effects of leaf extracts from Accacia salicina

    Directory of Open Access Journals (Sweden)

    Boubaker Jihed

    2011-12-01

    Full Text Available Abstract Background Three extracts were prepared from the leaves of Accacia salicina; ethyl acetate (EA, chloroform (Chl and petroleum ether (PE extracts and was designed to examine antimutagenic, antioxidant potenty and oxidative DNA damage protecting activity. Methods Antioxidant activity of A. salicina extracts was determined by the ability of each extract to protect against plasmid DNA strand scission induced by hydroxyl radicals. An assay for the ability of these extracts to prevent mutations induced by various oxidants in Salmonella typhimurium TA102 and TA 104 strains was conducted. In addition, nonenzymatic methods were employed to evaluate anti-oxidative effects of tested extracts. Results These extracts from leaf parts of A. salicina showed no mutagenicity either with or without the metabolic enzyme preparation (S9. The highest protections against methylmethanesulfonate induced mutagenicity were observed with all extracts and especially chloroform extract. This extract exhibited the highest inhibitiory level of the Ames response induced by the indirect mutagen 2- aminoanthracene. All extracts exhibited the highest ability to protect plasmid DNA against hydroxyl radicals induced DNA damages. The ethyl acetate (EA and chloroform (Chl extracts showed with high TEAC values radical of 0.95 and 0.81 mM respectively, against the ABTS.+. Conclusion The present study revealed the antimutagenic and antioxidant potenty of plant extract from Accacia salicina leaves.

  4. Spectroscopic characterization of radicals and radical pairs in fruit fly cryptochrome - protonated and nonprotonated flavin radical-states.

    Science.gov (United States)

    Paulus, Bernd; Bajzath, Csaba; Melin, Frédéric; Heidinger, Lorenz; Kromm, Viktoria; Herkersdorf, Christoph; Benz, Ulrike; Mann, Lisa; Stehle, Patricia; Hellwig, Petra; Weber, Stefan; Schleicher, Erik

    2015-08-01

    Drosophila melanogaster cryptochrome is one of the model proteins for animal blue-light photoreceptors. Using time-resolved and steady-state optical spectroscopy, we studied the mechanism of light-induced radical-pair formation and decay, and the photoreduction of the FAD cofactor. Exact kinetics on a microsecond to minutes timescale could be extracted for the wild-type protein using global analysis. The wild-type exhibits a fast photoreduction reaction from the oxidized FAD to the FAD(•-) state with a very positive midpoint potential of ~ +125 mV, although no further reduction could be observed. We could also demonstrate that the terminal tryptophan of the conserved triad, W342, is directly involved in electron transfer; however, photoreduction could not be completely inhibited in a W342F mutant. The investigation of another mutation close to the FAD cofactor, C416N, rather unexpectedly reveals accumulation of a protonated flavin radical on a timescale of several seconds. The obtained data are critically discussed with the ones obtained from another protein, Escherichia coli photolyase, and we conclude that the amino acid opposite N(5) of the isoalloxazine moiety of FAD is able to (de)stabilize the protonated FAD radical but not to significantly modulate the kinetics of any light-inducted reactions. PMID:25879256

  5. The amorphous solid dispersion of the poorly soluble ABT-102 forms nano/microparticulate structures in aqueous medium: impact on solubility

    Directory of Open Access Journals (Sweden)

    Frank KJ

    2012-11-01

    Full Text Available Kerstin J Frank,1,3 Ulrich Westedt,2 Karin M Rosenblatt,2 Peter Hölig,2 Jörg Rosenberg,2 Markus Mägerlein,2 Gert Fricker,3 Martin Brandl11Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Odense, Denmark; 2Abbott GmbH and Co. KG, Ludwigshafen, Germany; 3Department of Pharmaceutical Technology, University of Heidelberg, Heidelberg, GermanyAbstract: Amorphous solid dispersions (ASDs are a promising formulation approach for poorly soluble active pharmaceutical ingredients (APIs, because they ideally enhance both dissolution rate and solubility. However, the mechanism behind this is not understood in detail. In the present study, we investigated the supramolecular and the nano/microparticulate structures that emerge spontaneously upon dispersion of an ASD in aqueous medium and elucidated their influence on solubility. The ASD, prepared by hot melt extrusion, contained the poorly soluble ABT-102 (solubility in buffer, 0.05 µg/mL, a hydrophilic polymer, and three surfactants. The apparent solubility of ABT-102 from the ASD-formulation was enhanced up to 200 times in comparison to crystalline ABT-102. At the same time, the molecular solubility, as assessed by inverse equilibrium dialysis, was enhanced two times. Asymmetrical flow field-flow fractionation in combination with a multiangle light-scattering detector, an ultraviolet detector, and a refractometer enabled us to separate and identify the various supramolecular assemblies that were present in the aqueous dispersions of the API-free ASD (placebo and of binary/ternary blends of the ingredients. Thus, the supramolecular assemblies with a molar mass between 20,000 and 90,000 could be assigned to the polyvinylpyrrolidone/vinyl acetate 64, while two other kinds of assemblies were assigned to different surfactant assemblies (micelles. The amount of ABT-102 remaining associated with each of the assemblies upon fractionation was quantified offline with high-performance liquid chromatography–ultraviolet-visible. The polymeric and the micellar fraction contributed to the substantial increase in apparent solubility of ABT-102. Furthermore, a microparticulate fraction was isolated by centrifugation and analyzed by scanning electron microscopy, X-ray scattering, and infrared spectroscopy. The microparticles were found to be amorphous and to contain two of the surfactants besides ABT-102 as the main component. The amorphous microparticles are assumed to be the origin of the observed increase in molecular solubility ("true" supersaturation.Keywords: solid dispersion, AFlFFF, micelles, solubility, supersaturation

  6. Empirical antibiotic therapy (ABT) of lower respiratory tract infections (LRTI) in the elderly: application of artificial neural network (ANN). Preliminary results.

    Science.gov (United States)

    Gueli, Nicolò; Martinez, Andrea; Verrusio, Walter; Linguanti, Adele; Passador, Paola; Martinelli, Valentina; Longo, Giovanni; Marigliano, Benedetta; Cacciafesta, Flaminia; Cacciafesta, Mauro

    2012-01-01

    LRTI are among the most common diseases in developed countries, including chronic obstructive pulmonary disease (COPD), one of the most frequent conditions. Their treatment in general practice is often unsuccessful and this increases hospital admissions. We know, bacterial infections in the elderly show a higher morbidity and mortality, either for more severe symptoms, than in younger adults, or because the causing agent often remains unknown. The need for a quick initiation of ABT often requires to chose on empirical grounds. To date there are no official guidelines for empirical ABT of COPD exacerbations, but only heterogeneous and often conflicting recommendations exist. The aim of our study was to identify a tool to guide the choice of the most effective empirical ABT when symptoms are acute and bacteriological tests cannot be performed. We used an ANN to study 117 patients aged between 55 and 97 years (mean 81.5 ± 8.7 years) (± S.D.), admitted with a diagnosis of pneumonia, COPD exacerbation or pneumonia with respiratory failure. We registered symptoms at onset and some individual variables such as age, sex, risk factors, comorbidity, current drug therapies. Then the ANN was applied to choose ABT in 20 patients versus 20 subjects whose therapy was chosen by the physicians, comparing these groups for therapy's efficacy, mean durations of therapy and hospitalization (H). In the learning phase, the ANN could predict the resolution index 99.05% of the time (i.e., 104 times) with a ± S.D. = 0.23. After the training, during the test phase, the network predicted the resolution index 91.67% of the time (i.e., 11 times) with a ± S.D. = 0.54, thus proving the validity of the relations identified during the learning phase. Preliminary results of the application of our tool, show the ANN allowed us to greatly reduce the duration of the ABT and subsequently of the H. Based on preliminary results, we assume that the use of ANN can make a valuable contribution in the choice of empirical ABT in the course of acute lung diseases in elderly. PMID:21978414

  7. Radical Scavenging Efficacy of Thiol Capped Silver Nanoparticles

    Indian Academy of Sciences (India)

    Kumudini Chandraker; Sandeep Kumar Vaishanav; Rekha Nagwanshi; Manmohan L Satnami

    2015-12-01

    Radical scavenging efficacy of L-cysteine (L-Cys), glutathione (GSH) and thioctic acid (TA) in the presence of silver nanoparticles (AgNPs) were determined by 1,1-diphenyl 2-picryl hydrazil (DPPH), nitric oxide (NO) and hydroxyl (OH) radicals as spectrophotometric assay. The hydrogen peroxide (H2O2) scavenging efficacy has been determined by titration method. Ascorbic acid has been used as standard for all radical scavenging efficacies. In general, antioxidant activity decreases in the presence of AgNPs. The covalent interactions of thiols (-SH) were found to be a key factor for the decreases in scavenging activity. The effect of thiol concentrations has been discussed. The size and shape of the nanoparticles and AgNP-SR interactions have been characterized through Transmission Electron Microscopy (TEM) and Fourier Transform Infrared (FTIR) spectroscopy, respectively.

  8. Hydroxyl radical induced degradation of salicylates in aerated aqueous solution

    Science.gov (United States)

    Szabó, László; Tóth, Tünde; Homlok, Renáta; Rácz, Gergely; Takács, Erzsébet; Wojnárovits, László

    2014-04-01

    Ionizing radiation induced degradation of acetylsalicylic acid, its hydrolysis product salicylic acid and a salicylic acid derivative 5-sulpho-salicylic acid, was investigated in dilute aqueous solutions by UV-vis spectrophotometry, HPLC separation and diode-array or MS/MS detection, chemical oxygen demand, total organic carbon content and by Vibrio fischeri toxicity measurements. Hydroxyl radicals were shown to degrade these molecules readily, and first degradation products were hydroxylated derivatives in all cases. Due to the by-products, among them hydrogen peroxide, the toxicity first increased and then decreased with the absorbed dose. With prolonged irradiation complete mineralization was achieved.

  9. New knowledge on the antiglycoxidative mechanism of chlorogenic acid.

    Science.gov (United States)

    Fernandez-Gomez, Beatriz; Ullate, Monica; Picariello, Gianluca; Ferranti, Pasquale; Mesa, Maria Dolores; del Castillo, Maria Dolores

    2015-06-01

    The role of chlorogenic acid (CGA) in the formation of advanced glycation end-products (AGEs) (glycoxidation reaction) was studied. Model systems composed of bovine serum albumin (BSA) (1 mg mL(-1)) and methylglyoxal (5 mM) under mimicked physiological conditions (pH 7.4, 37 °C) were used to evaluate the antiglycoxidative effect of CGA (10 mM). The stability of CGA under reaction conditions was assayed by HPLC and MALDI-TOF MS. The glycoxidation reaction was estimated by analysis of free amino groups by the OPA assay, spectral analysis of fluorescent AGEs and total AGEs by ELISA, and colour formation by absorbance at 420 nm. Structural changes in protein were evaluated by analysis of phenol bound to the protein backbone using the Folin reaction, UV-Vis spectral analysis and MALDI-TOF-MS, while changes in protein function were measured by determining the antioxidant capacity using the ABTS radical cation decolourisation assay. CGA was isomerised and oxidised under our experimental conditions. Evidence of binding between BSA and multiple CGA and/or its derivative molecules (isomers and oxidation products) was found. CGA inhibited (p < 0.05) the formation of fluorescent and total AGEs at 72 h of reaction by 91.2 and 69.7%, respectively. The binding of phenols to BSA significantly increased (p < 0.001) its antioxidant capacity. Correlations between free amino group content, phenol bound to protein and antioxidant capacity were found. Results indicate that CGA simultaneously inhibits the formation of potentially harmful compounds (AGEs) and promotes the generation of neoantioxidant structures. PMID:26037734

  10. Energetics of reactions of O-sub(aq) and of O--transfer reactions between radicals

    International Nuclear Information System (INIS)

    Free energies of formation of various free radicals such as O-sub(aq), CO-sub(3aq), CO-sub(2aq), and X-sub(2aq) (X = Cl, Br and I) have been derived and used to calculate standard potentials of radicals and free energies of their reactions. O-sub(aq) is an oxidizing radical with a potential E0(O-sub(aq) + H2O/2OH-sub(aq)) = 1.9 V, i.e. electron pick-up is accompanied by simultaneous breakage of a water molecule in the hydration shell. Water is also decomposed in the reaction between two O-sub(aq) radicals, HO2- + OH- being much more probable products than O + 2OH-. O-sub(aq) is almost as strong a hydrogen atom abstracting radical as the hydroxyl radical. CO-sub(3aq) can donate O- to various radicals. These reactions may occur directly or via a complex that hydrolyses. O--transfer occurs in competition with electron transfer from the substrate radical to CO-sub(3aq). Transfer of O- from CO-sub(2aq) or HCOsub(3aq) radicals to form carbon monoxide is strongly exoergic. The formation of CO in the radiolysis of acid solutions of formate is explained by O--transfer between the intermediate radicals. O--transfer from a radical to an electrode is also considered. (author)

  11. Borra de café colombiano (Coffea arabica) como fuente potencial de sustancias con capacidad antirradicales libres in vitro / Colombian spent coffee grounds (Coffea arabica) as a potential source of substances with free radicals capacity in vitro

    Scientific Electronic Library Online (English)

    Miguel A, Puertas-Mejía; Paola, Villegas-Guzmán; Benjamín, Alberto Rojano.

    2013-09-01

    Full Text Available Introducción: Coffea arabica L., además de su importancia comercial, también se considera una planta medicinal, porque presenta propiedades biológicas diversas, pero por su comercialización como bebida genera muchos subproductos. La borra es uno de estos, que se obtiene por la preparación de la bebi [...] da, contiene una concentración significativa de compuestos polifenólicos y, por tanto, la recuperación de estas sustancias a partir de un residuo sin valor, sería potencialmente útil para la industria farmacéutica y alimentaria. Objetivos: recuperar compuestos fenólicos a partir de la borra de café y darle un valor agregado a un residuo de origen vegetal, como fuente de componentes con capacidad antirradicales libres in vitro. Métodos: la borra de café previamente secada se sometió a extracciones sólido-líquido usando diferentes sistemas de solventes. Se evaluaron las propiedades antioxidantes in vitro usando los métodos del catión radical del ácido 2,2´-azino-bis (3-etilbenzotiazoline-6-sulfónico) y del radical 1,1-difenil-2-picrilhidracilo. Se usó cromatografía líquida de alta resolución acoplada a espectrometría de masas para la caracterizaron de los principales componentes. Resultados: todos los extractos obtenidos mostraron buena capacidad antioxidante, con el extracto de etanol:agua como el mejor, seguido del extracto de metanol acidulado. Sin embargo, la capacidad antioxidante de la fracción en diclorometano del extracto etanol:agua resultó menor que la presentada por la taza de café. Se identificaron los ácidos clorogénico, isoclorogénico y feruloilquínico como los principales componentes de la borra de café. Conclusiones: todos los extractos presentaron buena capacidad protectora contra radicales libres. La borra de café, considerada un desecho obtenido del procesamiento industrial, se puede convertir en materia prima para la recuperación de sustancias antioxidantes; lo cual genera grandes expectativas sobre su posible uso en la industria farmacéutica y alimentaria, y le da al café un valor agregado importante. Abstract in english Introduction: besides its commercial importance, Coffee arabica L. is also considered a medicinal plant due to its various biological properties, but its marketing produces a large amount of residues. Spent coffee grounds are one of these residues, which are obtained after the preparation of the dri [...] nk and contain a significant concentration of polyphenolic compounds. Therefore, the recovery of these substances costless residual will be potentially useful for food and pharmaceutical industry. Objectives: to recover polyphenolic compounds from spent coffee grounds and to give an added value to a vegetable waste as a source of substances with free radicals capacity in vitro. Methods: dehydrated spent coffee grounds were subjected to solid-liquid extraction using different solvent systems. Antioxidant properties were evaluated in vitro using the radical monocation 2,2´-azino-bis-3-ethylbenzothiazoline-6-sulfonic acid (ABTS) and the stable free radical 2-2-diphenyl-1-picrylhydrazyl (DPPH). Liquid chromatography coupled to mass spectrometry was applied to characterize the main compounds. Results: all the extracts obtained showed a good antioxidant capacity with ethanol-water extract, followed by acidulated methanol extract. However, the antioxidant capacity of the ethanol-water extract was lower than coffee beverage. Chlorogenic, isochlorogenic and feruloylquinic acids were identified as the main compounds present in spent coffee grounds. Conclusions: all extracts showed a significant protection effect against free radicals; spent coffee ground, which is considered an undesirable solid waste from industrial processing, could be an add-value raw material in the recovery of antioxidant substances which generates great expectations about its possible use in the pharmaceutical and food industry and gives coffee an important added value.

  12. Free Radical Scavenging and Antioxidant Activities of Silymarin Components

    Directory of Open Access Journals (Sweden)

    Kevin P. Anthony

    2013-12-01

    Full Text Available Silymarin is an over the counter food supplement that is sold as a liver enhancement and liver protection preparation. It is a major constituent of the seeds of Silybum marianum which is composed of a mixture of seven major components and several minor compounds. The seven major components: taxifolin, silychristin, silydianin, silybin A, silybin B, iso-silybin A and iso-silybin B were isolated and purified from the crude mixture of silymarin using preparative high performance liquid chromatography to determine which were the most effective for liver protection. Free radical scavenging, hydroxyl radical antioxidant capacity, oxygen radical antioxidant capacity, trolox-equivalent antioxidant capacity and total antioxidant capacity antioxidant activities were determined for each of the individual purified components as well as the crude silymarin mixture. Taxifolin was the most effective component for scavenging free radicals in the DPPH assay with an EC50 of 32 µM far more effective than all other components which showed EC50 ranging from 115 to 855 µM. Taxifolin was also found to be the most effective antioxidant in the oxygen radical antioxidant capacity (ORAC assay with a trolox equivalent of 2.43 and the second most effective in the hydroxyl radical antioxidant capacity (HORAC assay with a gallic acid equivalent of 0.57. Other antioxidants assays did not show significant differences between samples.

  13. Anti-oxidation and scavenging effects of some extracts from Chinese medicines on free radicals

    International Nuclear Information System (INIS)

    The inhibiting effects of Chinonin, Quercetin and Tannic Acid on the lipid oxidation induced by radiation exposure were investigated by means of a modified TBA spectrophotometry. The scavenging effects on free radicals caused by ?-irradiation exposure of the three active principles were observed by technique of ESR. The results showed that anti-oxidation effects of Chinonin and Quercetin were better than that of Tannic Acid, while the scavenging effects of the three active principles on free radicals were similar

  14. The role of the acidity of N-heteroaryl sulfonamides as inhibitors of bcl-2 family protein-protein interactions.

    Science.gov (United States)

    Touré, B Barry; Miller-Moslin, Karen; Yusuff, Naeem; Perez, Lawrence; Doré, Michael; Joud, Carol; Michael, Walter; DiPietro, Lucian; van der Plas, Simon; McEwan, Michael; Lenoir, Francois; Hoe, Madelene; Karki, Rajesh; Springer, Clayton; Sullivan, John; Levine, Kymberly; Fiorilla, Catherine; Xie, Xiaoling; Kulathila, Raviraj; Herlihy, Kara; Porter, Dale; Visser, Michael

    2013-02-14

    Overexpression of the antiapoptotic members of the Bcl-2 family of proteins is commonly associated with cancer cell survival and resistance to chemotherapeutics. Here, we describe the structure-based optimization of a series of N-heteroaryl sulfonamides that demonstrate potent mechanism-based cell death. The role of the acidic nature of the sulfonamide moiety as it relates to potency, solubility, and clearance is examined. This has led to the discovery of novel heterocyclic replacements for the acylsulfonamide core of ABT-737 and ABT-263. PMID:24900652

  15. Poly(ADP-ribose) polymerase inhibitor ABT-888 potentiates the cytotoxic activity of temozolomide in leukemia cells: influence of mismatch repair status and O6-methylguanine-DNA methyltransferase activity

    OpenAIRE

    Terzah M. Horton; Jenkins, Gaye; Pati, Debananda; Zhang, Linna; Dolan, M. Eileen; Ribes-Zamora, Albert; Bertuch, Alison A; Blaney, Susan M; Delaney, Shannon L.; Hegde, Madhuri; Berg, Stacey L.

    2009-01-01

    The poly(ADP-ribose) polymerase (PARP) inhibitor ABT-888 potentiates the antitumor activity of temozolomide (TMZ). TMZ resistance results from increased O6-methylguanine-DNA methyltransferase (MGMT) activity and from mismatch repair (MMR) system mutations. We evaluated the relative importance of MGMT activity, MMR deficiency, nonhomologous end joining (NHEJ), and PARP activity in ABT-888 potentiation of TMZ. MMR-proficient and MMR-deficient leukemia cells with varying MGMT activity, as well a...

  16. Acetate peroxyl radicals, sup(.)O2CH2CO2-

    International Nuclear Information System (INIS)

    Hydroxyl radicals from the radiolysis of N2O/O2 (4:1 v/v)-saturated aqueous solutions have been reacted with acetate ions (10-2 M). As measured by pulse radiolysis, the resulting sup(.)CH2CO2- radicals react with oxygen yielding the corresponding peroxyl radicals, sup(.)O2CH2CO2- (k = 1.7 x 109 M-1s-1). These peroxyl radicals decay bimolecularly (2k = 1.5 x 108 M-1s-1) giving rise to the products (G values in brackets) glyoxylic acid (2.7), glycolic acid (0.7), formaldehyde (1.4), carbon dioxide (1.4), organic hydroperoxide (0.7) and hydrogen peroxide (2.5). Oxygen is consumed with a G value of 5.3. Aided by data from pulse radiolysis it is concluded that the intermediate tetroxide formed upon the bimolecular decay breaks down by various routes to yield: (i) hydrogen peroxide and two molecules of glyoxylic acid (ca. 27%); (ii) oxygen, glycolic acid and glyoxylic acid (ca. 25%); (iii) hydrogen peroxide and two molecules of formaldehyde, carbon dioxide and OH- (25%). These reactions do not involve free radicals as intermediates; (iv) There is some O2- (G proportional 0.5) formed in the decay of the peroxyl radicals, which is attributed to the decay of intermediate oxyl radicals (tetroxide -> O2 + 2 sup(.)OCH2CO2-) by 1,2-H shift, oxygen addition and HO2sup(.) elimination, a reaction sequence which gives rise to glyoxylic acid (10%); (v) The reaction of O2- with the organic peroxyl radical yields the hydroperoxide (13%). Reaction (iii) is a novel peroxyl radical reaction. (orig.)

  17. Guest Editorial: Processes of Radicalization and De-Radicalization

    Directory of Open Access Journals (Sweden)

    Donatella Della Porta

    2012-05-01

    Full Text Available The study of radicalization and de-radicalization, understood as processes leading towards the increased or decreased use of political violence, is central to the question of how political violence emerges, how it can be prevented, and how it can be contained. The focus section of this issue of the International Journal of Conflict and Violence addresses radicalization and de-radicalization, seeking to develop a more comprehensive understanding of the processes, dynamics, and mechanisms involved and taking an interdisciplinary approach to overcome the fragmentation into separate disciplines and focus areas. Contributions by Pénélope Larzillière, Felix Heiduk, Bill Kissane, Hank Johnston, Christian Davenport and Cyanne Loyle, Veronique Dudouet, and Lasse Lindekilde address repressive settings, legitimacy, institutional aspects, organizational outcomes, and dynamics in Europe, Asia, Africa, and North and South America.

  18. Formation of bromate in sulfate radical based oxidation: mechanistic aspects and suppression by dissolved organic matter.

    Science.gov (United States)

    Lutze, Holger V; Bakkour, Rani; Kerlin, Nils; von Sonntag, Clemens; Schmidt, Torsten C

    2014-04-15

    Sulfate radical based oxidation is discussed being a potential alternative to hydroxyl radical based oxidation for pollutant control in water treatment. However, formation of undesired by-products, has hardly been addressed in the current literature, which is an issue in other oxidative processes such as bromate formation in ozonation of bromide containing water (US-EPA and EU drinking water standard of bromate: 10 ?g L(-1)). Sulfate radicals react fast with bromide (k = 3.5 × 10(9) M(-1) s(-1)) which could also yield bromate as final product. The mechanism of bromate formation in aqueous solution in presence of sulfate radicals has been investigated in the present paper. Further experiments were performed in presence of humic acids and in surface water for investigating the relevance of bromate formation in context of pollutant control. The formation of bromate by sulfate radicals resembles the well described mechanism of the hydroxyl radical based bromate formation. In both cases hypobromous acid is a requisite intermediate. In presence of organic matter formation of bromate is effectively suppressed. That can be explained by formation of superoxide formed in the reaction of sulfate radicals plus aromatic moieties of organic matter, since superoxide reduces hypobromous acid yielding bromine atoms and bromide. Hence formation of bromate can be neglected in sulfate radical based oxidation at typical conditions of water treatment. PMID:24565691

  19. In Vitro Antioxidant and free Radical Scavenging activity of the Ethanolic extract of Aesculus hippocastanum

    Directory of Open Access Journals (Sweden)

    R. V. Geetha

    2013-09-01

    Full Text Available The aim of the present study was to evaluate the antioxidant and free radical scavenging activity of the ethanolic extract of Aesculus hippocastanum (Horse chest nut. Highly reactive free radicals and oxygen species are present in biological systems from a wide variety of sources. These free radicals may oxidize nucleic acids, proteins, lipids or DNA and can initiate degenerative disease. Antioxidants play an important role in protecting cellular damage caused by reactive oxygen species. Plants containing phenolic compounds have been reported to possess strong antioxidant properties. Antioxidant potential of the ethanolic extract of Aesculus hippocastanum was studied using different in vitro free radical scavenging models like DPPH and Hydrogen Peroxide. The DPPH results have been compared with the standard Ascorbic acid .The extract showed good dose dependent free radical scavenging property in both the models used in this study.

  20. Formation and reactions of radical cations of substituted benzenes in aqueous media

    International Nuclear Information System (INIS)

    Radical cations of anisole, methylated benzenes, ethylbenzene, isopropylbenzene, tert-butylbenzene and N,N-dimethylaniline were studied in aqueous media by pulse radiolytic technique. Absorption spectra and reaction kinetics of the radical cations were recorded. The radical cations are formed from the corresponding OH adducts by the elimination of OH-, either by a simple dissociation or by an acid catalyzed reaction. The rate constants of the formation of the radical cations and their reactions with water, OH- and Fe2+, or the reaction of a proton loss, were measured. The rate constants for the reaction with water and OH-, together with the rate constants for the dissociation of the OH adducts, are correlated with the ionization potential of the parent compound. These correlations offer a possibility of predicting the acid-base properties of radical cations of substituted benzenes, or the estimation of their ionization potential. (author)

  1. Effect of some naturally occurring iron ion chelators on the formation of radicals in the reaction mixtures of rat liver microsomes with ADP, Fe3+ and NADPH

    OpenAIRE

    Minakata, Katsuyuki; FUKUSHIMA, KAZUAKI; Nakamura, Masayuki; Iwahashi, Hideo

    2011-01-01

    In order to clarify the mechanism by polyphenols of protective effects against oxidative damage or by quinolinic acid of its neurotoxic and inflammatory actions, effects of polyphenols or quinolinic acid on the radical formation were examined. The ESR measurements showed that some polyphenols such as caffeic acid, catechol, gallic acid, D-(+)-catechin, L-dopa, chlorogenic acid and L-noradrenaline inhibited the formation of radicals in the reaction mixture of rat liver microsomes with ADP, Fe3...

  2. Propargyl radical chemistry: renaissance instigated by metal coordination.

    Science.gov (United States)

    Melikyan, Gagik G

    2015-04-21

    Over the last two decades, radical chemistry of propargyl systems was developed into a potent synthetic field providing access to classes of organic compounds that are otherwise hardly accessible. The levels of diastereoselection thus achieved (up to 100%) are unprecedented for free propargyl radicals, as well as for organic radicals ?-bonded to transition metals. These advances were enabled by the coordination of the triple bond to a Co2(CO)6 core that precluded an acetylene-allene rearrangement, stabilized requisite propargyl cations, created conformational constraints at the carbon-carbon bond formation site, configurationally altered the acetylenic moiety allowing for 1,3-steric induction upon the newly formed stereocenters, increased bulkiness of propargyl triads thus controlling the spatial orientation of converging radicals, and allowed for ?-to-? projection of the reaction site and alteration of the transiency of radical intermediates. In the course of these studies, a number of popular "beliefs" were proven to be untrue. First, cobalt-complexed propargyl cations, which have long been considered to be thermally labile species, were engaged in synthetically meaningful transformation at temperatures as high as 147 °C. Second, in radical dimerization reactions, higher reaction temperatures did not adversely impact the yields and levels of d,l-diastereoselectivity. Third, ?-bonded organometallic radicals, deemed unruly, were effectively controlled with complementary mechanistic tools, thus achieving the highest levels of stereoselectivity (up to 100%) in inter- and intramolecular reactions. Fourth, meso stereoisomers, being thermally labile and kinetically disfavored, were discovered to be major products in intramolecular cyclizations induced by cobaltocene. Fifth, propargyl cations were synthesized in the absence of strong acids, thus increasing the functional tolerance and achieving a long sought after compatibility with acid-sensitive functionalities. A concept of sequestered propargyl radicals was introduced to explain disparity in diastereoselectivity data: heterogeneous reducing agents allegedly produce "free" radicals, while homogeneous reductants generate "sequestered" radicals associated with reductant-derived oxidized species. Among mechanistic tools, a 1,3-steric induction was found to be most efficient for controlling the stereoselectivity of radical reactions (up to 100% d,l). In intramolecular reactions, a d,l-to-meso reversal of stereoselectivity was discovered with zinc being replaced with cobaltocene as a reductant. Among efficient tools for controlling the stereoselectivity in intramolecular cyclizations is a rigidity of the carbon tether that provides for an exclusive formation of d,l-diastereomers. Two novel reactions that belong to a new field of unorthodox organometallic radical chemistry were discovered: the spontaneous conversion of cobalt-complexed propargyl cations to radicals and the THF-mediated process wherein a THF molecule assumes a new role of an initiator in radical reactions. A multistep mechanism involves a THF-induced alteration of propargyl cations that facilitates a redox process between metal clusters. Novel stereoselective methods provide access to topologically and functionally diverse 3,4-diaryl and 3,4-dialkyl-1,5-alkadiynes, 3,4-disubstituted 1,5-cycloalkadiynes (C8-C12), 3,4-dialkoxy-1,5-(cyclo)alkadiynes, and 3,7-diene-1,9-alkadiynes, which can be used in targeted syntheses of organic assemblies of relevance to medicinal chemistry, materials science, and natural product syntheses. Novel mechanistic tools and methodologies for controlling stereoselectivity in radical reactions can be expanded toward new types of ?-bonded unsaturated units (dienes, arenes, diynes, and enynes) and transition metals other than cobalt (Fe, Cr, Mo, W, and Mn). PMID:25746443

  3. Evaluation of Free Radical Scavenging Activity of Hydroethanolic Extract of Bacopa monnieri Through DPPH Assay

    Directory of Open Access Journals (Sweden)

    DISHA PANT

    2015-05-01

    Full Text Available The antioxidant potential of Bacopa monnieri in vitro through DPPH free radical scavenging assay, was evaluated using ascorbic acid as standard. There was a concentration dependent increase in percentage inhibition of DPPH free radical by ascorbic acid and hydroethanolic extract of Bacopa monnieri. The IC50 of the extract was found to be 28µg/ml and 270µg/ml for ascorbic acid and plant extract, with regression coefficients (r2 0.94 and 0.89, respectively. The hydroethanolic extract of Bacopa monnieri has a significant antioxidant potentiality comparable to a standard antioxidant like ascorbic acid.

  4. Kinetics and mechanism of protection of thymine from sulphate radical anion under anoxic conditions

    Indian Academy of Sciences (India)

    M Sudha Swaraga; M Adinarayana

    2003-04-01

    The rates of photooxidation of thymine in presence of peroxydisulphate (PDS) have been determined by measuring the absorbance of thymine at 264 nm spectrophotometrically. The rates and the quantum yields () of oxidation of thymine by sulphate radical anion have been determined in the presence of different concentrations of caffeic acid. Increase in [caffeic acid] is found to decrease the rate of oxidation of thymine suggesting that caffeic acid acts as an efficient scavenger of SO$^{\\bullet -}_4$ and protects thymine from it. Sulphate radical anion competes for thymine as well as for caffeic acid. The rate constant of sulphate radical anion with caffeic acid has been calculated to be $1.24 \\times 10^{10}$ dm3 mol-1 s-1. The quantum yields of photooxidation of thymine have been calculated from the rates of oxidation of thymine and the light intensity absorbed by PDS at 254 nm, the wavelength at which PDS is activated to sulphate radical anion. From the results of experimentally determined quantum yields ($\\phi_{\\text{exptl}}$) and the quantum yields calculated ($\\phi_{\\text{cl}}$) assuming caffeic acid acting only as a scavenger of SO$^{\\bullet -}_4$ radicals show that $\\phi_{\\text{exptl}}$ values are lower than $\\phi_{\\text{cl}}$ values. The $\\phi'$ values, which are experimentally found quantum yield values at each caffeic acid concentration and corrected for SO$^{\\bullet-}_4$ scavenging by caffeic acid, are also found to be greater than $\\phi_{\\text{exptl}}$ values. These observations suggest that the thymine radicals are repaired by caffeic acid in addition to scavenging of sulphate radical anions.

  5. Thermochemistry of alkyl free radicals

    International Nuclear Information System (INIS)

    The group additivity difference method is used to estimate the thermochemical properties (Cp0(T), 298 0298, ?fH0298) of alkyl free radicals from ethyl through the C6 radicals. Revised values are calculated for the alkyl radical groups. Recent experimental and theoretical work on hindered rotor barrier heights necessitating these revised calculations is discussed. All Cp's are also expressed in polynomial form, Cp0(T) = a1 + a2T + a3T2 + a4T3. Polynomial coefficients are given for the calculation of the equilibrium constants for formation of the radicals from the elements: nC + 1/2(2n + 1)H2 ? CnH2n+1. 35 refs., 12 tabs

  6. CONTINENT RADICAL PROSTATECTOMY

    Directory of Open Access Journals (Sweden)

    Yu. P. Sernyak

    2014-07-01

    Full Text Available Objective: to evaluate the impact of dissection of the dorsal venous complex without pre-ligation, suturing, or coagulation during radical prostatectomy (RPE in patients with localized prostate cancer (PC on the quality of surgery and the function of urinary retention.Subjects and methods. The data of 42 patients who had undergone posterior and anterior anatomical repair and vesicourethral anastomosis using a V-lock suture after prostatectomy were analyzed. All the patients were divided into 2 groups. Group 1 consisted of 22 patients in whom the dorsal venous complex was closed using a 3-0 vicryl suture before urethral dissection. Group 2 included 20 patients in whom the urethra was dissected without suturing the venous complex.Results. In group 1, complete urinary retention after catheter removal was noted in 9 (40.9 % and 15 (68 % patients within 24 hours and after 3 months, respectively. Following 12 months, two (9 % patients were observed to have partial mild urinary incontinence (as many as 2 pads per day. Group 2 patients showed complete urinary retention in 17 (85 % cases on the first day after catheter removal; all the patients retained urine 3 months later.Conclusion. In patients with localized PC, dissection of the dorsal venous complex without presuturing during laparoscopic RPE exerts a considerable impact on the preservation of urinary retention, namely 45% more of the patients reported complete urinary retention in early periods and 10 % more did this in later periods. At the same time, there was no statistically significant increase in intraoperative blood loss (p > 0.05, the number of positive edges, or biochemical recurrences.

  7. FREE RADICAL SCAVENGING, IMMUNOMODULATORY ACTIVITY AND CHEMICAL COMPOSITION OF LUFFA ACUTANGULA VAR: AMARA (CUCURBITACEAE) PERICARP

    Scientific Electronic Library Online (English)

    KALASKAR, MOHAN G.; SURANA, SANJAY J..

    2014-03-01

    Full Text Available The Luffa acutangula Var. amara (Cucurbitaceae) is climbing shrub; commonly known as wild ridge gourd. Its aerial parts are used traditionally in diverse health ailments. Four successive extracts of L. amara pericarp (LAP) were evaluated for antioxidant using in vitro for DPPH, ABTS, superoxides rad [...] ical, reducing power and phosphomolybdenum assay. The bioactive ethanol extract was evaluated for immunomodulatory activity by in vivo phagocytosis using carbon clearance and neutrophil adhesion test. The bioactive ethanolic extracts showed potent in vitro antioxidant ability, increased phagocytic index (0.028 ± 0.002), and increased the % neutrophil adhesion (24.63 ± 0.87%). Furthermore, the potent plant phenolics such as gallic acid and p-hydroxybenzoic acid were isolated and identified spectroscopically. The presence of these plant phenolics and like constituents would be responsible for their potent antioxidant and immunomodulatory activity.

  8. Radical prostatectomy. Results and indications

    International Nuclear Information System (INIS)

    Radical prostatectomy is the surgical curative treatment of localized prostate cancer. The survival is good in young patients (<70) with T2 N0M0 tumors and more than 10 year's life expectancy. Side-effects are urinary incontinence, impotence and anastomosis stricture. Quality of life should be considered as an important factor for the choice of the patient between radical prostatectomy, radiotherapy and follow-up. (author)

  9. Muon investigations of fullerenyl radicals

    International Nuclear Information System (INIS)

    Four of the five possible isomeric C70Mu radicals have been detected by transverse-field ?SR in a C70 powder sample at 298K. Their assignment is based on the results of semi-empirical MNDO calculations. There are significant changes in intensity and lineshape of the signals at low temperature. The first ?SR spectrum of a fullerenyl radical in solution has been obtained. (orig.)

  10. The tricarbonylchromium template for stereocontrol in radical reactions of arenes.

    Science.gov (United States)

    Merlic, C A; Walsh, J C

    2001-04-01

    Chromium tricarbonyl complexed aryl aldeyhydes and ketones underwent Sm(II)-promoted radical lactone formation in the presence of alpha,beta-unsaturated esters to produce diastereomerically pure lactones in good yields. The completely diastereoselective lactone formation involves capture of the benzylic ketyl radical by the ester anti to the chromium tricarbonyl moiety. The relative stereochemistry of the lactone and chromium tricarbonyl moieties was proven by X-ray crystallography and supports the proposed mechanism. Enantiopure chromium tricarbonyl complexed arenes afforded single enantiomers when subjected to Sm(II)-promoted radical lactone formation condiditions. The enantio- and diastereomerically pure chromium tricarbonyl complexed lactones were subsequently treated with BF3.OEt2 to generate a mixture of diastereomers via Lewis acid promoted chromium tricabonyl directed cationic rearrangement. The diastereomers were separated and individually decomplexed with I2 to afford both of the corresponding chromium-free enantiomerically pure lactones starting from a single enantiomerically pure chromium tricarbonyl complex. PMID:11281765

  11. An improved chemical amplifier technique for peroxy radical measurements

    Energy Technology Data Exchange (ETDEWEB)

    Cantrell, C.A.; Shetter, R.E.; Lind, J.A.; McDaniel, A.H.; Calvert, J.G. (National Center for Atmospheric Research, Boulder, CO (United States)); Parrish, D.D.; Fehsenfeld, F.C.; Buhr, M.P.; Trainer, M. (National Oceanic and Atmospheric Administration Aeronomy Lab., Boulder, CO (United States))

    1993-02-20

    The chemical amplifier for atmospheric peroxy radical measurements, first described in the early 1980s has been improved relative to these earlier reports. The details of the instrument and a new radical calibration procedure are discussed as they relate to participation in a field study in the southeastern United States in the summer of 1990. The theoretical behavior of the chemical amplifier is also examined with the use of analytical solutions to the relevant kinetic equations as well as with a numerical model. Several issues of atmospheric relevance are addressed including the response of the instrument to organic peroxy radicals, interferences from PAN and peroxynitric acid, accuracy, precision, and detection limits studied through a number of laboratory and field investigations. Some new findings realized since the summer of 1990 are also included. 44 refs., 16 figs., 2 tabs.

  12. Crystalline bipyridinium radical complexes and uses thereof

    Energy Technology Data Exchange (ETDEWEB)

    Fahrenbach, Albert C.; Barnes, Jonathan C.; Li, Hao; Stoddart, J. Fraser; Basuray, Ashish Neil; Sampath, Srinivasan

    2015-09-01

    Described herein are methods of generating 4,4'-bipyridinium radical cations (BIPY.sup..cndot.+), and methods for utilizing the radical-radical interactions between two or more BIPY.sup..cndot.+ radical cations that ensue for the creation of novel materials for applications in nanotechnology. Synthetic methodologies, crystallographic engineering techniques, methods of physical characterization, and end uses are described.

  13. Radical Scavenging Activities of Tannin Extracted from Amaranth (Amaranthus caudatus L.).

    Science.gov (United States)

    Jo, Hyeon-Ju; Chung, Kang-Hyun; Yoon, Jin A; Lee, Kwon-Jai; Song, Byeong Chun; An, Jeung Hee

    2015-06-01

    This study investigates the bioactivity of tannin from amaranth (Amaranthus caudatus L.) extracts. The antioxidant activities of the extracts from amaranth leaves, flowers, and seeds were evaluated. Tannin from leaves of amaranth has been evaluated for superoxide scavenging activity by using DPPH and ABTS(+) analysis, reducing power, protective effect against H2O2-induced oxidative damage in L-132 and BNL-CL2 cells, and inhibition of superoxide radical effects on HL-60 cells. At a concentration of 100 ?g/ml, tannin showed protective effects and restored cell survival to 69.2% and 41.8% for L-132 and BNL-CL2 cells, respectively. Furthermore, at the same concentration, tannin inhibited 41% of the activity of the superoxide radical on HL-60 cells and 43.4% of the increase in nitric oxide levels in RAW 264.7 cells. The expression levels of the antioxidant-associated protein SOD-1 were significantly increased in a concentration-dependent manner in RAW 264.7 cells treated with tannin from amaranth leaves. These results suggest that tannin from the leaves of Amaranthus caudatus L. is a promising source of antioxidant component that can be used as a food preservative or nutraceutical. PMID:25639718

  14. Reactions of HOCO radicals through hydrogen-atom hopping utilizing clathrate hydrates as an observational matrix.

    Science.gov (United States)

    Oshima, Motoi; Tani, Atsushi; Sugahara, Takeshi; Kitano, Katsuhisa; Ohgaki, Kazunari

    2014-02-28

    The carboxyl (HOCO) radical, which is an important species in atmospheric chemistry and combustion, is an intermediate in the reaction: CO + OH ? CO2 + H and serves as a hydrogen donor to the reaction partners. The cis-HOCO radical, one of the ground-state HOCO radicals, is supposed to be decomposed into CO2 and the hydrogen atom by a tunneling effect. In order to prove the hypothesis, we performed electron spin resonance (ESR) measurements to investigate the decay mechanisms of the ground-state HOCO and DOCO radicals in gamma-ray-irradiated CO2 hydrates, which may hold the radicals stably. The ground-state HOCO and DOCO radicals decayed according to a second-order decay model and transformed into formic acid and CO2. The ratio of the decay rate constants of HOCO and DOCO radicals shows a good agreement with that in the kinetic isotope effect for the hydrogen and deuterium abstraction reactions. These results indicate that they react with another HOCO radical in the adjacent hydrate cage without the tunneling effect. This implies that the ground-state HOCO radicals are not decomposed by the tunneling effect but are decayed through reactions with some atoms, molecules, and/or radicals even in the gas phase. In addition, the hydrogen-atom hopping through the temporary hydrogen bonds between the HOCO radical and CO2 results in a seeming diffusion of the HOCO radicals in the CO2 hydrate; this would be an important concept for the studies of the radical diffusions and the supply of hydrogen atoms in gas, liquid, and solid phases. PMID:24430533

  15. Free radicals from purine nucleosides after hydroxyl radical attack

    International Nuclear Information System (INIS)

    Free radicals from imidazole, caffeine, guanosine, deoxyguanosine, inosine, adenosine, deoxyadenosine, and adenine, as well as ?-D-ribose and ?-D-deoxyribose, were generated by reaction with OH from H2O2--Ti3+ at pH 1.5-2 and studied by ESR, using a computerized, Q-band, fast-flow system. Purine base radicals, plus sugar radicals in nucleosides, were always observed. Prior deuteration of C8 made possible the assignment of the observed 10--15 gauss doublet splitting to the C8 proton in guanine derivatives, and to the C2 proton in adenine derivatives and inosine. Hueckel calculations (and INDO in a few cases) on possible radical species suggest that hydroxyl addition on nitrogens in the purine ring or on C5 may be responsible for the species which are observed. In imidazole, the radical species is a hydroxyl adduct. An anomalous effect of deuteration of CS on the spectrum obtained with caffeine is also reported

  16. Free-radical reactions induced by OH-radical attack on cytosine-related compounds: a study by a method combining ESR, spin trapping and HPLC.

    OpenAIRE

    Hiraoka, W; Kuwabara, M.; Sato, F.; Matsuda, A; Ueda, T.

    1990-01-01

    Free-radical reactions induced by OH-radical attack on cytosine-related compounds were investigated by a method combining ESR, spin trapping with 2-methyl-2-nitrosopropane and high-performance liquid chromatography (HPLC). Cytidine, 2'-deoxycytidine, cytidine 3'-monophosphate, cytidine 5'-monophosphate, 2'-deoxycytidine 5'-monophosphate and their derivatives, of which 5,6-protons at the base moiety were replaced by deuterons, and polycytidylic acid (poly(C] were employed as samples. OH radica...

  17. Free Radical Scavenging Activity of Some Nigerian Medicinal Plant Extracts

    Directory of Open Access Journals (Sweden)

    M.O. Sofidiya

    2006-01-01

    Full Text Available The present research evaluates the DPPH radical scavenging, total antioxidant activities, reducing power and total contents of phenolic compounds in methanolic leaf extracts of five Nigerian medicinal plants (Dalbergia saxatilis Hook.f. (Papilionacae, Ekebergia senegalensis A.Juss.(Meliaceae, Hymenocardia acida Tul. (Hymenocardiaceae, Icacina tricantha Oliv. (Icacinaceae and Salacia pallescens Oliv.(Celastraceae. Total phenols were analysed according to the Folin-Ciocalteu method. Each sample under assay condition, showed a dose-dependent effect both on free radical scavenging 1,1-diphenyl-2-picrylhydrazyl radical (DPPH and also on Fe3+ reducing power. The antioxidant activity of the plant extracts with the DPPH radical scavenging and reducing power method, were in the order Hymenocardia> Ekebergia> Salacia> Icacina> Dalbergia. H. acida and E. senegalensis possess very high radical scavenging activity in both assays. Potency of H. acida extract was of the same magnitude as that of reference ?-tocopherol. Total phenols in all the samples expressed as GAE (Gallic Acid Equivalent varied from 1.83 to 15.47mg g-1 of dry plant material. Total antioxidant activities correlated with total phenols (R2 = 0.6640 an indication that 66% of the antioxidant capacity of these extracts results from contribution of phenolic compounds. A linear positive relationship existed between the reducing power and total phenolics of the tested plant extracts (R2 = 0.9564.

  18. Peroxy radical partitioning during the AMMA radical intercomparison exercise

    Directory of Open Access Journals (Sweden)

    M. D. Andrés-Hernández

    2010-11-01

    Full Text Available Peroxy radicals were measured onboard two scientific aircrafts during the AMMA (African Monsoon Multidisciplinary Analysis campaign in summer 2006. This paper reports results from the flight on 16 August 2006 during which measurements of HO2 by laser induced fluorescence spectroscopy at low pressure (LIF-FAGE and total peroxy radicals (RO2* = HO2+?RO2, R = organic chain by two similar instruments based on the peroxy radical chemical amplification (PeRCA technique were subject of a blind intercomparison. The German DLR-Falcon and the British FAAM-BAe-146 flew wing tip to wing tip for about 30 min making concurrent measurements on 2 horizontal level runs at 697 and 485 hPa over the same geographical area in Burkina Faso. A full set of supporting measurements comprising photolysis frequencies, and relevant trace gases like CO, NO, NO2, NOy, O3 and a wider range of VOCs were collected simultaneously.

    Results are discussed on the basis of the characteristics and limitations of the different instruments used. Generally, no data bias are identified and the RO2* data available agree quite reasonably within the instrumental errors. The [RO2*]/[HO2] ratios, which vary between 1:1 and 3:1, as well as the peroxy radical variability, concur with variations in photolysis rates and in other potential radical precursors. Model results provide additional information about dominant radical formation and loss processes.

  19. Peroxy radical partitioning during the AMMA radical intercomparison exercise

    Directory of Open Access Journals (Sweden)

    M. D. Andrés-Hernández

    2010-04-01

    Full Text Available Peroxy radicals were measured onboard two scientific aircrafts during the AMMA (African Monsoon Multidisciplinary Analysis campaign in summer 2006. This paper reports results from the flight on 16 August 2006 during which measurements of HO2 by laser induced fluorescence spectroscopy at low pressure (LIF-FAGE and total peroxy radicals (RO2*=HO2+?RO2, R= organic chain by two similar instruments based on the peroxy radical chemical amplification (PerCA technique were subject of a blind intercomparison. The German DLR-Falcon and the British FAAM-BAe-146 flew wing tip to wing tip for about 30 min making concurrent measurements on 2 horizontal level runs at 697 and 485 hPa over the same geographical area in Burkina Faso. A full set of supporting measurements comprising photolysis frequencies, and relevant trace gases like CO, NO, NO2, NOy, O3 and a wider range of VOCs were collected simultaneously.

    Results are discussed on the basis of the characteristics and limitations of the different instruments used. Generally, no data bias are identified and the RO2* data available agree quite reasonably within the instrumental errors. The [RO2*]/[HO2] ratios, which vary between 1:1 and 3:1, as well as the peroxy radical variability, concur with variations in photolysis rates and in other potential radical precursors. Model results provide additional information about dominant radical formation and loss processes.

  20. Hydroxyl radical, sulfate radical and nitrate radical reactivity towards crown ethers in aqueous solutions

    International Nuclear Information System (INIS)

    Reaction rate constants of crown ethers (12-crown-4, 15-crown-5, 18-crown-6) and their analogs 1,4-dioxane (6C2) with some important oxidative radicals, hydroxyl radical (·OH), sulfate radical (SO4·?) and nitrate radical (NO3·), were determined in various aqueous solutions by pulse radiolysis and laser photolysis techniques. The reaction rate constants for 6C2 and crown ethers with ·OH and SO4·? increase with the number of hydrogen atoms in the ethers, indicating that the hydrogen-atom abstraction is a dominant reaction between crown ethers and these two radicals. The presence of cations in solution has negligible effect on the rate constants of crown ether towards ·OH and SO4·?. However, for the NO3·, the rate constants are not proportional to the number of hydrogen atoms in ethers, and 12-crown-4 (12C4) is the most reactive compared with other crown ethers. Except 12C4 and 6C2, the cations in the aqueous solution affect the reactivities of 15-crown-5 (15C5) and 18-crown-6 (18C6). The cations with high binding stability for crown ether would improve the reactivity of 15C5. For the studied crown ethers, the reaction rate constants of these oxidative radicals have the order ·OH>SO4·?>NO3·. Furthermore, the formation of radicals after the reaction of crown ethers with sulfate radical could be observed in the range of 260–280 nm using laser photolysis and pulse radiolysis. This is the first report on the kinetic behavior of crown ethers with NO3·, and it would be helpful for the understanding of stability of crown ethers in the processing of spent nuclear fuel. - Highlights: ? The rate constants of NO3· and SO4·? towards various crown ethers in aqueous solution were determined for the first time. ? The rate constants of these radicals towards crown ethers have the order ·OH>SO4·?>NO3·. ? Hydrogen atom abstraction is the dominant reaction between these radicals and crown ethers. ? The binding capacity of crown ethers with cations in solution will affect k (NO3·+ ethers).

  1. Free radical facilitated damage of ungual keratin.

    Science.gov (United States)

    Khengar, Rajeshree H; Brown, Marc B; Turner, Rob B; Traynor, Matthew J; Holt, Katherine B; Jones, Stuart A

    2010-09-01

    Thioglycolic acid (TA) and urea hydrogen peroxide (urea H(2)O(2)) are thought to disrupt alpha-keratin disulfide links in the nail. However, optimal clinical use of these agents to improve the treatment of nail disorders is currently hindered by a lack of fundamental data to support their mechanism of action. The aim of this study was to investigate how the redox environment of ungual keratin, when manipulated by TA and urea H(2)O(2), influenced the properties of the nail barrier. Potentiometric and voltammetric measurements demonstrated that urea H(2)O(2) obeyed the Nernst equation for a proton coupled one-electron transfer redox process while TA underwent a series of redox reactions that was complicated by electrode adsorption and dimer formation. The functional studies demonstrated that nail permeability, measured through TBF penetration (38.51+/-10.94 microg/cm(2)/h) and nail swelling (244.10+/-14.99% weight increase), was greatest when relatively low concentrations of the thiolate ion were present in the applied solution. Limiting the thiolate ion to low levels in the solution retards thiolate dimerisation and generates thiyl free radicals. It appeared that this free radical generation was fundamental in facilitating the redox-mediated keratin disruption of the ungual membrane. PMID:20550963

  2. Photochemical synthesis of simple organic free radicals on simulated planetary surfaces - An ESR study

    Science.gov (United States)

    Tseng, S.-S.; Chang, S.

    1975-01-01

    Electron spin resonance (ESR) spectroscopy provided evidence for formation of hydroxyl radicals during ultraviolet photolysis (254 nm) at -170 C of H2O adsorbed on silica gel or of silica gel alone. The carboxyl radical was observed when CO or CO2 or a mixture of CO and CO2 adsorbed on silica gel at -170 C was irradiated. The ESR signals of these radicals slowly disappeared when the irradiated samples were warmed to room temperature. However, reirradiation of CO or CO2, or the mixture CO and CO2 on silica gel at room temperature then produced a new species, the carbon dioxide anion radical, which slowly decayed and was identical with that produced by direct photolysis of formic acid adsorbed on silica gel. The primary photochemical process may involve formation of hydrogen and hydroxyl radicals. Subsequent reactions of these radicals with adsorbed CO or CO2 or both yield carboxyl radicals, CO2H, the precursors of formic acid. These results confirm the formation of formic acid under simulated Martian conditions and provide a mechanistic basis for gauging the potential importance of gas-solid photochemistry for chemical evolution on other extraterrestrial bodies, on the primitive earth, and on dust grains in the interstellar medium.

  3. Is Kant’s conception of radical evil radical enough

    Directory of Open Access Journals (Sweden)

    Loli? Marinko

    2011-01-01

    Full Text Available Kant’s philosophical critical attitudes provoked strong reactions, not only philosophical, but the general public. Among those of his ideas, which have been provoking severe philosophical misunderstandings and controversy are: “Which in theory is not worth, that has no use in practice”, “The rights not to lie”, “against the rights of citizens to revolt”, etc. After all, the most attention in the great public was provoked by his idea about radical evil. In this short reflection, we will try to point out the main points of this philosophical misunderstanding and to make a little more explicit the concept of radical evil.

  4. Salvage radiotherapy following radical prostatectomy

    International Nuclear Information System (INIS)

    Recurrent disease following radical prostatectomy will occur in approximately 20% of patients, for whom the therapeutic options include surveillance, salvage radiotherapy, or hormonal therapy. This review will focus on the evidence for salvage radiotherapy. Efficacy results of 30-50% have been reported from multiple retrospective series, with minimal morbidity. Unfortunately there are no randomized or prospective studies in this area. Results of salvage radiotherapy improve when given earlier, ideally with the serum prostate-specific antigen <1 ng/mL. Other positive prognosticators are positive margins at radical prostatectomy, longer prostate-specific antigen doubling times, lower radical prostatectomy Gleason scores, and the absence of lymph node metastases. Current standard dosage is 64 Gy or slightly higher, although the optimal dosage has yet to be defined with prospective randomized trials. Salvage radiotherapy can provide a durable response when given early, and patients with recurrent disease should be considered for treatment or enrolment in clinical trials. (author)

  5. Photoionization of the OH radical

    International Nuclear Information System (INIS)

    The hydroxyl radical (OH) is one of the most thoroughly studied free radicals because of its importance in atmospheric chemistry, combustion processes, and the interstellar medium. Detailed experimental and theoretical studies have been performed on the ground electronic state (X 2PI/sub i/) and on the four lowest bound excited electronic states (A 2?+, B 2?+, D 2?-, and C2?+). However, because it is difficult to distinguish the spectrum of OH from the spectra of the various radical precursors, the absorption spectrum in the wavelength region below 1200 A has not been well characterized. In the present work, the spectrum of OH has been determined in the wavelength region from 750 to 950 A using the technique of photoionization mass spectrometry. This technique allows complete separation of the spectrum of OH from that of the other components of the discharge and permits the unambiguous determination of the spectrum of OH

  6. Epistemological barriers to radical behaviorism.

    Science.gov (United States)

    O'Donohue, W T; Callaghan, G M; Ruckstuhl, L E

    1998-01-01

    The historian and philosopher of science Gaston Bachelard proposed the concept of epistemological barriers to describe the intellectual challenges encountered by scientists in their work. In order to embrace novel ways of approaching a problem in science, scientists must overcome barriers or obstacles posed by their prior views. For example, Einsteinian physics presents scientists with claims that space is curved and that time and space are on the same continuum. We utilize Bachelard's concept of epistemological barriers to describe the differences between the intellectual journeys students pursuing advanced studies face when attempting to accept cognitive psychology or radical behaviorism. We contend that the folk psychological beliefs that students typically hold when entering these studies pose less challenge to cognitive psychology than to radical behaviorism. We also suggest that these barriers may also partly be involved in the problematic exegesis that has plagued radical behaviorism. In close, we offer some suggestions for dealing with these epistemological barriers. PMID:22478314

  7. Efficient scavenging of ?-carotene radical cations by antiinflammatory salicylates

    DEFF Research Database (Denmark)

    Cheng, Hong; Liang, Ran

    2014-01-01

    The radical cation generated during photobleaching of ?-carotene is scavenged efficiently by the anion of methyl salicylate from wintergreen oil in a second-order reaction approaching the diffusion limit with k = 3.2 × 10 L mol s in 9:1 v/v chloroform-methanol at 23 °C, less efficiently by the anion of salicylic acid with 2.2 × 10 L mol s, but still of possible importance for light-exposed tissue. Surprisingly, acetylsalicylate, the aspirin anion, reacts with an intermediate rate in a reaction assigned to the anion of the mixed acetic-salicylic acid anhydride formed through base induced rearrangements. The relative scavenging rate of the ?-carotene radical cation by the three salicylates is supported by DFT-calculations. © 2014 The Royal Society of Chemistry.

  8. On radical square zero rings

    CERN Document Server

    Ringel, Claus Michael

    2011-01-01

    Let A be a connected left artinian ring with radical square zero and with n simple modules. If A is not self-injective, then we show that any module M with Ext^i(M,A) = 0 for 1 \\le i \\le n + 1 is projective. We also determine the structure of the artin algebras with radical square zero and n simple modules which have a non-projective module M such that Ext^i(M,A) = 0 for 1 \\le i \\le n.

  9. O conceito de mal radical / The concept of radical evil

    Scientific Electronic Library Online (English)

    Adriano, Correia.

    Full Text Available A noção de mal radical aparece em Kant no contexto da discussão da religião nos limites da simples razão e busca dar conta da complexa relação entre o respeito pela lei moral e o amor-próprio na definição do móbil para a ação. Na busca por identificar o fundamento da propensão para o mal no homem, K [...] ant se vê diante da dificuldade de ter de articular natureza e liberdade, e ainda que a noção de mal radical possa conservar algumas ambigüidades, permite conceber uma noção de responsabilidade compatível com uma inata propensão para o mal. Neste texto busco explicitar alguns passos fundamentais na construção do conceito por Kant. Abstract in english The concept of radical evil appears in Kant's theory when he discusses the religion in the limits of the mere reason and aims explain the complex relationship between respect for the moral law and the self-love, for establish the motive of the action. By aiming identify the basis of human inclinatio [...] n to evil, Kant is faced with the trouble of have to put nature and freedom in connection. Despite of the concept of radical evil retain some ambiguity, it allows conceive a notion of responsibility suitable to an inherent inclination to evil. In this paper is my purpose to explain some basic moments of Kantian formulation of that notion.

  10. Polyenyl cations and radical cations – synthesis, spectroscopic properties and reactions

    OpenAIRE

    Kildahl-Andersen, Geir

    2007-01-01

    In the present work, polyene precursors for the formation of charged polyenyl species were synthesised. Their conversion to charge delocalised radical cations and diamagnetic mono- and dications was carried out by treatment with Brønsted and Lewis acids. Reaction conditions were optimised to achieve sufficient stability of the charged polyenes for characterisation by modern spectroscopic methods; in particular nearinfrared absorption spectroscopy (NIR), two-dimensional nuclear magnetic resona...

  11. The Games Radicals Play: Special Issue on Free Radicals and Radical Ions

    Directory of Open Access Journals (Sweden)

    John C. Walton

    2015-02-01

    Full Text Available Chemistry and Physics have aptly been described as “most excellent children of Intellect and Art” [1]. Both these “children” engage with many playthings, and molecules rank as one of their first favorites, especially radicals, which are amongst the most lively and exciting. Checking out radicals dancing to the music of entropy round their potential energy ballrooms is surely both entertaining and enlightening. Radicals’ old favorite convolutions are noteworthy, but the new styles, modes and arrangements appearing on the scene are even more interesting. Some of these are ephemeral and enjoy only a brief appearance, others are retro-types reappearing in new guises, still others are genuinely new and “go viral” in the scientific world. This Special Issue of Molecules contains the observations and reflections of a select group of chemists and physicists fascinated by this spectacle. It contains an eclectic mix reflecting on new modes and advances as well as on permutations and combinations that revive mature themes. [...

  12. The poly(ADP-Ribose) polymerase inhibitor ABT-888 reduces radiation-induced nuclear EGFR and augments head and neck tumor response to radiotherapy

    International Nuclear Information System (INIS)

    Background and purpose: Current therapies for head and neck cancer frequently are not curative, necessitating novel therapeutic strategies. Thus, we studied whether inhibition of poly(ADP-Ribose) polymerase (PARP), a key DNA repair enzyme, could improve efficacy of radiotherapy in human head and neck cancer. Materials and methods: UM-SCC1, UM-SCC5, UM-SCC6, and FaDu human head and neck cancer cellular susceptibility to the PARP inhibitor (PARPi) ABT-888 and/or radiation (IR) was assessed using colony formation assays. DNA damage was evaluated using the alkaline comet assay and immunostaining for ?-H2AX foci. Non-homologous end-joining (NHEJ) mediated repair was measured using phospho-DNA-Pk foci. Epidermal growth factor receptor (EGFR) location was assessed by immunostaining. Poly ADP-Ribose polymerization (PAR) levels were assessed using immunoblotting. Results: Human head and neck cancer cells exhibited enhanced cytotoxicity with IR and ABT-888 compared to either agent alone. This increased susceptibility correlated with reduced nuclear EGFR, attenuation of NHEJ, and persistence of DNA damage following IR. Interestingly, a subset of head and neck cancer cells which had elevated basal PAR levels was susceptible to PARPi alone. Conclusions: Combining radiotherapy and PARP inhibition may improve outcomes and quality of life for head and neck cancer patients treated with radiotherapy. Furthermore, this novel strategy may also be feasible in other tumor types. Moreover, PAR levels should be investigated as a potential biomarker for tumor susceptibility to PARP inhibition.

  13. ESTIMATION OF HYDROXYL AND HYDROPEROXYL RADICALS CONCENTRATIONS IN THE URBAN ATMOSPHERE OF SANTIAGO

    Scientific Electronic Library Online (English)

    M. Angélica, Rubio; Eduardo, Liss; Guillermo, Villena; Victoria, Caroca; Ernesto, Gramsch; Álvaro, Ruiz.

    2005-06-01

    Full Text Available Photochemical smog episodes are frequent in Santiago of Chile city. We have measured the concentration of the main free radical precursors (formaldehyde, ozone, nitrogen dioxide, peroxyacetyl nitrate and nitrous acid), nitrogen monoxide and the irradiance. Calculations of the rate of OH* production [...] were performed for different periods of the year and at emission (Cerrillos and Estacion Central) and receptor sites (Las Condes). From these data and simple steady state considerations were derived the concentrations of hydroxyl and hydroperoxyl radicals. Daily profiles of both radicals show a noticeable accumulation during early afternoon, the time of most intense oxidants accumulation. During summer time, hydroperoxyl radical concentrations are higher in Las Condes than in Cerrillos. The concentrations calculated for both radicals are higher than those estimated in other cities, suggesting a particularly high photochemical activity in the urban atmosphere of Santiago of Chile

  14. ESTIMATION OF HYDROXYL AND HYDROPEROXYL RADICALS CONCENTRATIONS IN THE URBAN ATMOSPHERE OF SANTIAGO

    Directory of Open Access Journals (Sweden)

    M. Angélica Rubio

    2005-06-01

    Full Text Available Photochemical smog episodes are frequent in Santiago of Chile city. We have measured the concentration of the main free radical precursors (formaldehyde, ozone, nitrogen dioxide, peroxyacetyl nitrate and nitrous acid, nitrogen monoxide and the irradiance. Calculations of the rate of OH* production were performed for different periods of the year and at emission (Cerrillos and Estacion Central and receptor sites (Las Condes. From these data and simple steady state considerations were derived the concentrations of hydroxyl and hydroperoxyl radicals. Daily profiles of both radicals show a noticeable accumulation during early afternoon, the time of most intense oxidants accumulation. During summer time, hydroperoxyl radical concentrations are higher in Las Condes than in Cerrillos. The concentrations calculated for both radicals are higher than those estimated in other cities, suggesting a particularly high photochemical activity in the urban atmosphere of Santiago of Chile

  15. Characterization of Supersonic Radical Source.

    Czech Academy of Sciences Publication Activity Database

    Mašát, M.; Votava, Ond?ej

    Prague : MATFYZPRESS, 2008, s. 81-87. ISBN 978-80-7378-066-1. [WDS´08. Prague (CZ), 03.06.2009-06.06.2009] Institutional research plan: CEZ:AV0Z40400503 Keywords : spectroscopy * supersonic radical sources Subject RIV: CF - Physical ; Theoretical Chemistry

  16. Radical surgery for pilonidal sinus.

    OpenAIRE

    Thomson, James P S; Lee, Joseph

    1983-01-01

    Pilonidal sinus disease in 72 patients was treated by radical excision and primary wound closure and the results compared with those other currently practised techniques. A number of factors have been examined in an attempt to identify a group of patients in whom the risk of delayed healing is high.

  17. CO capture and conversion to HOCO radical by ionized water clusters.

    Science.gov (United States)

    Lee, Han Myoung; Youn, Il-Seung; Kim, Kwang S

    2014-09-01

    The CO molecule can interact with the hydroxyl radical ((•)OH) via either a weak noncovalent interaction or strong covalent bonding. Upon the ionization of neutral water clusters, the resulting water cluster cations produce protonated water clusters and hydroxyl radicals. In this regard, we investigate the interactions of a CO molecule with water dimer and trimer cations using density functional theory (DFT), Möller-Plesset second-order perturbation theory (MP2), and coupled cluster theory with single, double, and perturbative triple excitations [CCSD(T)]. It is found that the reaction products of CO by the water dimer and trimer cations form a HO?O radical solvated by a protonated water monomer and dimer, respectively. These radicals are useful intermediates to make oxalic acids, formic acids, metal ligands, and so on, which is important in green chemistry. PMID:24641201

  18. Antioxidant Effects of Herbal Tea Leaves from Yacon (Smallanthus sonchifolius) on Multiple Free Radical and Reducing Power Assays, Especially on Different Superoxide Anion Radical Generation Systems.

    Science.gov (United States)

    Sugahara, Shintaro; Ueda, Yuto; Fukuhara, Kumiko; Kamamuta, Yuki; Matsuda, Yasushi; Murata, Tatsuro; Kuroda, Yasuhiro; Kabata, Kiyotaka; Ono, Masateru; Igoshi, Keiji; Yasuda, Shin

    2015-11-01

    Yacon (Smallanthus sonchifolius), a native Andean plant, has been cultivated as a crop and locally used as a traditional folk medicine for the people suffering from diabetes and digestive/renal disorders. However, the medicinal properties of this plant and its processed foods have not been completely established. This study investigates the potent antioxidative effects of herbal tea leaves from yacon in different free radical models and a ferric reducing model. A hot-water extract exhibited the highest yield of total polyphenol and scavenging effect on 1,1-diphenyl-2-picryl hydrazyl (DPPH) radical among four extracts prepared with hot water, methanol, ethanol, and ethylacetate. In addition, a higher reducing power of the hot-water extract was similarly demonstrated among these extracts. Varying concentrations of the hot-water extract resulted in different scavenging activities in four synthetic free radical models: DPPH radical (EC50 28.1 ?g/mL), 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) cation radical (EC50 23.7 ?g/mL), galvinoxyl radical (EC50 3.06 ?g/mL), and chlorpromazine cation radical (EC50 475 ?g/mL). The yacon tea-leaf extract further demonstrated superoxide anion (O2 (-) ) radical scavenging effects in the phenazine methosulfate-NADH-nitroblue tetrazolium (EC50 64.5 ?g/mL) and xanthine oxidase assay systems (EC50 20.7 ?g/mL). Subsequently, incubating human neutrophilic cells in the presence of the tea-leaf extract could suppress the cellular O2 (-) radical generation (IC50 65.7 ?g/mL) in a phorbol 12-myristate 13-acetate-activated cell model. These results support yacon tea leaves may be a good source of natural antioxidants for preventing O2 (-) radical-mediated disorders. PMID:26457985

  19. Quantum Mechanical Calculations of Cytosine, Thiocytosine and Their Radical Ions

    Science.gov (United States)

    Singh, Rashmi

    2010-08-01

    The RNA and DNA are polymer that share some interesting similarities, for instance it is well known that cytosine is the one of the common nucleic acid base. The sulfur is characterized as a very reactive element and it has been used, in chemical warfare agents. Since the genetic information is based on the sequence of the nucleic acid bases. The quantum mechanical calculations of the energies, geometries, charges and vibrational characteristics of the cytosine and thiocytosine. and their corresponding radicals were carried out by using DFT method with b3lyp/6-311++g** basis set.

  20. Organic peroxy free radicals as ultimate agents in oxygen toxicity

    International Nuclear Information System (INIS)

    The role of organic peroxy free radicals in the interaction of oxygen with important biomolecules in in vitro radiation damage studies is reviewed. These studies include the reaction of RO2. but not R. or 02-. with NADH, antioxidants, unsaturated fatty acids, anti-inflammatory drugs and amino acids; the effects of 02-. and CCl302. on the survival of bacterio-phage T2 in the absence and presence of several anti-inflammatory drugs; the inactivation of lyzozyme by CCl302-.; the inactivation of alcohol dehydrogenase by RO2. generally but not 02.; and the protection of ADH by antioxidants and superoxide dismutase. (U.K.)

  1. Effect of electron-withdrawing power of the substituted group on ${}^{\\bullet}$OH radical reaction with substituted aryl sulphides: A pulse radiolysis study

    Indian Academy of Sciences (India)

    Hari Mohan

    2002-12-01

    In neutral aqueous solution of (phenylthio)acetic acid, hydroxyl radical is observed to react with a bimolecular rate constant of $7.2 \\times 10^9$ dm3 mol-1 s-1 and the transient absorption bands are assigned to ${}^{\\bullet}$OH radical addition to benzene and sulphur with a rough estimated values of 50 and 40% respectively. The reaction of the ${}^{\\bullet}$OH radical with diphenyl sulphide ($k = 4.3 \\times 10^8$ dm3 mol-1 s-1) is observed to take place with formation of solute radical cation, OH-adduct at sulphur and benzene with estimated values of about 12, 28 and 60% respectively. The transient absorption bands observed on reaction of ${}^{\\bullet}$OH radical, in neutral aqueous solution of 4-(methylthio) phenyl acetic acid, are assigned to solute radical cation ($\\lambda_{\\text{max}} = 550$ and 730 nm), OH-adduct at sulphur ($\\lambda_{\\text{max}} = 360$ nm) and addition at benzene ring ($\\lambda_{\\text{max}} = 320$ nm). The fraction of ${}^{\\bullet}$OH radical reacting to form solute radical cation is observed to depend on the electron-withdrawing power of substituted group. In acidic solutions, depending on the concentration of acid and electron-withdrawing power, solute radical cation is the only transient species formed on reaction of ${}^{\\bullet}$OH radical with the sulphides studied.

  2. Myeloperoxidase as an effective inhibitor of hydroxyl radical production. Implications for the oxidative reactions of neutrophils.

    OpenAIRE

    Winterbourn, C C

    1986-01-01

    Hydroxyl radicals have been generated from hydrogen peroxide and superoxide (produced with xanthine oxidase), and an iron (EDTA) catalyst, and detected with deoxyribose, or in some cases with benzoate or alpha-keto-gamma-methiolbutyric acid. Purified myeloperoxidase, and neutrophils stimulated with fMet-Leu-Phe and cytochalasin B, strongly inhibited this hydroxyl radical production in a concentration-dependent manner. Supernatants from stimulated cells also inhibited, and inhibition by cells ...

  3. Arene-thioether mixed complex radical cations

    International Nuclear Information System (INIS)

    Studies of radiolytically generated radical cations in aromatic hydrocarbon solvents have led to the first direct characterization of monomeric thioether radical cations in liquid solution. Observation of these very reactive chemical intermediates is made possible by the great sensitivity of fluorescence-detected magnetic resonance (FDMR) and by solvent stabilization of the thioether radical cations via electron donation. Monomeric thioether radical cations in arene solvents such as toluene exist as arene-thioether mixed complex radical cations -- the first ?-lone pair mixed complex radical cations ever observed. Such orbital interactions are of fundamental importance for open-shell intermediates as they have consequences for both electronic structure and reactivity. Thioether radical cations provide a valuable test system to probe the chemical influence of orbital interactions that are generic to all ?-type and heteroatom-containing organic radical cations, and magnetic resonance provides unsurpassed structural resolution for condensed-phase paramagnetic intermediates

  4. A time-resolved Raman study of the reaction of OH radicals with p-phenylenediamine

    International Nuclear Information System (INIS)

    In a previous study of the reaction of OH with aromatic diamines the absorption spectrum attributed to the OH adducts was reported to be virtually identical with that of the radical cations, differing only in intensity. Here we apply pulse radiolysis methods with time-resolved resonance Raman detection to examine the intermediates formed in the OH oxidation of p-phenylenediamine. These studies show that in neutral and basic solution the OH adducts, if formed, have a very short lifetime, that the absorption spectrum previously assigned to the OH adduct is, in fact, that of the radical cation, and that this radical cations does not protonate in moderately acidic solutions

  5. Screening of various botanical extracts for antioxidant activity using DPPH free radical method.

    Science.gov (United States)

    Waqas, Muhammad Khurram; Saqib, Najam-Us; Rashid, Saeed-Ur; Shah, Pervaiz Akhtar; Akhtar, Naveed; Murtaza, Ghulam

    2013-01-01

    Aiming at the exploration of herbal use by society, crude extracts of the seeds of some commonly used medicinal plants (Vitis vinifera, Tamarindus indica and Glycin max) were screened for their free radical scavenging properties using ascorbic acid as standard antioxidant. Free radical scavenging activity was evaluated using 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical. The overall antioxidant activity of grape seeds (Vitis vinifera) was the strongest, followed in descending order by soybean (Glycin max) and tamarind (Tamarindus indica). The seeds extract of Vitis vinifera, Glycin max and Tamarindus indica showed 85.61%, 83.45% and 79.26%, DPPH scavenging activity respectively. PMID:24311867

  6. The radiation chemistry of connective tissue; hyaluronic acid

    International Nuclear Information System (INIS)

    Aqueous solutions of hyaluronic acid have been irradiated under various conditions and the amount of strand scission was determined viscometrically. OH radicals were found to be some 1.5 times more potent than H atoms at inducing breaks, methanol, propan-2-ol and t-butanol radicals produced relatively little breakage (potency less than 3% that of .OH). Tetranitromethane (TNM) has been used to measure the yield of reducing radicals produced on OH radical attack on hyaluronic acid, around 80% of the hyaluronic acid radicals reacted with TNM (i.e. are reducing radicals) with a rate constant of 4.5x108 mol-1 dm3 s-1. In contrast similar measurements on the polysaccharide model, ?-cyclodextrin, indicated that all the radicals formed were reducing. The presence of TNM or oxygen during radiolysis caused a 30% fall in chain breakage. The majority of radicals produced in both hyaluronic acid and ?-cyclodextrin are either 1,2 dihydroxy or 1-hydroxy 2-alkoxy type radicals, both of which form ?-carbonyl radicals by the acid (and base) catalysed elimination of water or alcohol. These ?-carbonyl radicals are considerably less reducing than their parent ?-hydroxy radicals and are not expected to react with TNM. By determining the extent of reaction with TNM as a function of TNM concentration, the first order rate constant for the formation of the ?-carbonyl radicals can be calculated on applying simple competition kinetics. The rate constant at pH 4 was found to be about 4x103 s-1 in the case of hyaluronic acid radicals, with the ?-cyclodextrin system even at pH 2.8 the rate constant was less than 2x103 s-1. (author). 12 refs, 1 fig., 1 tab

  7. Muonium radicals in benzene-styrene mixtures

    International Nuclear Information System (INIS)

    Muonium radicals were observed through their ?+SR precession frequencies in high transverse magnetic fields in pure benzene, pure styrene and their mixtures, all as liquids at room temperature. In benzene-styrene mixtures, the radicals obtained in each pure liquid are both present, so no slow (10-9-10-5 s) intermolecular exchange occurs; but strong selectivity was found with the formation of the radical from styrene being about eight-times more probable than the radical from benzene. (Auth.)

  8. Generation of OH radicals at palladium oxide nanoparticle modified electrodes, and scavenging by fluorescent probes and antioxidants.

    OpenAIRE

    Liu, J.; Lagger, G; Tacchini, P; GIRAULT, H. H.

    2008-01-01

    The reduction of palladium oxide nanoparticles in the presence of hydrogen peroxide or dissolved oxygen gives rise to a catalytic reduction current dependent on the hydrogen peroxide concentration or the oxygen concentration. Using terephthalic acid as an OH radical scavenger yielding the fluorescent 2-hydroxyterephthalic acid, we demonstrate that the catalytic current stems from the freshly exposed palladium metal re-oxidation by OH radicals. A kinetic model is presented to account for thes...

  9. Establishment of activity indicator of TiO2 photocatalytic reaction-Hydroxyl radical trapping method

    International Nuclear Information System (INIS)

    In this study, a new, low cost and easy method, hydroxyl radical trapping method, was employed to investigate the photo-activity of UV/TiO2 photocatalytic reaction. The Taguchi method was utilized to optimize the preparation of titanium dioxide (TiO2) thin-film reactor through the modified chemical vapor deposition (CVD) method. The optimal yield of hydroxyl radicals was then evaluated by calculating the conversion ratio of salicylic acid under the optimal conditions. In the experiments, salicylic acid was used as the free-radical scavenger and the formation of three different intermediates were examined to shed light on the trend and kinetics of reaction of hydroxyl radical with organic substance under different operation conditions. The results indicated that the yield of hydroxyl radicals increased with increasing irradiation intensity and dissolved oxygen level. The optimal experimental conditions obtained in this study were irradiation with intensity of 2.9 mW cm-2 on salicylic acid at concentration of 250 mg L-1 by both agitation and aeration processes (dissolved oxygen level = 8.2 mg O2 L-1) at pH 5. Such conditions could achieve the optimal hydroxyl radical yield of 5.1 x 10-17 M.

  10. Radical carbonylations using a continuous microflow system

    Directory of Open Access Journals (Sweden)

    Takahide Fukuyama

    2009-07-01

    Full Text Available Radical-based carbonylation reactions of alkyl halides were conducted in a microflow reactor under pressurized carbon monoxide gas. Good to excellent yields of carbonylated products were obtained via radical formylation, carbonylative cyclization and three-component coupling reactions, using tributyltin hydride or TTMSS as a radical mediator.

  11. The Radical Axis: A Motion Study

    Science.gov (United States)

    McGivney, Ray; McKim, Jim

    2006-01-01

    Interesting problems sometimes have surprising sources. In this paper we take an innocent looking problem from a calculus book and rediscover the radical axis of classical geometry. For intersecting circles the radical axis is the line through the two points of intersection. For nonintersecting, nonconcentric circles, the radical axis still…

  12. Electron spin resonance study of radiation-induced radicals in polycrystalline oligopeptides containing methionine

    International Nuclear Information System (INIS)

    The radicals formed on ?-radiolysis of oligopeptides containing methionine and glycine residues in the polycrystalline state at 77 k and subsequent warming over the temperature range 77-293 K were identified using the electron spin resonance (ESR) technique. In all oligopeptides studied, anion peptide radicals and monomeric sulfur radical cations over the temperature range 77-95 K and decarboxylation and deamination radicals over the temperature range 180-250 K were detected. In addition, in oligopeptides containing adjacent methionyl residues, three-electron-bonded dimeric sulfur radical cations (S:.S)+ were detected at 110 K. In oligopeptides containing N-terminal methionine residue, H-abstraction radicals in the side chain of methionine residue were observed over the temperature range of 180-250 K. H-abstraction radicals at the ?-carbon of the C-terminal amino acid residue were detected at 293 K in most of oligopeptides studied, in contrast to Met-Gly-Met and Met-Gly-Met-Met peptides were H-abstraction radicals at the ?-carbon of the integral glycine residue were observed. (author)

  13. FREE RADICAL SCAVENGING ACTIVITY OF RANDIA DUMETORUM LAMK FRUITS

    Directory of Open Access Journals (Sweden)

    Movalia Dharmishtha

    2010-12-01

    Full Text Available Free radicals are implicated for many diseases including Diabetes mellitus, arthritis, cancer, ageing etc. In treatment of these diseases, antioxidant therapy has gained utmost importance. Antioxidants can also help to repair damage already sustained by cells. Randia dumetorum Lamk. is a plant of medicinal important belongs to the family Rubiaceae. Polyphenols are good antioxidant. Fruits consist of Phenolic in large amount. It is traditionally used to cure diseases but no scientific data is available. Thus the objective of present study was aimed to check the antioxidant potential of Aqueous extract of Randia dumetorum fruits using different models viz. DPPH radical scavenging, iron chelating activity and nitric oxide scavenging assay. The results were analyzed statistically by regression method. The % scavenging activity at different concentrations was determined and the IC50 value of the extracts was compared with that of standard, ascorbic acid. Its antioxidant activity was estimated by IC50 value and the values are 45.02 ?g/ml (reducing power assay, 66 ?g/ml, (DPPH scavenging assay and 79.09 ?g/ml (nitric oxide scavenging assay. In all the testing, a significant correlation existed between concentrations of the extract and percentage inhibition of free radicals, metal chelation. According to these results, it may be hypothesized that antioxidant effect of fruits could be related to presence of polyphenolic compounds. These results clearly indicate that Randia dumetorum is effective against free radical mediated diseases.

  14. Pulsed radiation studies of carotenoid radicals and excited states

    International Nuclear Information System (INIS)

    The one-electron reduction potentials of the radical cations of five dietary carotenoids, in aqueous micellar environments, have been obtained from a pulse radiolysis study of electron transfer between the carotenoids and tryptophan radical cations as a function of pH, and lie in the range 980 to 1060 mV. The decays of the carotenoid radical cations suggest a distribution of exponential lifetimes. The radicals persist for up to about one second, depending on the medium and may re-orientate within a biological environment to react with other biomolecules, such as tyrosine, cysteine or ascorbic acid, which was indeed confirmed. Spectral information of carotenoid pigmented liposomes has been collected, subsequently pulse radiolysis was used to generate the radical cations of ?-carotene, zeaxanthin and lutein, in unilamellar vesicles of dipalmitoyl phosphatidyl choline. The rate constants for the 'repair' of these carotenoid radical cations by water-soluble vitamin C were found to be similar (?1 x 107 M-1s-1) for ?-carotene and zeaxanthin and somewhat lower (?0.5 x 107 M-1s-1) for lutein. The results are discussed in terms of the microenvironment of the carotenoids and suggest that for ?-carotene, a hydrocarbon carotenoid, the radical cation is able to interact with a water-soluble species even though the parent hydrocarbon carotenoid is probably entirely in the non-polar region of the liposome. Studies investigating the ability of ingested lycopene to protect human lymphoid cells against singlet oxygen and nitrogen dioxide radical mediated cell damage have shown that a high lycopene diet is beneficial in protecting human cells against reactive oxygen species. Triplet states of carotenoids were produced in benzene solvent and their triplet lifetimes were found to depend on the concentration of the parent molecule. The rate constants obtained for ground state quenching correlate with the number of conjugated double bonds, the longer chain systems having higher quenching rate constants. The efficiency of deactivation of singlet oxygen by three asymmetric carotenoids was measured via time-resolved luminescence detection. In benzene, the deactivation efficiency was found to fit the trend reported previously, in that quenching efficiency increases with increasing wavelength of ??* absorption of the maxima of carotenoids. Both hydroxyl and carbonyl groups were shown to lower the quenching ability. The singlet oxygen deactivation efficiency of carotenoids incorporated within the bilayer of dipalmitoyl phosphotidyl choline liposomes and water/alcohol mixtures was determined concluding that out of the two xanthophylls and one carotene investigated, ?-carotene was the most efficient at singlet oxygen deactivation. The results are discussed in terms of the microenvironment of the carotenoids. (author)

  15. [Erectile rehabilitation after radical prostatectomy].

    Science.gov (United States)

    Droupy, S; Giuliano, F; Costa, P

    2009-12-01

    The concept of penile rehabilitation involves the procedures designed to improve oxygen delivery the penile erectile tissue to minimized tissue damage during the period of neural recovery following radical prostatectomy. Many basic research studies support the rationale and mechanism of the concept of penile rehabilitation, however they are few clinical studies in the literature that provide a clear medical evidence of its efficacy in patients. Waiting for new data, it is recommended to propose to the patients, following a radical prostatectomy, an active pharmacological penile rehabilitation. This rehabilitation involves counselling with the couple to have regular sexual activities, ideally 1 to 3 times a week. Penile erections could be induced by intracavernosal injections of PGE1 or improved by using PDE5 inhibitors on demand. The results of daily use of PDE5 inhibitor are conflicting and then it cannot be recommended systematically waiting for new data. The rehabilitation could be maintained for about 2 years as results improve with time. PMID:20123519

  16. Free radicals and Dupuytren's contracture.

    OpenAIRE

    Murrell, G A; Francis, M. J.; Bromley, L

    1987-01-01

    The concentration of substrate expressed as hypoxanthine capable of reacting with xanthine oxidase to release superoxide free radicals (O2-) was measured in control and Dupuytren's contracture palmar fascia. In Dupuytren's contracture palmar fascia the concentration of hypoxanthine was six times that of control and was greatest in "nodular" areas. Xanthine oxidase activity was also detected in Dupuytren's contracture palmar fascia. These results suggest a greater potential for hypoxanthine-xa...

  17. Penile rehabilitation after radical prostatectomy

    DEFF Research Database (Denmark)

    Fode, Mikkel; Ohl, Dana A; Ralph, David; Sønksen, Jens

    2013-01-01

    The pathophysiology of erectile dysfunction after radical prostatectomy (RP) is believed to include neuropraxia, which leads to temporarily reduced oxygenation and subsequent structural changes in penile tissue. This results in veno-occlusive dysfunction, therefore, penile rehabilitation programmes focus on tissue oxygenation. Animal studies support the use of phosphodiesterase type 5 inhibitors (PDE5Is) after cavernous nerve damage but results from human studies are contradictory. The largest s...

  18. Urogynaecological dysfunction after radical hysterectomy

    DEFF Research Database (Denmark)

    Axelsen, S M; Petersen, L K; Axelsen, Susanne Maigaard

    2006-01-01

    AIMS: To identify self-reported urogynaecological dysfunctions in women treated by radical hysterectomy, and predict risk factors. METHODS: A survey using questionnaires. Questionnaires were mailed to 396 patients. RESULTS: Symptoms of urinary incontinence and urinary retention were reported by more than one-third, respectively. One-third of the patients reported cystitis and dysuria. However, 78% of the women did not consider their symptoms as a problem. Analyses identified body mass index, at ...

  19. Remembering Dutch-Moluccan radicalism

    DEFF Research Database (Denmark)

    Marselis, Randi Lorenz

    2016-01-01

    This article examines memory politics in relation to radical actions of young Dutch-Moluccans, more specifically a train hijacking in 1977 at the village of De Punt in the Netherlands. The article examines how these historical events were remembered in the drama-documentary television film, De Punt (Smitsman, 2009), as well as in user-generated comments in an online discussion. The television film represented an inclusive memory culture that made room for the difficult memories of all parties in...

  20. Remembering Dutch-Moluccan radicalism

    DEFF Research Database (Denmark)

    Marselis, Randi

    1800-01-01

    This article examines memory politics in relation to radical actions of young Dutch-Moluccans, more specifically a train hijacking in 1977 at the village of De Punt in the Netherlands. The article examines how these historical events were remembered in the drama-documentary television film, De Punt (Smitsman, 2009), as well as in user-generated comments in an online discussion. The television film proposed an inclusive memory discourse that acknowledged the difficult memories of all involved par...

  1. Free radical mediated cellulose degradation

    OpenAIRE

    Johansson, Erik

    2003-01-01

    This thesis addresses the mechanisms involved in cellulosedegradation in general and Totally Chlorine Free (TCF) bleachingof pulp in particular. The thesis shows that the cellulosedegradation during high consistency ozone bleaching is explainedby free radical chain reactions. By simulation, it has been shown that the number, weight andviscosity average of liner polymer chain length can be used tocalculate the number of random scissions in a linear polymer ofany molecular weight distribution, ...

  2. Detecting Social Polarization and Radicalization

    DEFF Research Database (Denmark)

    Qureshi, Pir Abdul Rasool; Memon, Nasrullah

    2011-01-01

    This paper proposes a novel system to detect social polarization and to estimate the chances of violent radicalization associated with it. The required processes for such a system are indicated; it is also analyzed how existing technologies can be integrated into the proposed system to fulfill the objectives. We propose a scalable design to enable integration and extension of future state of the art technologies into the system.

  3. 213 nm Ultraviolet Photodissociation on Peptide Anions: Radical-Directed Fragmentation Patterns

    Science.gov (United States)

    Halim, Mohammad A.; Girod, Marion; MacAleese, Luke; Lemoine, Jérôme; Antoine, Rodolphe; Dugourd, Philippe

    2015-11-01

    Characterization of acidic peptides and proteins is greatly hindered due to lack of suitable analytical techniques. Here we present the implementation of 213 nm ultraviolet photodissociation (UVPD) in high-resolution quadrupole-Orbitrap mass spectrometer in negative polarity for peptide anions. Radical-driven backbone fragmentation provides 22 distinctive fragment ion types, achieving the complete sequence coverage for all reported peptides. Hydrogen-deficient radical anion not only promotes the cleavage of C?-C bond but also stimulates the breaking of N-C? and C-N bonds. Radical-directed loss of small molecules and specific side chain of amino acids are detected in these experiments. Radical containing side chain of amino acids (Tyr, Ser, Thr, and Asp) may possibly support the N-C? backbone fragmentation. Proline comprising peptides exhibit the unusual fragment ions similar to reported earlier. Interestingly, basic amino acids such as Arg and Lys also stimulated the formation of abundant b and y ions of the related peptide anions. Loss of hydrogen atom from the charge-reduced radical anion and fragment ions are rationalized by time-dependent density functional theory (TDDFT) calculation, locating the potential energy surface (PES) of ??* and repulsive ??* excited states of a model amide system.

  4. Reactions of hydrocarbon radicals and biradicals.

    Science.gov (United States)

    Pilling, Michael J

    2013-05-01

    Experimental measurements of the rate coefficients for several types of gas phase radical reactions are reviewed. They include radical isomerization and dissociation, radical + radical association, and unimolecular reactions of peroxy radicals. Some reactions of methylene in its lowest singlet state are also considered. The links to theories of chemical reaction rates and especially of capture rates for radical + radical reactions are examined. Many of the reactions involve formation of adducts, which can isomerize and dissociate. Such reactions frequently involve energy distributions of the adducts that are far from Boltzmann, and the interpretation of measurements requires the use of master equation techniques. The basis of these methods and the use of matrix diagonalization and eigenvector/eigenvalue analysis to extract phenomenological rate coefficients are discussed. The relevance of the measurements to applications in atmospheric chemistry and, especially, in combustion is briefly considered. PMID:23570237

  5. Sensitization of Microorganisms and Enzymes by Radiation-Induced Selective Inorganic Radical Anions

    International Nuclear Information System (INIS)

    Bacterial survival and enzymatic inactivation were examined following exposure to radiolytically-generated radical anions, X-2 , where X = Cl, Br, I, or CNS. Depending on pH, radical anions react selectively or specifically with cysteine, tryptophan, tyrosine and histidine. Consequently, when one or more of these amino acids is crucial for enzymatic activity or bacterial survival and is attacked by a radical anion, a high degree or radiosensitization may be realized. Halide radical anions can form free chlorine, bromine or iodine. However, these bactericidal halogens are destroyed by reaction with the hydrated electron, e-aq, or at pHs > 9, as occurs, for example, when a medium saturated with nitrous oxide, N2O , and e-aq scavenger, is replaced by nitrogen or oxygen. Increasing concentration of other e-aq scavengers, such as phosphate buffer, promotes formation of halogen from halides. The conditions producing formation and élimination o f halogens in irradiated media m ust be appreciated to avoid confusing radiosensitization by X2 to X-2. Radiosensitization by radical anions o f several microorganisms: S. faecalis, S. typhimurium, E. coli, and M. radiodurens is described. A crucial amino acid for survival of S. faecalis appears to be tyrosine, while both tyrosine and tryptophan seem essential for recovery of S. typhimurium from effects of ionizing radiation. It is postulated that the radiosensitizing action o f radical anions involves inhibition of DNA repair of strand-breaks by depriving the cells of energy. In view of the high OH scavenging power of foods, it is concluded that the radiosensitization of bacteria and enzymes in foods by radical anions, except for special cases, is not practical. Rather, radical anions serve to identify crucial amino acids to radiosensitization mechanisms in model systems, and possibly in radiotherapy. (author)

  6. In vivo positron emission tomography studies on the novel nicotinic receptor agonist [{sup 11}C]MPA compared with [{sup 11}C]ABT-418 and (S)(-)[{sup 11}C]nicotine in Rhesus monkeys

    Energy Technology Data Exchange (ETDEWEB)

    Sihver, Wiebke E-mail: Wiebke.Sihver@pet.uu.se; Fasth, Karl-Johan; Oegren, Matthias; Lundqvist, Hans; Bergstroem, Mats; Watanabe, Yasuyoshi; Laangstroem, Bengt; Nordberg, Agneta

    1999-08-01

    The novel {sup 11}C-labeled nicotinic agonist (R,S)-1-[{sup 11}C]methyl-2(3-pyridyl)azetidine ([{sup 11}C]MPA) was evaluated as a positron emission tomography (PET) ligand for in vivo characterization of nicotinic acetylcholine receptors in the brain of Rhesus monkeys in comparison with the nicotinic ligands (S)-3-methyl-5-(1-[{sup 11}C]methyl-2-pyrrolidinyl)isoxazol ([{sup 11}C]ABT-418) and (S)(-)[{sup 11}C]nicotine. The nicotinic receptor agonist [{sup 11}C]MPA demonstrated rapid uptake into the brain to a similar extent as (S)(-) [{sup 11}C]nicotine and [{sup 11}C]ABT-418. When unlabeled (S)(-)nicotine (0.02 mg/kg) was administered 5 min before the radioactive tracers, the uptake of [{sup 11}C]MPA was decreased by 25% in the thalamus, 19% in the temporal cortex, and 11% in the cerebellum, whereas an increase was found for the uptake of (S)(-)[{sup 11}C]nicotine and [{sup 11}C]ABT-418. This finding indicates specific binding of [{sup 11}C]MPA to nicotinic receptors in the brain in a simple classical displacement study. [{sup 11}C]MPA seems to be a more promising radiotracer than (S)(-)[{sup 11}C]nicotine or [{sup 11}C]ABT-418 for PET studies to characterize nicotinic receptors in the brain.

  7. In vivo positron emission tomography studies on the novel nicotinic receptor agonist [11C]MPA compared with [11C]ABT-418 and (S)(-)[11C]nicotine in Rhesus monkeys

    International Nuclear Information System (INIS)

    The novel 11C-labeled nicotinic agonist (R,S)-1-[11C]methyl-2(3-pyridyl)azetidine ([11C]MPA) was evaluated as a positron emission tomography (PET) ligand for in vivo characterization of nicotinic acetylcholine receptors in the brain of Rhesus monkeys in comparison with the nicotinic ligands (S)-3-methyl-5-(1-[11C]methyl-2-pyrrolidinyl)isoxazol ([11C]ABT-418) and (S)(-)[11C]nicotine. The nicotinic receptor agonist [11C]MPA demonstrated rapid uptake into the brain to a similar extent as (S)(-) [11C]nicotine and [11C]ABT-418. When unlabeled (S)(-)nicotine (0.02 mg/kg) was administered 5 min before the radioactive tracers, the uptake of [11C]MPA was decreased by 25% in the thalamus, 19% in the temporal cortex, and 11% in the cerebellum, whereas an increase was found for the uptake of (S)(-)[11C]nicotine and [11C]ABT-418. This finding indicates specific binding of [11C]MPA to nicotinic receptors in the brain in a simple classical displacement study. [11C]MPA seems to be a more promising radiotracer than (S)(-)[11C]nicotine or [11C]ABT-418 for PET studies to characterize nicotinic receptors in the brain

  8. New Spectrophotometric Method for Determining Nitrogen Dioxide in Air Using 2,2-azino-bis(3-ethyl benzothiazoline)-6-Sulfonic Acid-Diammonium Salt and Passive Sampling

    OpenAIRE

    Alaa A. Salem; Soliman, Ahmed A.; El-Haty, Ismail A.

    2011-01-01

    A new simple and highly sensitive spectrophotometric method for determining nitrogen dioxide in air was developed. The method is based on converting atmospheric nitrogen dioxide to nitrite ions within the IVL passive samplers used for samples collection. Acidifying nitrite ions with concentrated HCl produced the peroxynitrous acid oxidizing agent which was measured using 2, 2-azino-bis(3-ethyl benzothiazoline)-6-sulfonic acid-diammonium salt (ABTS) as reducing coloring agent. A parallel serie...

  9. DNA lesions derived from the site selective oxidation of Guanine by carbonate radical anions.

    Science.gov (United States)

    Joffe, Avrum; Geacintov, Nicholas E; Shafirovich, Vladimir

    2003-12-01

    Carbonate radical anions are potentially important oxidants of nucleic acids in physiological environments. However, the mechanisms of action are poorly understood, and the end products of oxidation of DNA by carbonate radicals have not been characterized. These oxidation pathways were explored in this work, starting from the laser pulse-induced generation of the primary radical species to the identification of the stable oxidative modifications (lesions). The cascade of events was initiated by utilizing 308 nm XeCl excimer laser pulses to generate carbonate radical anions on submicrosecond time scales. This laser flash photolysis method involved the photodissociation of persulfate to sulfate radical anions and the one electron oxidation of bicarbonate anions by the sulfate radicals to yield the carbonate radical anions. The latter were monitored by their characteristic transient absorption band at 600 nm. The rate constants of reactions of carbonate radicals with oligonucleotides increase in the ascending order: 5'-d(CCATCCTACC) [(5.7 +/- 0.6) x 10(6) M(-)(1) s(-)(1)] laser desorption/ionization time-of-flight mass spectrometry. These assignments were supported by the characteristic circular dichroism spectra of opposite signs of the two lesions. The oxidation of guanine to Sp diastereomers occurs, at least in part, via the formation of 8-oxo-G lesions as intermediates. The Sp lesions can be considered as the terminal products of the oxidation of G and 8-oxo-G in DNA by carbonate radical anions. The mechanistic aspects and biological implications of these site selective reactions in DNA initiated by carbonate radicals are discussed. PMID:14680366

  10. Online radicalization: the net or the netizen?

    Directory of Open Access Journals (Sweden)

    Femi Richard Omotoyinbo

    2014-10-01

    Full Text Available Purpose - Radicalization has gained some unusual prominence in the academic circles; maintaining a generic existence not only in the political sector. And with the advent of the Information Communication Technology (ICT, radicalization has begun to have some virtual dimension even in the remotest of human communities. This study seeks to mobilize a universal awareness on the collective urgency to oppose Online Radicalization (a radicalization that happens through the internet due to its propensity to engendering conflicts. It also aims at identifying the principal cause of online radicalization and steer a clear course for a practical reversal in the systems of online radicalization.Design/methodology/approach - The study is divided into three primary parts. The general notion of radicalization is the focus of the first part; which is further analysed into the levels of online radicalization with its accompanying developments and segments. The second part utilizes analytic and historical method to pinpoint the principal cause of online radicalization amidst the suspected causal factors (the Net and the Netizen. The final part analytically focuses on the Netizen (a user/citizen of the internet as the primary cause of online radicalization, and how the global community can bring about a corresponding change in the Net by the application of some measures on the Netizen.Findings - By virtue of the analytic plus historical methods employed by this study; it was initially identified that radicalization is basically having two versions which are online and offline. Further emphasis on the online version reveals that its existence is only made possible by the availability of the internet (the Net. Since the Net is a global phenomenon online radicalization is considered to be worldwide: a menace of globalization. However, the study later indicated that the Net is a facilitator and a cause of online radicalization. A view was deduced that the Netizen is of two categories that include the broad category and the jargon category. The Netizen in the former category was later on conceived as the principal cause of online radicalization.Research limitations/implications - The study averred that all attempts/measures to bring about a reversal in the status quo of online radicalization [De-Radicalization measures] should be directly applied to the principal cause, which is the Netizen. Although the content of the de-radicalization measures were not fully provided by this study due to the reason that the contents can best be supplied by almost everyone that has a vivid understanding of online radicalization. The study continues to affirm that the application of the measures of de-radicalization on the Netizen will bring a corresponding ameliorative effect on the Net against its perpetuation of online radicalization.Practical implications - It is important for domain name providers, governments, internet service providers, mass media, NGOs, parents, politicians, religious organisations, schools, teachers, and web hosting companies to collaborate to create practicable contents for a Gradual Online De-Radicalization (G.O.D which will suppress the perturbing rate of Online Radicalization to the minimal. No unit or sector can singly tackle online radicalization effectively. Therefore, measures of De-Radicalization should be governed by international treaties and laws, and there should be credible agents to legislate and execute the laws respectively.Originality and value - This study broadens the possibilities of reducing online radicalization to the barest minimum globally with some novel strategies categorized broadly as Gradual Online De-Radicalization (G.O.D. The analytic methods applied were plausible skills from the realm of Philosophy and Science respectively. Thus, the findings and suggestions of this study are considered reasonable and universally pragmatic.Research type - general review and viewpoint.

  11. Chemical composition and free radical scavenging activity of the essential oil of Achillea ligustica growing wild in Lipari (Aeolian Islands, Sicily).

    Science.gov (United States)

    Rouis, Zyed; Maggio, Antonella; Venditti, Alessandro; Bruno, Maurizio; Senatore, Felice

    2013-11-01

    In the present study the chemical composition of the essential oils from aerial parts and flowers of Achillea ligustica All., collected in Lipari (Aeolian Islands) was evaluated by GC and GC-MS. (Z)-Chrysanthenyl acetate was the most abundant component of both oils (29.6% in A1 and 27.8% in F1), followed by viridiflorol (16.8% in A1 and 21.6% in F1), bornyl acetate (8.7% in A1 and 11.6% in F1) and 1,8-cineole (7.4% in A1 and 9.3% in F1). A comparison was made of the composition of the different populations studied so far. Futhermore, the free radical scavenging activity of the oil was determined by DPPH and ABTS methods. PMID:24427958

  12. ?-Tocopherol impact on oxy-radical induced free radical decomposition of DMSO: Spin trapping EPR and theoretical studies

    Science.gov (United States)

    Jerzykiewicz, Maria; ?wiel?g-Piasecka, Irmina; Witwicki, Maciej; Jezierski, Adam

    2011-05-01

    EPR spin trapping and theoretical methods such as density functional theory (DFT) as well as combined DFT and quadratic configuration interaction approach (DFT/QCISD) were used to identify the radicals produced in the reaction of oxy-radicals and dimethyl sulfoxide (DMSO) in the presence and absence of ?-tocopherol. Additionally, the mixtures of ?-tocopherol with linolenic acid and glyceryl trilinoleate as well as bioglycerols (glycerol fractions from biodiesel production) were tested. ?-Tocopherol inhibited oxidation of the main decomposition product of DMSO, •CH 3 to •OCH 3 but did not prevent the transformation process of N-t-butyl- ?-phenylnitrone (PBN) into 2-methyl-2-nitrosopropane (MNP). Theoretical investigations confirmed the structures of proposed spin adducts and allowed to correlate the EPR parameters observed in the experiment with the spin adducts electronic structure.

  13. Laser spectroscopy of hydrocarbon radicals

    Energy Technology Data Exchange (ETDEWEB)

    Chen, P. [Harvard Univ., Cambridge, MA (United States)

    1993-12-01

    The author reports the application of supersonic jet flash pyrolysis to the specific preparation of a range of organic radicals, biradicals, and carbenes in a skimmed molecular beam. Each species was produced cleanly and specifically, with little or no secondary reactions by the thermal dissociation of appropriately designed and synthesized organic precursors. Photoelectron spectra of the three isomeric C{sub 3}H{sub 2} carbenes, ortho-benzyne, and the {alpha},3-dehydrotoluene biradical, were used to establish adiabatic ionization potentials for use in thermochemical determinations.

  14. Aromatic-radical oxidation chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Glassman, I.; Brezinsky, K. [Princeton Univ., NJ (United States)

    1993-12-01

    The research effort has focussed on discovering an explanation for the anomalously high CO{sub 2} concentrations observed early in the reaction sequence of the oxidation of cyclopentadiene. To explain this observation, a number of plausible mechanisms have been developed which now await experimental verification. One experimental technique for verifying mechanisms is to probe the reacting system by perturbing the radical concentrations. Two forms of chemical perturbation of the oxidation of cyclopentadiene were begun during this past year--the addition of NO{sub 2} and CO to the reacting mixture.

  15. Study by ESR of free radicals created by irradiation in some organic substances. Application for dosimetry of the measure of free radicals produced in alanine

    International Nuclear Information System (INIS)

    This report complete the results obtained with free radicals created in glycine. The nature and number of these radicals produced by irradiation in cysteine and glutathion have been investigated free radicals generated in alanine have specially been studied. A linear law exists in a large scale of doses between the number of radicals and the absorbed dose. This property in connection with the high stability of these radicals is very interesting for an use of this amino-acid in dosimetry field. The background of non irradiated alanine is a limit for the best sensibility. With 1 g of alanine in powder, it is possible to make ? measurements between 5 rads and 5. 106 rads. For neutrons, the radicals production yield is lower than for ?. By adding paraffin, it is possible to get a larger yield and to realize compacts dosimeters easier for use than alanine in powder. By adjunction of a higher Z constituent (Ca or Ba for example), it would be possible to improve the yield of the dosimeter for ? energy less than 70 keV. (authors)

  16. Notes on free radicals in the field of human and environmental protection against ionizing radiations

    International Nuclear Information System (INIS)

    It is well known that ionizing radiations, in vitro and in vivo produce, free radicals which may be considered as mediators between physical agents and biological targets. Some aspects of this vast problem are accentuated. Ionizing radiations act either directly on the organic molecules of tissues or indirectly by creating, in the surroundings and in tissular water, inorganic free radicals which act on biochemical molecules to gives new radicals. Analysis of the free radical initiation phenomenon in vivo shows that many initiating agents exist, ionizing radiations representing only one group. The role of oxydants, especially oxydising polluants, and the part played by various enzyme systems (super-oxide dismutase, oxydases etc...) are emphasized. After propagation the chain reactions end in combinations between radicals are stopped by certain organic molecules (radical scavengers). Examples are given (free radical formation from compounds of great biological importance: puric and pyrimidic bases, nucleic acids in particular). These aspects are discussed from the viewpoint of their effects on human and environmental protection against both ionizing radiations and certain chemical pollution

  17. Analysis of phenolic compounds and radical scavenging activity of Echinacea spp.

    Science.gov (United States)

    Pellati, Federica; Benvenuti, Stefania; Magro, Lara; Melegari, Michele; Soragni, Fabrizia

    2004-04-16

    The aim of this study was to set up and validate an RP-LC method with DAD-detection to quantify caffeic acid derivatives in various Echinacea spp. Samples were extracted with 80% methanol. The analyses were carried out on a Lichrospher RP-18 column (125 mm x 4 mm i.d., 5 microm), with a mobile phase gradient, which increases the acetonitrile level in a phosphoric acid solution (0.1%). The flow rate was 1.5 ml/min. Detection was set at 330 nm. This method allowed the identification and quantification of caftaric acid, chlorogenic acid, caffeic acid, cynarin, echinacoside and cichoric acid in Echinacea roots and derivatives. The total phenolic content was 10.49 mg/g for E. angustifolia, 17.83 mg/g for E. pallida and 23.23 mg/g for E. purpurea. Among Echinacea commercial herbal medicines, a certain variability in the concentrations of phenolic compounds was observed. The radical scavenging activity of Echinacea methanolic extracts was evaluated in vitro with a spectrophotometric method based on the reduction of an alcoholic 2,2-diphenyl-1-picrylhydrazyl (DPPH*) radical solution at 517 nm in the presence of a hydrogen donating antioxidant. As for pure compounds, echinacoside had the highest capacity to quench DPPH* radicals (EC50 = 6.6 microM), while caftaric acid had the lowest (EC50 = 20.5 microM). The average EC50 values for E. purpurea, E. pallida and E. angustifolia were 134, 167 and 231 microg/ml, respectively. The radical scavenging activity of Echinacea root extracts reflected their phenolic composition. The results indicate that Echinacea roots and derivatives are a good source of natural antioxidants and could be used to prevent free-radical-induced deleterious effects. PMID:15063463

  18. Antioxidant Mechanisms of Polyphenolic Caffeic Acid Oligomers, Constituents of Salvia officinalis

    OpenAIRE

    WOLF BORS; MICHEL CHRISTA; KURT STETTMAIER; LU YINRONG; FOO L. YEAP

    2004-01-01

    Caffeic acid, rosmarinic acid and oligomers of caffeic acid with multiple catechol groups are all constituents of Salvia officinalis. Their antioxidant potential was investigated with regard to their radical scavenging activity and the stability and structure of the intermediate radicals. Pulse-radiolytic studies revealed very high rate constants with hydroxyl radicals. Evidence from kinetic modeling calculations suggested an unusual complex behavior due to the presence of both O4- and O3-sem...

  19. Radicalization In Pakistan And The Spread Of Radical Islam In Pakistan

    Directory of Open Access Journals (Sweden)

    Bahir ahmad

    2015-08-01

    Full Text Available ABSTRACT It is pertinent to mention that radicalism is not intrinsic to Islam and radical interpretations of the religion or for that matter may occur within any way of life and religion Saikal 2003 and yet the question remains as to why Muslims in certain geographical regions have more radical approaches towards their religion and also that what are the causes of such radicalization. Becoming a radical Muslim is not even a matter of a day nor is it a sudden process. There are several reasons behind making a person radical peaceful angry smiling or tolerant. For knowing the reason behind radicalization or radicals persons one has to understand the causes. Tracing these causes is one of the ways to eliminate such behavior. The first step in the elimination of the radical sentiments in a person is to develop peace in his personality Fair Malhotra amp Shapiro 2010. The chapter which has been addressed here is going to shed light on the roots and symptoms of the radicalism. There will be a brief discussion on how the roots of radicalism can be traced and can be eliminated. The assessment and discussion will be conducted on the parameters of the economy media politics and theology from social cultural point of view. According to the analysis of Ahrari 2000 political factor is one of the major and direct factors which have resulted in causing of the radicalism. These factors however intertwine with one another. Radical actions cannot take place only because of the political factors.

  20. A pulse radiolysis study of salicylic acid and 5-sulpho-salicylic acid in aqueous solutions

    International Nuclear Information System (INIS)

    Reactions of H, OH, eaq- and some one-electron oxidants have been studied with salicylic acid and 5-sulpho-salicylic acid in aqueous solutions. Rate constants for the reaction of eaq- with these compounds were of the order of 109dm3mol-1s-1 and this reaction led to the formation of reducing radicals which could transfer electron to methyl viologen. Other one-electron reductants were not able to reduce these compounds. OH radicals reacted with these compounds by addition pathway with very high rate constants (>1010dm3mol-1s-1) while O- radical anions could oxidize these molecules to give phenoxyl type of radicals. Amongst the one-electron oxidants, only N3 radicals and SO4- radicals could oxidize salicylic acid while 5-sulpho-salicylic acid could be oxidized only by SO4- radicals indicating that while one-electron reduction potential for semi-oxidized SA may beo1 for N3? radical), it is more than 1.33V vs. NHE for semi-oxidized SSA species

  1. A scalable and operationally simple radical trifluoromethylation.

    Science.gov (United States)

    Beatty, Joel W; Douglas, James J; Cole, Kevin P; Stephenson, Corey R J

    2015-01-01

    The large number of reagents that have been developed for the synthesis of trifluoromethylated compounds is a testament to the importance of the CF3 group as well as the associated synthetic challenge. Current state-of-the-art reagents for appending the CF3 functionality directly are highly effective; however, their use on preparative scale has minimal precedent because they require multistep synthesis for their preparation, and/or are prohibitively expensive for large-scale application. For a scalable trifluoromethylation methodology, trifluoroacetic acid and its anhydride represent an attractive solution in terms of cost and availability; however, because of the exceedingly high oxidation potential of trifluoroacetate, previous endeavours to use this material as a CF3 source have required the use of highly forcing conditions. Here we report a strategy for the use of trifluoroacetic anhydride for a scalable and operationally simple trifluoromethylation reaction using pyridine N-oxide and photoredox catalysis to affect a facile decarboxylation to the CF3 radical. PMID:26258541

  2. Radiation inactivation analysis of enzymes. Effect of free radical scavengers on apparent target sizes

    International Nuclear Information System (INIS)

    In most cases the apparent target size obtained by radiation inactivation analysis corresponds to the subunit size or to the size of a multimeric complex. In this report, we examined whether the larger than expected target sizes of some enzymes could be due to secondary effects of free radicals. To test this proposal we carried out radiation inactivation analysis on Escherichia coli DNA polymerase I, Torula yeast glucose-6-phosphate dehydrogenase, Chlorella vulgaris nitrate reductase, and chicken liver sulfite oxidase in the presence and absence of free radical scavengers (benzoic acid and mannitol). In the presence of free radical scavengers, inactivation curves are shifted toward higher radiation doses. Plots of scavenger concentration versus enzyme activity showed that the protective effect of benzoic acid reached a maximum at 25 mM then declined. Mannitol alone had little effect, but appeared to broaden the maximum protective range of benzoic acid relative to concentration. The apparent target size of the polymerase activity of DNA polymerase I in the presence of free radical scavengers was about 40% of that observed in the absence of these agents. This is considerably less than the minimum polypeptide size and may reflect the actual size of the polymerase functional domain. Similar effects, but of lesser magnitude, were observed for glucose-6-phosphate dehydrogenase, nitrate reductase, and sulfite oxidase. These results suggest that secondary damage due to free radicals generated in the local environment as a result of ionizing radiation can influence the apparent target size obtained by this method

  3. Free radical scavenging properties of pyrimidine derivatives

    OpenAIRE

    Bano, Tabassum; Kumar, Nitin; Rupesh DUDHE

    2012-01-01

    Free radicals are well known for playing a dual role in our body- deleterious as well as beneficial. It includes a metabolic pathway for its generation. Oxidative stress in our body occurs due to excessive generation of free radicals and reduced level of antioxidants, but at low concentrations, these radicals help to perform normal physiological functions of the body. Scientific evidence suggests that antioxidants reduce the risk for chronic diseases including cancer and heart disease. This r...

  4. Optimal pain management for radical prostatectomy surgery

    DEFF Research Database (Denmark)

    Joshi, Grish P; Jaschinski, Thomas; Bonnet, Francis; Kehlet, Henrik

    2015-01-01

    BACKGROUND: Increase in the diagnosis of prostate cancer has increased the incidence of radical prostatectomy. However, the literature assessing pain therapy for this procedure has not been systematically evaluated. Thus, optimal pain therapy for patients undergoing radical prostatectomy remains controversial. METHODS: Medline, Embase, and Cochrane Central Register of Controlled Trials were searched for studies assessing the effects of analgesic and anesthetic interventions on pain after radical...

  5. Oxygen free radical scavenger properties of dehydroepiandrosterone.

    OpenAIRE

    POLI, Giuseppe; BOCCUZZI, Giuseppe; Danni, Oliviero; TAMAGNO, Elena; ARAGNO, Manuela

    1998-01-01

    The microsomes from dehydroepiandrosterone (DHEA)-supplemented animals are good hydroxyl radical scavengers, as demonstrated through electron spin resonance and deoxyribose degradation. The ability of DHEA-supplemented microsomes to react with superoxide radical was also demonstrated through the inhibition of nitroblue-tetrazolium reduction determined by superoxide radicals produced in a hypoxanthine-xanthine oxidase system. DHEA-enriched microsomes, obtained from acutely DHEA-treated rats, b...

  6. Customers as Partners in Radical Service Innovation

    DEFF Research Database (Denmark)

    Scupola, Ada; Nicolajsen, Hanne Westh

    2009-01-01

      Purpose- The main purpose of this paper is to investigate customer involvement and related challenges in radical service innovations in engineering consulting services Design/methodology/approach - The paper uses a case study approach and so called rich descriptions to investigate customer involvement, roles and related challenges and conditions in radical service innovations.Findings- One main finding is that customers can engage in radical service innovations in engineering consultancy servi...

  7. Customers as Partners in Radical Service Innovation

    OpenAIRE

    Scupola, Ada; Nicolajsen, Hanne Westh

    2009-01-01

      Purpose- The main purpose of this paper is to investigate customer involvement and related challenges in radical service innovations in engineering consulting services Design/methodology/approach - The paper uses a case study approach and so called rich descriptions to investigate customer involvement, roles and related challenges and conditions in radical service innovations.Findings- One main finding is that customers can engage in radical service innovations in engineering consultancy se...

  8. Identity and Islamic Radicalization in Western Europe

    OpenAIRE

    Murshed, Syed Mansoob; Pavan, Sara

    2009-01-01

    This paper argues that both socio-economic disadvantage and political factors, such as the West’s foreign policy with regard to the Muslim world, along with historical grievances, play a part in the development of Islamic radicalized collective action in Western Europe. We emphasise the role of group identity based individual behaviour in organising collective action within radicalized Muslim groups. Inasmuch as culture plays any role at all in radicalization, it is because individuals feel a...

  9. Prostatectomía radical laparoscópica versus robótica / Laparoscopic radical prostatectomy versus robotic

    Scientific Electronic Library Online (English)

    Felipe, Cáceres; Carlos, Sánchez; Luis, Martínez-Piñeiro; Angel, Tabernero; Sergio, Alonso; Jesús, Cisneros; Pedro Manuel, Cabrera Castillo; Mario, Álvarez Maestro; Mario, Martín Hernández; Manolo, Pérez-Utrilla Pérez; Jesús J. de la, Peña.

    2007-05-01

    Full Text Available Objetivo: La cirugía laparoscópica ha demostrado ser una buena alternativa a la cirugía abierta para el tratamiento del cáncer de próstata localizado. La cirugía robótica podría ser una opción terapéutica. Pretendemos hacer una evaluación de ambas técnicas, analizando una serie de parámetros que nos [...] permitan describir las ventajas e inconvenientes de ambas técnicas. Métodos: Hemos realizado una búsqueda en MED-LINE, revisando las mayores series de Prostatectomía Radical Laparoscópica (PRL) y Prostatectomía Radical Robótica (PRR)y hemos analizado los siguientes parámetros de cada técnica: resultados oncológicos, resultados funcionales, pérdida sanguínea, tasa de transfusión, tiempo quirúrgico, tasa de complicaciones, curva de aprendizaje y coste. Resultados: Ambas técnicas tienen la ventaja de ser mínimamente invasivas, con ventajas en la recuperación del paciente y en los resultados estéticos. La curva de aprendizaje es menor para la prostatectomía robótica, siendo de 10 a 20 casos para ésta y de 50 a 60 casos para la PRL. El análisis de los costes económicos es más favorable para la PRL que tiene un gasto en fungibles por paciente de 533 dólares, siendo éste de 1.705 dólares para la robótica. El precio del robot es de 1.200.000 dólares más un gasto anual de mantenimiento de 100.000 dólares (1). El tiempo operatorio es de 182 min. [141-250] para la robótica y de 234 min. [151-453] para la PRL. Dentro de una misma institución, como ocurre en Montsouris, los tiempos son muy parecidos tardando 155 min. para la robótica y 181 min. para la PRL (tabla 3). El sangrado medio operatorio es de 234 ml. [75-500] para la robótica y de 482 ml. [185-859] para la PRL, dependiendo de la técnica utilizada y de las distintas instituciones. El porcentaje de complicaciones es similar con ambas técnicas. El porcentaje de márgenes quirúrgicos positivos es de 20.6% para la PRL y del 19.24% para la robótica. No se pueden dar todavía resultados a largo plazo sobre recurrencia bioquímica del PSA debido a la corta existencia de ambas técnicas. La tasa de continencia para la PRL es de 56-100% y para la robótica del 70-98%. La tasa de potencia para la PRL es del 25-82% y para la robótica del 79-100%. No existen datos lo suficientemente claros para decir que existan diferencias significativas en cuanto a resultados funcionales. Es difícil evaluar la estancia postoperatoria ya que muchas veces depende de la política de la instituciones médicas, aunque en conjunto no parece que existan diferencias significativas entre ambas técnicas. Conclusiones: La ventajas intraoperatorias y postoperatorias son comparables con las dos técnicas. La prostatectomía robótica tiene una curva de aprendizaje más corta. Son necesarios estudios prospectivos con mayor seguimiento para poder comparar los resultados oncológicos y funcionales. El coste de la PRL es menor que el de la robótica. Abstract in english Objectives: Laparoscopic surgery has demonstrated that it is a good alternative to conventional surgery for the treatment of localized prostate cancer. Robotic surgery could be a therapeutic option. We try to evaluate both techniques, analyzing a series of parameters that allow us to describe the ad [...] vantages and disadvantages of both techniques. Methods: We performed a MEDLINE search and reviewed the main series of laparoscopic radical prostatectomy (LRP) and robotic radical prostatectomy (RRP). The parameters analyzed for each techniques were: oncological results, functional results, blood loss, transfusion rates, surgical times, complications rates, learning curve and cost. Results: Both techniques have the advantage of being minimally invasive, which results in better recovery and aesthetic results. The learning curve of the robotic prostatectomy is shorter, 10 to 20 cases in comparison with 50 to 60 for the LRP. Cost analysis is more favourable for LRP, with a single-use instrument expenditure of 533 dollars per patient in comparison with 1.705 dollars with the robot.

  10. Efficient scavenging of ?-carotene radical cations by antiinflammatory salicylates

    DEFF Research Database (Denmark)

    Cheng, Hong; Liang, Ran; Han, Rui-Min; Zhang, Jian-Ping; Skibsted, Leif Horsfelt

    2014-01-01

    The radical cation generated during photobleaching of ?-carotene is scavenged efficiently by the anion of methyl salicylate from wintergreen oil in a second-order reaction approaching the diffusion limit with k = 3.2 × 10 L mol s in 9:1 v/v chloroform-methanol at 23 °C, less efficiently by the anion of salicylic acid with 2.2 × 10 L mol s, but still of possible importance for light-exposed tissue. Surprisingly, acetylsalicylate, the aspirin anion, reacts with an intermediate rate in a reaction a...

  11. Spin trapping evidence for myeloperoxidase-dependent hydroxyl radical formation by human neutrophils and monocytes

    Energy Technology Data Exchange (ETDEWEB)

    Ramos, C.L.; Pou, S.; Britigan, B.E.; Cohen, M.S.; Rosen, G.M. (Department of Pharmacology and Toxicology, University of Maryland School of Pharmacy, Baltimore (United States))

    1992-04-25

    Using the electron spin resonance/spin trapping system, 4-pyridyl 1-oxide N-tert-butylnitrone (4-POBN)/ethanol, hydroxyl radical was detected as the alpha-hydroxyethyl spin trapped adduct of 4-POBN, 4-POBN-CH(CH3)OH, from phorbol 12-myristate 13-acetate-stimulated human neutrophils and monocytes without the addition of supplemental iron. 4-POBN-CH(CH3)OH was stable in the presence of a neutrophil-derived superoxide flux. Hydroxyl radical formation was inhibited by treatment with superoxide dismutase, catalase, and azide. Treatment with a series of transition metal chelators did not appreciably alter 4-POBN-CH(CH3)OH, which suggested that hydroxyl radical generation was mediated by a mechanism independent of the transition metal-catalyzed Haber-Weiss reaction. Kinetic differences between transition metal-dependent and -independent mechanisms of hydroxyl radical generation by stimulated neutrophils were demonstrated by a greater rate of 4-POBN-CH(CH3)-OH accumulation in the presence of supplemental iron. Detection of hydroxyl radical from stimulated monocyte-derived macrophages, which lack myeloperoxidase, required the addition of supplemental iron. The addition of purified myeloperoxidase to an enzymatic superoxide generating system resulted in the detection of hydroxyl radical that was dependent upon the presence of chloride and was inhibited by superoxide dismutase, catalase, and azide. These findings implicated the reaction of hypochlorous acid and superoxide to produce hydroxyl radical. 4-POBN-CH(CH3)OH was not observed upon stimulation of myeloperoxidase-deficient neutrophils, whereas addition of myeloperoxidase to the reaction mixture resulted in the detection of hydroxyl radical. These results support the ability of human neutrophils and monocytes to generate hydroxyl radical through a myeloperoxidase-dependent mechanism.

  12. Screening of Antioxidant and Radical Scavenging Activity of Vigna ungiculata, Bidens pilosa and Cleome gynandra

    Directory of Open Access Journals (Sweden)

    T. Murenje

    2007-01-01

    Full Text Available This study was conducted to investigate the total phenolics content and the antioxidant activities from methanolic extracts of Vigna ungiculata, Bidens pilosa and Cleome gynandra. Antioxidant and free radical scavenging activity were studied using DPPH and reducing power assays, a?-carotene linoleic acid model system and the inhibition of lipid peroxidation in rat brain. Phenolic compounds were also quantified using HPLC. Total phenolic compounds for Vigna ungiculata, Bidens pilosa and Cleome gynandra were 1136.603±3.869 g g-1, 1102.797±2.239 mg g-1 and 1327.333±1.658 mg g-1 dry mass, respectively. All three vegetable extracts contained vanillin, caffeic acid, p-coumaric acid and ferulic acid. There was an increase in the reducing power effects and inhibition of lipid peroxidation in all samples. All samples showed a time dependent decrease in radical scavenging of DPPH and?-carotene.

  13. Sulfonation of alkyl-benzo[B] thiophene and their 2,3-dihydro derivatives, containing long hydrocarbon radicals

    International Nuclear Information System (INIS)

    The methods of obtaining of sodium salts of sulfonic acids of alkyl-benzo[B] thiophene and their 2,3-dihydro derivatives, containing long hydrocarbon radicals are described in this work. The results of element analysis of sodium salts of sulfonic acids of alkyl-benzo[B] thiophene are presented. The results of infrared spectral analysis are presented as well.

  14. Real-time probing of radical events with sulfide molecules

    Science.gov (United States)

    Gauduel, Yann A.; Glinec, Yannick; Malka, Victor

    2007-02-01

    The physio-pathological roles of sulfide biomolecules in cellular environments involves redox processes and radical reactions that alter or protect the functional properties of enzymatic systems, proteins and nucleic acids repair. We focus on micromolar monitoring of sulfur-centered radical anions produced by direct electron attachment, using sulfide molecules (a thioether and a disulfide biomolecule) and two complementary spectroscopic approaches: low energy radiation femtochemistry (1-8 eV) and high energy radiation femtochemistry (2.5-15 MeV). The early step of a disulfide bond making RS?SR from thiol molecules involves a very-short lived odd-electron bonded intermediate for which an excess electron is transiently localized by a preexisting two sulfide monomers complex. The reactive center of oxidized glutathione (cystamine), a major cytoplasmic disulfide biomolecule, is also used as sensor for the real-time IR investigation of effective reaction radius r eff in homogenous aqueous environments and interfacial water of biomimetic systems. Femtosecond high-energy electrons beams, typically in the 2.5 - 15 MeV range, may conjecture the picosecond observation of primary radical events in nanometric radiation spurs. The real-time investigation of sulfide and disulfide molecules opens exciting opportunities for sensitisation of confined environments (aqueous groove of DNA, protein pockets, sub-cellular systems) to ionizing radiation. Low and high-energy femtoradical probing foreshadow the development of new applications in radiobiology (low dose effect at the nanometric scale) and anticancer radiotherapy (pro-drogue activation).

  15. Photoionisation of the tropyl radical

    Directory of Open Access Journals (Sweden)

    Kathrin H. Fischer

    2013-04-01

    Full Text Available We present a study on the photoionisation of the cycloheptatrienyl (tropyl radical, C7H7, using tunable vacuum ultraviolet synchrotron radiation. Tropyl is generated by flash pyrolysis from bitropyl. Ions and electrons are detected in coincidence, permitting us to record mass-selected photoelectron spectra. The threshold photoelectron spectrum of tropyl, corresponding to the X+ 1A1’ ? X 2E2” transition, reveals an ionisation energy of 6.23 ± 0.02 eV, in good agreement with Rydberg extrapolations, but slightly lower than the value derived from earlier photoelectron spectra. Several vibrations can be resolved and are reassigned to the C–C stretch mode ?16+ and to a combination of ?16+ with the ring breathing mode ?2+. Above 10.55 eV dissociative photoionisation of tropyl is observed, leading to the formation of C5H5+ and C2H2.

  16. Study of free-radical centers in lignin with 2-mm band ESR spectroscopy

    International Nuclear Information System (INIS)

    The nature of paramagnetic centers in pristine lignin and lignin, treated with molecular chlorine, aqueous solutions of acids and alkalis, and ?- and UV-irradiated, was studied with 2-mm band ESR spectroscopy. Most of the observed singlet ESR lines are accounted for by radicals with conjugated bonds. High reactivity of double bonds of polyconjugated systems was in the processes studied

  17. Lipophilic and hydrophilic antioxidants, lipid peroxidation inhibition and radical scavenging activity of two Lamiaceae food plants

    OpenAIRE

    S.F.; Barros, Lillian; Carvalho, Ana Maria; Ferreira, Isabel C. F. R.

    2010-01-01

    Medicinal and aromatic plants are highly prized all over the world. According to local cuisine and pharmacopoeias, they used to be important as dietary supplements, providing bioactive compounds. Herein, we describe lipophilic (fatty acids, tocopherols and carotenoids) and hydrophilic (ascorbic acid, sugars and phenolic compounds) antioxidants, lipid peroxidation inhibition and free radical scavenging activity in aerial parts of two Lamiaceae species (Mentha pulegium and Thymus pulegioides). ...

  18. Reactions of isoprene and sulphoxy radical-anions - a possible source of atmospheric organosulphites and organosulphates

    Science.gov (United States)

    Rudzi?ski, K. J.; Gmachowski, L.; Kuznietsova, I.

    2009-03-01

    Transformation of isoprene coupled with auto-oxidation of SIV in aqueous solutions was studied experimentally and by chemical-kinetic modelling over a broad range of solution acidities (pH=3-9) to complement the research on aqueous-phase and heterogeneous transformation of isoprene reported recently by many laboratories. Isoprene significantly slowed down the auto-oxidation in acidic and basic solutions, and accelerated it slightly in neutral solutions. Simultaneously, production of sulphate ions and formation of solution acidity were significantly reduced. Formation of sulphite and sulphate derivatives of isoprene - sulphurous acid mono-(2-methyl-4-oxo-but-2-enyl) ester (m/z=163), sulphurous acid mono-(4-hydroxy-2-methyl-but-2-enyl) ester (m/z=165), sulphuric acid mono-(2-methyl-4-oxo-but-2-enyl) ester (m/z=179), sulphuric acid mono-(4-hydroxy-2-methyl-but-2-enyl) ester (m/z=181), and possible structural isomers of these species - was indicated by electrospray ionisation mass spectrometric analysis of post-reaction mixtures. The experimental results were explained by changes in a subtle quantitative balance of three superimposed processes whose rates depended in different manner on the acidity of reacting solutions - the scavenging of sulphoxy radical-anions by isoprene, the formation of sulphoxy radical-anions during further reactions of isoprene radicals, and the auto-oxidation of SIV itself. A chemical mechanism based on this idea was explored numerically to show good agreement with experimental data. In basic and neutral solutions, the model overestimated the consumption of isoprene, probably because reactions of primary sulphite and sulphate derivatives of isoprene with sulphoxy radical-anions were not included. Interaction of isoprene with sulphur(IV) species and oxygen can possibly result in formation of new organosulphate and organosulphite components of atmospheric aerosols and waters, and influence the distribution of reactive sulphur and oxygen species in isoprene-emitting organisms exposed to SIV pollutants.

  19. Victimology: A Consideration of the Radical Critique.

    Science.gov (United States)

    Friedrichs, David O.

    1983-01-01

    Discusses the emergence of a new radical model in criminology and a new subdisciplinary area of concern, victimology, with roots in Marx and Engels' original formulations. Argues that the radical understanding of victimization provides an important corrective to mainstream approaches and broadens the focus of the concept of victimization. (JAC)

  20. Radiolysis study of sulfarlem radical reactions

    International Nuclear Information System (INIS)

    Sulfarlem is a sulfured heterocyclic compound which exhibits antioxidant properties. The quantitative study of the monoelectronic exchanges involved in this action has been performed by gamma radiolysis in ethanolic solution. The obtained results indicate that Sulfarlem seems not to be reactive towards peroxyl radicals and superoxide anions. In return it is an efficient scavenger of non oxygenated radicals

  1. Muon spin rotation in free radical chemistry

    International Nuclear Information System (INIS)

    Free radicals have been recognized as reactive intermediates in many important chemical reactions in chemistry, biology and medicine, and consequently free radical research has gained widespread attention. The author introduces the non-specialist to fundamental problems of the field and summarizes established and possible future contributions of ?SR. (Auth.)

  2. Radical Voices; A Film Course Study Guide.

    Science.gov (United States)

    Kernan, Margot

    The leftist radical ideas current in the 1960s and 1970s are expressed in the films discussed in this cinema study guide. The radical film takes extreme and avant-garde approaches to the somewhat publicly taboo topics of sex, social issues, and religion. Among the films discussed, I AM CURIOUS (YELLOW) and SOMETHING DIFFERENT show women in their…

  3. Radical Behaviorism and Buddhism: Complementarities and Conflicts

    Science.gov (United States)

    Diller, James W.; Lattal, Kennon A.

    2008-01-01

    Comparisons have been made between Buddhism and the philosophy of science in general, but there have been only a few attempts to draw comparisons directly with the philosophy of radical behaviorism. The present review therefore considers heretofore unconsidered points of comparison between Buddhism and radical behaviorism in terms of their…

  4. Prostatectomía radical laparoscópica extraperitoneal Extraperitoneal laparoscopic radical prostatectomy

    Directory of Open Access Journals (Sweden)

    OCTAVIO CASTILLO C

    2006-02-01

    Full Text Available Objetivo: Presentamos nuestra experiencia en Prostatectomía Radical Laparoscópica Extraperitoneal (PRLE, destacando la técnica quirúrgica, resultados y complicaciones. Material y Método: Se incluyen 106 pacientes con cáncer de próstata tratados en forma consecutiva en nuestra Unidad mediante PRLE entre mayo del 2000 y enero del 2004. Resultados: La edad promedio fue 61 años (rango: 40-78 años y el valor promedio del antígeno prostático específico fue de 10,31 ng/ml (rango: 1,6-66,8 ng/ml. La técnica quirúrgica fue reproducida en la totalidad de los pacientes. El tiempo quirúrgico promedio fue de 156 min (rango: 80-390 min. El sangrado intraoperatorio promedio fue 577 ml y la tasa de transfusión fue del 26%. Se administró analgesia endovenosa en las siguientes 36 horas a la cirugía y en ningún paciente hubo necesidad de utilizar analgésicos opiáceos. La deambulación ocurrió en las primeras 24 horas del postoperatorio en todos los pacientes y excepto por 3 casos, el drenaje tubular sólo se necesitó en las primeras 24 a 48 horas. La media de la estadía hospitalaria fue 3 días y el tiempo promedio de cateterización vesicouretral fue 7 días. Las complicaciones más frecuentes fueron retención urinaria (6,6%, lesión de recto (5,6%, estrechez de la anastomosis (5,6%, fístula recto-vesical (2.8% y filtración de la anastomosis (2,8%. Conclusión: Nuestra serie ratifica que la PRLE es un procedimiento bien tolerado, con buenos resultados en lo referente a dolor postoperatorio y tiempo de hospitalización. Cuando ocurren complicaciones, éstas tienden a ser más severas que cuando se presentan en cirugía abierta y son dependientes de la experiencia del cirujanoBackground: The extraperitoenal approach for radical prostatectomy is a minimally invasive technique with a low incidence of complications. Aim: To report a series of patients with localized prostate cancer, managed with extraperitoneal laparoscopic radical prostatectomy (ELRP. Patients and Methods: Report of 106 patients (age range 40-78 yearssuccessively subjected to ELRP between May 2002 and January 2004. Results: Preoperative prostate specific antigen ranged from 1.6 to 66.8 ng/ml. Mean operative time was 156 minutes (range: 80-390 minutes. Mean blood loss was 577 mL and transfusion rate was 26%. Analgesics were used in the first 36 hours after surgical procedure and opiates were not required. Mean hospital stay was 3 days and average urinary catheter use was 7 days. The most common complications were urinary retention in 6.6% , rectal lesions in 5.6%, vesico-urethral anastomosis stricture in 5.6%, vesico-rectal fistula in 2.8% and vesico-urethral anastomosis leak in 2.8% of patients. Conclusions: ELRP is a well tolerated procedure, with good operative results in terms of postoperative pain and hospital stay. However, when complications occur, they tend to be more severe than in open surgery

  5. Prostatectomía radical laparoscópica extraperitoneal / Extraperitoneal laparoscopic radical prostatectomy

    Scientific Electronic Library Online (English)

    OCTAVIO, CASTILLO C; RENATO, CABELLO; OSCAR, CORTÉS O; IVÁN, PINTO G; LEONARDO, ARELLANO; MOISÉS, RUSSO.

    2006-02-01

    Full Text Available Objetivo: Presentamos nuestra experiencia en Prostatectomía Radical Laparoscópica Extraperitoneal (PRLE), destacando la técnica quirúrgica, resultados y complicaciones. Material y Método: Se incluyen 106 pacientes con cáncer de próstata tratados en forma consecutiva en nuestra Unidad mediante PRLE e [...] ntre mayo del 2000 y enero del 2004. Resultados: La edad promedio fue 61 años (rango: 40-78 años) y el valor promedio del antígeno prostático específico fue de 10,31 ng/ml (rango: 1,6-66,8 ng/ml). La técnica quirúrgica fue reproducida en la totalidad de los pacientes. El tiempo quirúrgico promedio fue de 156 min (rango: 80-390 min). El sangrado intraoperatorio promedio fue 577 ml y la tasa de transfusión fue del 26%. Se administró analgesia endovenosa en las siguientes 36 horas a la cirugía y en ningún paciente hubo necesidad de utilizar analgésicos opiáceos. La deambulación ocurrió en las primeras 24 horas del postoperatorio en todos los pacientes y excepto por 3 casos, el drenaje tubular sólo se necesitó en las primeras 24 a 48 horas. La media de la estadía hospitalaria fue 3 días y el tiempo promedio de cateterización vesicouretral fue 7 días. Las complicaciones más frecuentes fueron retención urinaria (6,6%), lesión de recto (5,6%), estrechez de la anastomosis (5,6%), fístula recto-vesical (2.8%) y filtración de la anastomosis (2,8%). Conclusión: Nuestra serie ratifica que la PRLE es un procedimiento bien tolerado, con buenos resultados en lo referente a dolor postoperatorio y tiempo de hospitalización. Cuando ocurren complicaciones, éstas tienden a ser más severas que cuando se presentan en cirugía abierta y son dependientes de la experiencia del cirujano Abstract in english Background: The extraperitoenal approach for radical prostatectomy is a minimally invasive technique with a low incidence of complications. Aim: To report a series of patients with localized prostate cancer, managed with extraperitoneal laparoscopic radical prostatectomy (ELRP). Patients and Methods [...] : Report of 106 patients (age range 40-78 years)successively subjected to ELRP between May 2002 and January 2004. Results: Preoperative prostate specific antigen ranged from 1.6 to 66.8 ng/ml. Mean operative time was 156 minutes (range: 80-390 minutes). Mean blood loss was 577 mL and transfusion rate was 26%. Analgesics were used in the first 36 hours after surgical procedure and opiates were not required. Mean hospital stay was 3 days and average urinary catheter use was 7 days. The most common complications were urinary retention in 6.6% , rectal lesions in 5.6%, vesico-urethral anastomosis stricture in 5.6%, vesico-rectal fistula in 2.8% and vesico-urethral anastomosis leak in 2.8% of patients. Conclusions: ELRP is a well tolerated procedure, with good operative results in terms of postoperative pain and hospital stay. However, when complications occur, they tend to be more severe than in open surgery

  6. Biosynthesis of butenoic acid through fatty acid biosynthesis pathway in Escherichia coli.

    Science.gov (United States)

    Liu, Xiping; Yu, Haiying; Jiang, Xu; Ai, Guomin; Yu, Bo; Zhu, Kun

    2015-02-01

    Butenoic acid is a C4 short-chain unsaturated fatty acid mainly used in the preparation of resins, pharmaceuticals, and fine chemicals. However, butenoic acid derived from petroleum is costly and unfriendly to the environment. Here, we report a novel biosynthetic strategy to produce butenoic acid by utilizing the intermediate of fatty acid biosynthesis pathway in engineered Escherichia coli. A thioesterase gene (B. thetaiotaomicron thioesterase (bTE)) from Bacteroides thetaiotaomicron was heterologously expressed in E. coli to specifically convert butenoyl-acyl carrier protein (ACP), a fatty acid biosynthesis intermediate, to butenoic acid. The titer of butenoic acid ranged from 0.07 to 11.4 mg/L in four different E. coli strains with varied expressing vectors. Deletion of endogenous fadD gene (encoding acyl-CoA synthetase) to block fatty acid oxidation improved the butenoic acid production in all strains to some extent. The highest butenoic acid accumulation of 18.7 mg/L was obtained in strain XP-2 (BL21-?fadD/pET28a-bTE). Moreover, partially inhibiting the enoyl-ACP reductase (FabI) of strain XP-2 by triclosan increased butenoic acid production by threefold, and the butenoic acid titer was further increased to 161.4 mg/L by supplying glucose and tryptone in the M9 medium. Fed-batch fermentation of this strain further enhanced butenoic acid production to 4.0 g/L within 48 h. The butenoic acid tolerance assay revealed that this strain could tolerate 15-20 g/L of butenoic acid. PMID:25472435

  7. Physicochemical aspects of isomerisation of free radicals

    Energy Technology Data Exchange (ETDEWEB)

    Denisov, Evgenii T; Denisova, Taisa G [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region (Russian Federation)

    2004-11-30

    Kinetic data on intramolecular abstraction of hydrogen atoms in alkyl, alkoxyl and peroxyl radicals are generalised and analysed. It is shown that the activation energies of these reactions are affected by ring strain. The kinetic parameters of mono- and bimolecular elimination reactions are compared. The difference between the activation energies of these reactions is interpreted using the model of intersecting parabolas. The same model is used to discuss the results of analysis of cyclisation of alkyl radicals; the ring strain energy is shown to play an important role in the activation of these reactions. It is noted that the difference between the electron affinities of the C, N and O atoms is clearly manifested in the cyclisation of aminyl and {omega}-formylalkyl radicals. The kinetic parameters of cyclisation and bimolecular radical addition reactions are compared. The experimental data on the transfer of the vinyl and aryl groups in alkyl radicals are analysed.

  8. Red chicories as potent scavengers of highly reactive radicals: a study on their phenolic composition and peroxyl radical trapping capacity and efficiency.

    Science.gov (United States)

    Rossetto, Monica; Lante, Anna; Vanzani, Paola; Spettoli, Paolo; Scarpa, Marina; Rigo, Adelio

    2005-10-19

    Eight varieties of Cichorium genus vegetables (five heavily red colored, one red spotted, and two fully green) were investigated for their phenolic content (by HPLC and UV-vis spectrophotometry) and for their antioxidant activity. In particular, the capacity (that is, the amount of trapped peroxyl radicals) and the efficiency (that is, the amount of antioxidant necessary to halve the steady-state concentration of peroxyl radicals) were measured. All of the studied chicories are characterized by the presence of a large amount of hydroxybenzoic and hydroxycinnamic acids, whereas the red color is due to cyanidin glycosides. The presence of these phenolics in red chicories confers to them an exceptionally high peroxyl radical scavenging activity in terms of both capacity and efficiency, particularly in their early stage of growth, and makes this popular and low-cost foods comparable or superior to many foods having well-known antioxidant properties such as red wine, blueberry, and tomato. PMID:16218660

  9. HPLC Quantification of Phenolic Acids from Vetiveria zizanioides (L.) Nash and Its Antioxidant and Antimicrobial Activity

    Science.gov (United States)

    Prajna, Jha; Richa, Jindal; Dipjyoti, Chakraborty

    2013-01-01

    Extraction procedure was standardized and for the soluble, glycoside, and wall-bound fractions of phenolic acids from Vetiveria zizanioides. The water soluble alkaline extract which represents the cell wall-bound fraction contained the highest amount of phenolic acids (2.62?±?1.2??M/g fwt GA equivalents). Increased phenolic content in the cell wall indicates more lignin deposition which has an important role in plant defense and stress mitigation. Antioxidant property expressed as percentage TEAC value obtained by ABTS assay was correlated with the amount of phenolic acids and showed a Pearson's coefficient 0.988 (significant at 0.01 level). The compounds p-coumaric acid, p-dihydroxybenzoic acid, and ferulic acid were detected in the acidic extracts by HPLC analysis. The plant extracts exhibited considerable antimicrobial activity against tested bacterial and fungal strains.

  10. Hydroxyl-radical-induced oxidation of cyclic dipeptides: Reactions of free peptide radicals and their peroxyl radicals

    International Nuclear Information System (INIS)

    In the course of this study investigations were carried out into the reactions of hydroxyl radicals and hydrogen atoms with cyclic dipeptides as well as the subsequent reactions of peptide radicals and their peroxyl radicals in aqueous solution. The radiolysis products formed in the absence and presence of oxygen or transient metal complexes were characterized and determined on a quantitative basis. The linking of information from product analyses to the kinetic data for transient species obtained by time-resolving UV/VIS and conductivity measurements (pulse radiolysis) as well as computer-assisted simulations of individual events during the reaction permitted an evaluation of the mechanisms underlying the various processes and an identification of interim products with short life-times, which did or did not belong to the group of radicals. Through the characterization of key reactions of radicals and peroxyl radicals of this substance class a major advance has been made towards a better understanding of the role of radicals in the peptide compound and the mechanisms involved in indirect radiation effects on long-chain peptides and proteins. (orig.)

  11. Oxidative capacity of the Mexico City atmosphere – Part 1: A radical source perspective

    Directory of Open Access Journals (Sweden)

    M. J. Molina

    2007-04-01

    Full Text Available A detailed analysis of OH, HO2 and RO2 radical sources is presented for the near field photochemical regime inside the Mexico City Metropolitan Area (MCMA. During spring of 2003 (MCMA-2003 field campaign an extensive set of measurements was collected to quantify time resolved ROx (sum of OH, HO2, RO2 radical production rates from day- and nighttime radical sources. The Master Chemical Mechanism (MCMv3.1 was constrained by measurements of (1 concentration time-profiles of photosensitive radical precursors, i.e., nitrous acid (HONO, formaldehyde (HCHO, ozone (O3, glyoxal (CHOCHO, and other oxygenated volatile organic compounds (OVOCs; (2 respective photolysis-frequencies (J-values; (3 concentration time-profiles of alkanes, alkenes, and aromatic VOCs (103 compound are treated and oxidants, i.e., OH- and NO3 radicals, O3; and (4 NO, NO2, meteorological and other parameters. The ROx production rate was calculated directly from these observations; MCM was used to estimate further ROx production from unconstrained sources, and express overall ROx production as OH-equivalents (i.e., taking into account the propagation efficiencies of RO2 and HO2 radicals into OH radicals. Daytime radical production is found to be about 10-25 times higher than at night; it does not track the abundance of sunlight. 12-h average daytime contributions of individual sources are: HCHO and O3 photolysis, each about 20%; O3/alkene reactions and HONO photolysis, each about 15%; unmeasured sources about 30%. While the direct contribution of O3/alkene reactions appears to be moderately small, source-apportionment of ambient HCHO and HONO identifies O3/alkene reactions as being largely responsible for jump-starting photochemistry about one hour after sunrise. The peak radical production is found to be higher than in any other urban influenced environment studied to date; further, differences exist in the timing of radical production. Our measurements and analysis comprise a database that enables testing of the representation of radical sources in photochemical models. Since the photochemical processing of pollutants is radical-limited in the MCMA, our analysis identifies the drivers for such processing. Three pathways are identified by which reductions in VOC emissions induce reductions in peak concentrations of secondary pollutants, such as O3 and secondary organic aerosol (SOA.

  12. Detection of glutathione free radical catalyzed by prostaglandin hydroperoxidase present in intact epidermal cells

    International Nuclear Information System (INIS)

    The authors report the application of the electron spin resonance technique to detect free radicals catalyzed by prostaglandin hydroperoxidase in intact cells. Studies were done using skin epithelial cells obtained from hairless mice which possess significant prostaglandin H synthase (PHS) activity. A technique was developed using ram seminal vesicles for magnification of the enzymatic activity based on the ability of some free radicals formed by PHS to oxidize glutathione to a thiyl radical which was trapped by DMPO. Using this approach they detected a GSH-DMPO adduct catalyzed by cellular PHS. The addition of glutathione stimulated the formation of GSH-DMPO adduct which suggests that most of the oxidation of GSH occurred extracellularly. The addition of the peroxidase substrate phenol greatly stimulated the oxidation of 3H-arachidonic acid to prostaglandins. The addition of glutathione peroxidase completely inhibited the oxidation of arachidonic acid and the formation of the GSH-DMPO radical adduct. These results suggest that prostaglandin H synthase dependent co-oxidation of chemicals can result in the intracellular formation of free radical metabolites

  13. Oxidation of caffeine by phosphate radical anion in aqueous solution under anoxic conditions

    Indian Academy of Sciences (India)

    Maram Ravi Kumar; Mundra Adinarayana

    2000-10-01

    The photooxidation of caffeine in presence of peroxydiphosphate (PDP) in aqueous solution at natural H (?7 5) has been carried out in a quantum yield reactor using a high-pressure mercury lamp. The reactions were followed spectrophotometrically by measuring the absorbance of caffeine at {}_${\\max}$ (272 nm). The rates of reaction were calculated under different experimental conditions. The quantum yields were calculated from the rates of oxidation of caffeine and the intensity of light at 254 nm which was measured by using peroxydisulphate solution as a standard chemical actinometer. The reaction rates of oxidation of caffeine by PDP increase with increase in [PDP] as well as with increase in light intensity, while they are independent of [caffeine]. The quantum yields of oxidation of caffeine by PDP are independent of [PDP] as well as light intensity. However, quantum yields of oxidation of caffeine by PDP increase with increase in caffeine concentration. On the basis of these experimental results and product analysis, a probable mechanism has been suggested in which PDP is activated to phosphate radical anions (PO$_4^{.2-}$) by direct photolysis of PDP and also by the sensitizing effect of caffeine. The phosphate radical anions thus produced react with caffeine by electron transfer reaction, resulting in the formation of caffeine radical cation, which deprotonates in a fast step to produce C8OH adduct radicals. These radicals might react with PDP to give final product 1,3,7-trimethyluric acid and PO$_4^{.2-}$ radicals, the latter propagates the chain reaction.

  14. Alginate oligosaccharides

    DEFF Research Database (Denmark)

    Falkeborg, Mia; Cheong, Ling-Zhi; Gianfico, Carlo; Magdalena Sztukiel, Katarzyna; Kristensen, Kasper; Glasius, Marianne; Xu, Xuebing; Guo, Zheng

    2014-01-01

    Alginate oligosaccharides (AOs) prepared from alginate, by alginate lyase-mediated depolymerization, were structurally characterized by mass spectrometry, infrared spectrometry and thin layer chromatography. Studies of their antioxidant activities revealed that AOs were able to completely (100%) inhibit lipid oxidation in emulsions, superiorly to ascorbic acid (89% inhibition). AOs showed radical scavenging activity towards ABT?, hydroxyl, and superoxide radicals, which might explain their excel...

  15. Hypochlorite-induced oxidation of thiols : formation of thiyl radicals and the role of sulfenyl chlorides as intermediates

    DEFF Research Database (Denmark)

    Davies, Michael Jonathan; Hawkins, C L

    2000-01-01

    Activated phagocytic cells generate hypochlorite (HOCl) via release of hydrogen peroxide and the enzyme myeloperoxidase. HOCl plays an important role in bacterial cell killing, but excessive or misplaced production of HOCI is also known to cause tissue damage. Studies have shown that low-molecular-weight thiols such as reduced glutathione (GSH), and sulfur-containing amino acids in proteins, are major targets for HOCl. Radicals have not generally been implicated as intermediates in thiol oxidation by HOCl, though there is considerable literature evidence for the involvement of radicals in the metal ion-, thermal- or UV light-catalysed decomposition of sulfenyl or sulfonyl chlorides which are postulated intermediates in thiol oxidation. In this study we show that thiyl radicals are generated on reaction of a number of low-molecular-weight thiols with HOCl. With sub-stoichiometric amounts of HOCl, relative to the thiol, thiyl radicals are the major species detected by EPR spin trapping. When the HOCl is presentin excess over the thiol, additional radicals are detected with compounds which contain amine functions; these additional radicals are assigned to nitrogen-centered species. Evidence is presented for the involvement of sulfenyl chlorides (RSCl) in the formation of these radicals, and studies with an authentic sulfenyl chloride have demonstrated that this compound readily decomposes in thermal-, metal-ion- or light-catalysed reactions to give thiyl radicals. The formation of thiyl radicals on oxidation of thiols with HOCl appears to compete with non-radical reactions. The circumstances under which radical formation may be important are discussed.

  16. Tyrosine radicals in photosystem II and related model compounds. Characterization by isotopic labeling and EPR spectroscopy

    International Nuclear Information System (INIS)

    Deuteration at selected positions on the phenol ring and at the beta-methylene carbon for the YD.tyrosine radical in Photosystem II in the cyanobacterium Synechocystis 6803 was achieved by growing the organism under conditions in which it is a functional aromatic amino acid auxotroph. A series of model tyrosine radicals, also deuterated at specific sites on the aromatic ring and the methylene group, was generated by UV irradiation of frozen solutions. The EPR spectra of the specifically deuterated in vivo radicals confirm that YD.is a tyrosine; nevertheless its spectra differ from those of the tyrosine models. By comparing the EPR spectra of the specifically deuterated radicals with those of the fully protonated, the hyperfine couplings of the various protons of both YD.and the model compound radicals were determined. For both species, the unpaired electron spin density distribution is essentially identical and follows an odd-alternant pattern with high rho values at the carbons ortho and para to the tyrosine phenol oxygen; the meta positions have low spin densities. The differences in EPR spectral characteristics for the two radicals are rationalized as arising from variations in the conformation of the beta-methylene group with respect to the phenol head group. Considering these EPR results and those reported for other model and naturally occurring tyrosine radicals, we conclude that this situation is general; there is little deviation in this class of compounds from the odd-alternant spin density distribution; variations in EPR lineshapes arise primarily from variations in beta-methylene orientation. The conformation of the -CH2- group in biologically active tyrosine radicals deviates from that observed in the models and may be functionally significant

  17. Evaluation of Antioxidant and Free Radical Scavenging Activities of Plumeria acuminata Leaves

    Directory of Open Access Journals (Sweden)

    M. Gupta

    2007-01-01

    Full Text Available The present study was aimed out to evaluate the antioxidant and free radical scavenging activity of methanolic extract of Plumeria acuminata leaves (Apocynaceae in various systems. DPPH radical, superoxide anion radical, nitric oxide radical and hydroxyl radical scavenging assays were carried out to evaluate the antioxidant potential of the extract. The antioxidant activity of methanolic extract increased in a dose dependent manner. About 50, 100, 200, 300, 400 and 500 ?g of Methanol Extract of Plumeria acuminata (MEPA showed 46.01, 52.83, 57.43, 61.38, 68.27 and 73.14% inhibition, respectively on peroxidation of linoleic acid emulsion. Like antioxidant activity, the effect of MEPA on reducing power increases in a dose dependent manner. In DPPH radical and nitric oxide radical scavenging assays, MEPA exhibited maximum activity of 60.42 and 56.38% inhibition at the concentration of 125 ?g mLG-1. Moreover, the MEPA was found to scavenge the superoxide generated by PMS/NADH-NBT system. MEPA was also found to inhibit the hydroxyl radical generated by Fenton`s reaction, where the IC50 value of MEPA was found to be 74.39 ?g mLG-1 and for catechin the IC50 value was found to be 5.27 ?g mLG-1, which indicates the prooxidant activity of MEPA. The amounts of total phenolic compounds were also determined in this study. The results obtained in the present study indicate that the MEPA can be a potential source of natural antioxidant.

  18. Effects of natural water constituents on the photo-decomposition of methylmercury and the role of hydroxyl radical

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Moon-Kyung; Zoh, Kyung-Duk, E-mail: zohkd@snu.ac.kr

    2013-04-01

    Photo-decomposition of methylmercury (MeHg) in surface water is thought to be an important process that reduces the bioavailability of mercury (Hg) to aquatic organisms. In this study, photo-initiated decomposition of MeHg was investigated under UVA irradiation in the presence of natural water constituents including NO{sub 3}{sup ?}, Fe{sup 3+}, and HCO{sub 3}{sup ?} ions, and dissolved organic matter such as humic and fulvic acid. MeHg degradation followed the pseudo-first-order kinetics; the rate constant increased with increasing UVA intensity (0.3 to 3.0 mW cm{sup ?2}). In the presence of NO{sub 3}{sup ?}, Fe{sup 3+}, and fulvic acid, the decomposition rate of MeHg increased significantly due to photosensitization by reactive species such as hydroxyl radical. The presence of humic acid and HCO{sub 3}{sup ?} ions lowered the degradation rate through a radical scavenging effect. Increasing the pH of the solution increased the degradation rate constant by enhancing the generation of hydroxyl radicals. Hydroxyl radicals play an important role in the photo-decomposition of MeHg in water, and natural constituents in water can affect the photo-decomposition of MeHg by changing radical production and inhibition. - Highlights: ? The abiotic photodecomposition of methylmercury (MeHg) in water was examined. ? UVA light is a primary factor inducing MeHg photodecomposition in water. ? Fulvic acid, NO{sub 3}{sup ?}, and Fe{sup 3+} ion increased MeHg photo-decomposition rate significantly. ? Humic acid and HCO{sub 3}{sup ?} ions inhibited photodecomposition through radical scavenging. ? OH radical is an important compound affecting photodecomposition of MeHg in water.

  19. Effects of natural water constituents on the photo-decomposition of methylmercury and the role of hydroxyl radical

    International Nuclear Information System (INIS)

    Photo-decomposition of methylmercury (MeHg) in surface water is thought to be an important process that reduces the bioavailability of mercury (Hg) to aquatic organisms. In this study, photo-initiated decomposition of MeHg was investigated under UVA irradiation in the presence of natural water constituents including NO3?, Fe3+, and HCO3? ions, and dissolved organic matter such as humic and fulvic acid. MeHg degradation followed the pseudo-first-order kinetics; the rate constant increased with increasing UVA intensity (0.3 to 3.0 mW cm?2). In the presence of NO3?, Fe3+, and fulvic acid, the decomposition rate of MeHg increased significantly due to photosensitization by reactive species such as hydroxyl radical. The presence of humic acid and HCO3? ions lowered the degradation rate through a radical scavenging effect. Increasing the pH of the solution increased the degradation rate constant by enhancing the generation of hydroxyl radicals. Hydroxyl radicals play an important role in the photo-decomposition of MeHg in water, and natural constituents in water can affect the photo-decomposition of MeHg by changing radical production and inhibition. - Highlights: ? The abiotic photodecomposition of methylmercury (MeHg) in water was examined. ? UVA light is a primary factor inducing MeHg photodecomposition in water. ? Fulvic acid, NO3?, and Fe3+ ion increased MeHg photo-decomposition rate significantly. ? Humic acid and HCO3? ions inhibited photodecomposition through radical scavenging. ? OH radical is an important compound affecting photodecomposition of MeHg in water

  20. Kinetics of Propargyl Radical Dissociation.

    Science.gov (United States)

    Klippenstein, Stephen J; Miller, James A; Jasper, Ahren W

    2015-07-16

    Due to the prominent role of the propargyl radical for hydrocarbon growth within combustion environments, it is important to understand the kinetics of its formation and loss. The ab initio transition state theory-based master equation method is used to obtain theoretical kinetic predictions for the temperature and pressure dependence of the thermal decomposition of propargyl, which may be its primary loss channel under some conditions. The potential energy surface for the decomposition of propargyl is first mapped at a high level of theory with a combination of coupled cluster and multireference perturbation calculations. Variational transition state theory is then used to predict the microcanonical rate coefficients, which are subsequently implemented within the multiple-well multiple-channel master equation. A variety of energy transfer parameters are considered, and the sensitivity of the thermal rate predictions to these parameters is explored. The predictions for the thermal decomposition rate coefficient are found to be in good agreement with the limited experimental data. Modified Arrhenius representations of the rate constants are reported for utility in combustion modeling. PMID:25871530

  1. Urogynaecological dysfunction after radical hysterectomy

    DEFF Research Database (Denmark)

    Axelsen, S M; Petersen, L K

    2006-01-01

    AIMS: To identify self-reported urogynaecological dysfunctions in women treated by radical hysterectomy, and predict risk factors. METHODS: A survey using questionnaires. Questionnaires were mailed to 396 patients. RESULTS: Symptoms of urinary incontinence and urinary retention were reported by more than one-third, respectively. One-third of the patients reported cystitis and dysuria. However, 78% of the women did not consider their symptoms as a problem. Analyses identified body mass index, at least one delivery, pre-operative urinary incontinence, and pulmonary disease as predictors for development of post-operative urinary incontinence. Predictive variables for urinary retention symptoms were age, cystitis and/or dysuria, previous rupture of the anal sphincter, fetal weight at delivery > or =4000 g, sensation of vaginal dryness, and pre-operative urinary retention symptoms. Considering post-operative cystitis and/or dysuria, fetal weight > or =4000 g, sensation of vaginal dryness, cystitis and/or dysuriabefore the operation, and physical activity were predictive variables. CONCLUSIONS: Patients can be informed and advised about possible urinary tract symptoms. Special attention in the pre- and post-operative period can be paid to a subgroup of patients at high risk of later urogynaecological problems.

  2. ORGASMIC FUNCTION AFTER RADICAL PROSTATECTOMY

    Directory of Open Access Journals (Sweden)

    D. Yu. Pushkar

    2014-07-01

    Full Text Available Objective: to study orgasmic function (OF in patients undergoing radical prostatectomy (RPE.Subjects and methods. Seventy-nine patients who had undergone RPE for locally advanced prostate cancer without hormone and radiation therapies were examined. The patients’ mean age was 59.3 years. The mean EF-IIEF domain score was 24.4. OF was estimated by IIEF question 10 and the authors’ questionnaire. The Spearman rank correction coefficient and Mann-Whitney U-Wilcoxon tests were used.Results. After RPE, there was a reduction in the mean IIEF question 10 score from 3.9 (confidence interval 3.7–4.1 to 3.3 (3–3.5 (p = 0.000. The following changes were found in orgasm intensity: no changes in 43 %, mild worsening in 42 %, severe worsening in 8 %, and enhancement in 4 %; orgasm could not be achieved in 4 % of the patients. Pain usually of low intensity was reported by 8.8 %. The poor factors for preserving OF were its low baseline level, elderly age, or severe post-RPE erectile dysfunction.Conclusion. There were significant OF changes after RPE, which should be kept in mind while treating this category of patients.

  3. Radical Testing of Firewall Schemes

    Directory of Open Access Journals (Sweden)

    Vagolu Vanaja1 , Sandhya2 , Betam Suresh

    2013-08-01

    Full Text Available Firewall is an application software that plays a major role in securing the private networks, so that is the reason why this firewalls are becoming as a popular applications in enterprise security as the quality of protection provided by a firewall directly depends on the quality of its policy (i.e., configuration, ensuring the correctness of firewall policies is important and yet difficult. To help ensure the correctness, we propose a radical testing approach for firewall policies. Here in this paper we are proposing a test that can successfully test the firewall policy which will check for two things one is Authentication and one more is malware if the node is not in the list of authenticated and also if it found any packet having malware automatically it blocks that particular IP from the next time onwards.We have conducted a test on a set of firewall policies and a set of faulty policies to detect malicious packets with default packets. Generally, our experimental results state that a higher structural coverage packet has the higher fault detection capability. Coming to the reduced Structural coverage maintains the same fault detection level with the original set.

  4. Radiation effects on crystalline L-asparagine, revisited: Radical formation by EMR and periodic DFT after X-irradiation at 275 K

    International Nuclear Information System (INIS)

    Radical formation by X-irradiation of single crystals of L-asparagine monohydrate at 275 K has been investigated at 240 K and 295 K using Electron Paramagnetic Resonance (EPR), Electron Nuclear DOuble Resonance (ENDOR) and ENDOR-Induced EPR spectroscopic techniques. Free radical structures suggested by detailed analysis of the experimental data were assessed by Density Functional Theory calculations in a periodic approach. The combined experimental and computational evidence revealed three stable radical species at room temperature. Two of these could reliably be established as net H-abstracted species, one from the methylene group in the amino acid side chain and the second from the amino acid back-bone carbon atom. For the third room temperature radical species, a variety of deamination- and decarboxylation products were investigated and dismissed. Even if an unambiguous structure could not be established, this radical is tentatively suggested to descend from a side-chain O3-protonated amide anion by hydrogen atom transfer from the C3 to the C4 position. - Highlights: • Radicals in L-aspargine at 295 K investigated using EPR, ENDOR, EIE and DFT. • Radicals by net loss of H-atom from the backbone and sidechain are identified. • A possible successor from a primary side-chain amide anion has been observed. • Radical characterization has been supported by periodic boundary DFT calculations. • Deamination and decarboxylation radicals at room temperature were not observed

  5. Prostatectomía radical extraperitoneal Da Vinci / Extraperitoneal radical prostatectomy Da Vinci

    Scientific Electronic Library Online (English)

    H., John; D.M., Schmid; J.L., Fehr.

    2007-06-01

    Full Text Available Objetivo. Informar de la evolución de 100 prostatectomías radicales laparoscópicas asistidas por robot (RALPs), una alternativa minimamente invasiva para el tratamiento del cáncer de próstata. Pacientes y métodos. Se realizó un abordaje extraperitoneal asistidos por el sistema quirúrgico robótico Da [...] Vinci. Los datos prospectivos incluyeron cuestionarios de calidad de vida, demografía básica (peso, altura e índice de masa corporal), niveles de PSA, estadio clínico y suma de Gleason. Las variables intraoperatorias evaluadas fueron duración de la cirugía, pérdida sanguínea estimada (EBL) y complicaciones. Post-operatoriamente se evaluaron los días de estancia en el hospital, días con catéter uretral, histopatología, niveles de PSA, recuperación de la continencia y la potencia. Resultados. La duración media de la RALP fue de 180 minutos (rango 140-295); todos los procedimientos tuvieron éxito y no se registraron transfusiones sanguíneas ni muertes relacionadas con la cirugía. La EBL media fue 300 cc (40 -1100); 97 % de los pacientes fueron dados de alta el primer dia de post-operatorio con 36 % de hematocrito. La duración media del cateterismo uretral fue 7 días (5-21). La tasa de margenes positivos fue del 14 %. La continencia a los 6 meses fue del 95 %. La supervivencia libre de recidiva bioquímica fue del 95 % al año. Al año 78 % de los pacientes eran potentes( con o sin ayuda farmacológica), 15 % no eran capaces de mantener la erección para penetrar y 7 % necesitaban aún inyecciones intracavernosas. Conclusión: La prostatectomía radical laparoscópica asistida por robot se caracteriza por un control máximo en cuanto a la resección de tejido, una pérdida de sangre mínima y unos resultados funcionales muy buenos. Abstract in english Objetive. To report the outcomes of 100 robotically assisted laparoscopic radical prostatectomies (RALPs), a minimally invasive alternative for treating prostate cancer. Patients and methods. In all patients was used RALP with an extraperitoneal approach assisted by the da Vinci robotic surgical sys [...] tem (Intuitive Surgical, Sunnyvale, CA, USA). Prospective data collection included quality-of-life questionnaires, basic demographics (height, weight and body mass index), prostate specific antigen (PSA) levels, clinical stage and Gleason grade. Variables assessed during RALP were operative duration, estimated blood loss (EBL) and complications, and after RALP were hospital stay, catheter time, pathology, PSA level, return of continence and potency. Results. The mean (range) duration of RALP was 180 (140-295) min; all procedures were successful, with no intraoperative transfusions or deaths. The mean EBL was 300 mL (40 - 1100); 97% of patients were discharged home on the first day after RALP with a mean haematocrit of 36%. The mean duration of catheterization was 7 (5-21) days. The positive margin rate was 14% for all patients. The overall biochemical recurrence free (PSA level

  6. Measurement of Hydroxyl-Radical Formation in the Rat Striatum by In Vivo Microdialysis and GC–MS

    OpenAIRE

    Nguyen, V.; Bonds, D. V.; Prokai, L

    2008-01-01

    A GC-MS method was developed for measuring hydroxyl-radical capture products of salicylic acid, a common trapping agent for this reactive oxygen species, in samples obtained by in vivo cerebral microdialysis experiments. The assay employed liquid-liquid extraction followed by derivatization of 2,3- and 2,5-dihydroxybenzoic acid, along with 3,5-dihydroxybenzoic acid added as an internal standard. Due to their simple electron ionization mass spectra featuring [M – 57]+ ions through the loss of ...

  7. Radiation effect on polyadenylic acid in aqueous solution

    International Nuclear Information System (INIS)

    In this study, dilute solution properties of polyadenylic acid (polyA), G values for single strand break formation G(ssb), Arrhenius parameters (25-45 oC), the kinetics of strand break in the absence and presence of radical scavengers have been studied. OH radicals were produced from gamma radiolysis of water, which is supposed to be the main primary radical causing single strand break formation. (Author)

  8. Aspartic acid

    Science.gov (United States)

    Aspartic acid is a nonessential amino acids . Amino acids are building blocks of proteins. "Nonessential" means that our ... this amino acid from the food we eat. Aspartic acid is also called asparaginic acid. Aspartic acid helps ...

  9. Generation of radicals by bimolecular reactions

    Energy Technology Data Exchange (ETDEWEB)

    Denisov, Evgenii T; Denisova, Taisa G [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region (Russian Federation)

    2002-05-31

    The published data on bimolecular processes of radical generation in chain degradation, polymerisation, oxidation and halogenation reactions of organic compounds are systematised and analysed within the framework of the parabolic model of homolytic bimolecular reactions. The specific features of these highly endothermic reactions are discussed with a special emphasis on their striking similarity to radical abstraction processes with identical reaction centres in the transition state. The feasibility of theoretical evaluation of the activation energies and the rate constants of bimolecular reactions in radical generation is demonstrated. The bibliography includes 86 references.

  10. Echinacoside and caffeoyl conjugates protect collagen from free radical-induced degradation: a potential use of Echinacea extracts in the prevention of skin photodamage.

    Science.gov (United States)

    Facino, R M; Carini, M; Aldini, G; Saibene, L; Pietta, P; Mauri, P

    1995-12-01

    The protective effect of caffeoyl derivatives (echinacoside, chlorogenic acid, chicoric acid, cynarine, and caffeic acid, typical constituents of Echinacea species) on the free radical-induced degradation of Type III collagen has been investigated. The macromolecule was exposed to a flux of oxygen radicals (superoxide anion and hydroxyl radical) generated by the xanthine/xanthine oxidase/Fe2+/EDTA system and its degradation assessed qualitatively by SDS-PAGE and quantitatively as the amount of soluble peptides (according to the 4-hydroxyproline method) released from native collagen after oxidative stress. The SDS-PAGE pattern of native collagen is markedly modified by free radical attack, with formation of a great number of peptide fragments with molecular masses below 97 kDa: in the presence of microM concentrations of echinacoside, there is a complete recovery of the native profile. Collagen degradation was, in fact, dose-dependently inhibited by all the compounds, with the following order of potency: echinacoside approximately chicoric acid > cynarine approximately caffeic acid > chlorogenic acid, with IC50 ranging from 15 to 90 microM. These results indicate that this representative class of polyphenols of Echinacea species protects collagen from free radical damage through a scavenging effect on reactive oxygen species and/or C-, N-, S-centered secondary radicals, and provide an indication for the topical use of extracts from Echinacea species for the prevention/treatment of photodamage of the skin by UVA/UVB radiation, in which oxidative stress plays a crucial role. PMID:8824943

  11. Secoiridoid glucosides with free radical scavenging activity from the leaves of Syringa dilatata.

    Science.gov (United States)

    Oh, Hyuncheol; Ko, Eun-Kyoung; Kim, Do-Hoon; Jang, Kyu-Kwan; Park, Sung-Eun; Lee, Ho-Sub; Kim, Youn-Chul

    2003-04-01

    Activity-guided fractionation of the EtOAc and MeOH extract of the leaves of Syringa dilatata NAKAI furnished one free radical scavenger, the secoiridoid glucoside oleuropein together with ligstroside and an iridoid glucoside, syringopicroside. Oleuropein interacted with the stable free radical, 1,1-diphenyl-2-picrylhydrazyl (DPPH), and showed an IC(50) value of 40.4 microM. L-Ascorbic acid as a positive control showed an IC(50) value of 50.3 microM. PMID:12722154

  12. Biochemical and radical-scavenging properties of sea cucumber (Stichopus vastus) collagen hydrolysates.

    Science.gov (United States)

    Abedin, Md Zainul; Karim, Alias A; Latiff, Aishah A; Gan, Chee-Yuen; Ghazali, Farid Che; Barzideh, Zoha; Ferdosh, Sahena; Akanda, Md Jahurul Haque; Zzaman, Wahidu; Karim, Md Rezaul; Sarker, Md Zaidul Islam

    2014-01-01

    The molecular mass distribution, amino acid composition and radical-scavenging activity of collagen hydrolysates prepared from collagen isolated from the sea cucumber Stichopus vastus were investigated. ? and ?1 chains of the collagen were successfully hydrolysed by trypsin. The molecular mass distribution of the hydrolysates ranged from 5 to 25 kDa, and they were rich in glycine, alanine, glutamate, proline and hydroxyproline residues. The hydrolysates exhibited excellent radical-scavenging activity. These results indicate that collagen hydrolysates from S. vastus can be used as a functional ingredient in food and nutraceutical products. PMID:24670209

  13. Determination of the rate constant of hydroperoxyl radical reaction with phenol

    International Nuclear Information System (INIS)

    The rate constant of HO2· reaction with phenol (kHO2·+phenol) was investigated. The primary radical set produced in water ? radiolysis (·OH, eaq? and H·) was transformed to HO2·/O2·? by using dissolved oxygen and formate anion (in the form of either formic acid or sodium formate). The concentration ratio of HO2·/O2·? was affected by the pH value of the solution: under acidic conditions (using HCOOH) almost all radicals were converted to HO2·, while under alkaline conditions (using HCOONa) to O2·?. The degradation rate of phenol was significantly higher using HCOOH. From the ratio of reaction rates under the two reaction conditions kHO2·+phenol was estimated to be (2.7±1.2)×103 L mol?1 s?1. - Highlights: • Using formic acid and dissolved O2 almost all radicals are converted to HO2·. • Using sodium formate and dissolved O2 almost all radicals are converted to O2·?. • The kHO2·+phenol was estimated to be (2.7±1.2)×103 L mol?1 s?1. • HO2· is suggested to contribute significantly to the degradation of phenol

  14. Pulsed radiation studies of carotenoid radicals and excited states

    Energy Technology Data Exchange (ETDEWEB)

    Burke, M

    2001-04-01

    The one-electron reduction potentials of the radical cations of five dietary carotenoids, in aqueous micellar environments, have been obtained from a pulse radiolysis study of electron transfer between the carotenoids and tryptophan radical cations as a function of pH, and lie in the range 980 to 1060 mV. The decays of the carotenoid radical cations suggest a distribution of exponential lifetimes. The radicals persist for up to about one second, depending on the medium and may re-orientate within a biological environment to react with other biomolecules, such as tyrosine, cysteine or ascorbic acid, which was indeed confirmed. Spectral information of carotenoid pigmented liposomes has been collected, subsequently pulse radiolysis was used to generate the radical cations of {beta}-carotene, zeaxanthin and lutein, in unilamellar vesicles of dipalmitoyl phosphatidyl choline. The rate constants for the 'repair' of these carotenoid radical cations by water-soluble vitamin C were found to be similar ({approx}1 x 10{sup 7} M{sup -1}s{sup -1}) for {beta}-carotene and zeaxanthin and somewhat lower ({approx}0.5 x 10{sup 7} M{sup -1}s{sup -1}) for lutein. The results are discussed in terms of the microenvironment of the carotenoids and suggest that for {beta}-carotene, a hydrocarbon carotenoid, the radical cation is able to interact with a water-soluble species even though the parent hydrocarbon carotenoid is probably entirely in the non-polar region of the liposome. Studies investigating the ability of ingested lycopene to protect human lymphoid cells against singlet oxygen and nitrogen dioxide radical mediated cell damage have shown that a high lycopene diet is beneficial in protecting human cells against reactive oxygen species. Triplet states of carotenoids were produced in benzene solvent and their triplet lifetimes were found to depend on the concentration of the parent molecule. The rate constants obtained for ground state quenching correlate with the number of conjugated double bonds, the longer chain systems having higher quenching rate constants. The efficiency of deactivation of singlet oxygen by three asymmetric carotenoids was measured via time-resolved luminescence detection. In benzene, the deactivation efficiency was found to fit the trend reported previously, in that quenching efficiency increases with increasing wavelength of {pi}{pi}* absorption of the maxima of carotenoids. Both hydroxyl and carbonyl groups were shown to lower the quenching ability. The singlet oxygen deactivation efficiency of carotenoids incorporated within the bilayer of dipalmitoyl phosphotidyl choline liposomes and water/alcohol mixtures was determined concluding that out of the two xanthophylls and one carotene investigated, {beta}-carotene was the most efficient at singlet oxygen deactivation. The results are discussed in terms of the microenvironment of the carotenoids. (author)

  15. Development and validation of a simple high performance thin layer chromatography method combined with direct 1,1-diphenyl-2-picrylhydrazyl assay to quantify free radical scavenging activity in wine.

    Science.gov (United States)

    Agatonovic-Kustrin, Snezana; Morton, David W; Yusof, Ahmad P

    2016-04-15

    The aim of this study was to: (a) develop a simple, high performance thin layer chromatographic (HPTLC) method combined with direct 1,1-diphenyl-2-picrylhydrazyl (DPPH) assay to rapidly assess and compare free radical scavenging activity or anti-oxidant activity for major classes of polyphenolics present in wines; and (b) to investigate relationship between free radical scavenging activity to the total polyphenolic content (TPC) and total antioxidant capacity (TAC) in the wine samples. The most potent free radical scavengers that we tested for in the wine samples were found to be resveratrol (polyphenolic non-flavonoid) and rutin (flavonoid), while polyphenolic acids (caffeic acid and gallic acid) although present in all wine samples were found to be less potent free radical scavengers. Therefore, the total antioxidant capacity was mostly affected by the presence of resveratrol and rutin, while total polyphenolic content was mostly influenced by the presence of the less potent free radical scavengers gallic and caffeic acids. PMID:26616951

  16. Ultrasound-assisted MnO2 catalyzed homolysis of peracetic acid for phenol degradation: The assessment of process chemistry and kinetics

    OpenAIRE

    Rokhina, E.V.; Makarova, K.; Lathinen, M.; Golovina, E.A.; Van As, H.; Virkutyte, J.

    2013-01-01

    The combination of peracetic acid (PAA) and heterogeneous catalyst (MnO2) was used for the degradation of phenol in an aqueous solution in the presence of ultrasound irradiation (US). As a relevant source of free radicals (e.g. OH), peracetic acid was comprehensively studied by means of electron spin resonance (ESR) spin trapping (ST) techniques with the subsequent identification of free radicals by simulation based fitting (SBF) technique. The radical reaction mechanism, where hydroxyl radic...

  17. Photochemical free radical production rates in the eastern Caribbean

    Science.gov (United States)

    Dister, Brian; Zafiriou, Oliver C.

    1993-02-01

    Potential photochemical production rates of total (NO-scavengeable) free radicals were surveyed underway (> 900 points) in the eastern Caribbean and Orinoco delta in spring and fall 1988. These data document seasonal trends and large-scale (˜ 10-1000 km) variability in the pools of sunlight-generated reactive transients, which probably mediate a major portion of marine photoredox transformations. Radical production potential was detectable in all waters and was reasonably quantifiable at rates above 0.25 nmol L-1 min-1 sun-1. Radical production rates varied from ˜ 0.1-0.5 nmol L-1 min-1 of full-sun illumination in "blue water" to > 60 nmol L-1 min-1 in some estuarine waters in the high-flow season. Qualitatively, spatiotemporal potential rate distributions strikingly resembled that of "chlorophyll" (a riverine-influence tracer of uncertain specificity) in 1979-1981 CZCS images of the region [Müller-Karger et al., 1988] at all scales. Basin-scale occurrence of greatly enhanced rates in fall compared to spring is attributed to terrestrial chromophore inputs, primarily from the Orinoco River, any contributions from Amazon water and nutrient-stimulus effects could not be resolved. A major part of the functionally photoreactive colored organic matter (COM) involved in radical formation clearly mixes without massive loss out into high-salinity waters, although humic acids may flocculate in estuaries. A similar conclusion applies over smaller scales for COM as measured optically [Blough et al., this issue]. Furthermore, optical absorption and radical production rates were positively correlated in the estuarine region in fall. These cruises demonstrated that photochemical techniques are now adequate to treat terrestrial photochemical chromophore inputs as an estuarine mixing problem on a large scale, though the ancillary data base does not currently support such an analysis in this region. Eastern Caribbean waters are not markedly more reactive at comparable salinities than waters of the Gulf of Maine and North Atlantic Bight, despite large inputs of colored waters from two large tropical rivers with substantial "black water" tributaries. Other sources of reactive COM, such as grazing, sedimentary diagenesis, and "marine humus" may increase temperate waters' photoreactivity; alternatively, northern waters may be chromophore-rich because they are light-poor and photobleaching is a major sink of photoreactive COM.

  18. Chlorine radicals measured in Eyjafjallajökull volcanic plume

    Science.gov (United States)

    Balcerak, Ernie

    2011-08-01

    When the Icelandic volcano Eyjafjallajökull erupted in spring 2010, it disrupted commercial air travel, stranding passengers across Europe and beyond. In response to the lack of information on the volcanic ash load and dispersion, scientific instruments were deployed on a number of special flights to observe the composition and chemistry of the volcanic plume and included three deployments aboard a Lufthansa aircraft of the Civil Aircraft for the Regular Investigation of the Atmosphere Based on an Instrument Container (CARIBIC) observational instrument package. Baker et al. report on the first observation-based estimates of chlorine radical concentrations in the volcanic plume. Previous studies had suggested that chlorine radicals could exist in volcanic plumes. This study, the first to identify chlorine radical chemistry and quantify chlorine radicals in a volcanic plume, will help researchers to more fully understand volcanic chemistry, particularly halogen chemistry, and its effects on the atmosphere. (Geophysical Research Letters, doi:10.1029/2011GL047571, 2011)

  19. Radicalization and the Use of Social Media

    Directory of Open Access Journals (Sweden)

    Robin Thompson

    2011-01-01

    Full Text Available The use of social media tools by individuals and organizations to radicalize individuals for political and social change has become increasingly popular as the Internet penetrates more of the world and mobile computing devices are more accessible. To establish a construct for radicalization,the power and reach of social media will be described so there is common understanding of what social media is and how it is utilized by various individuals and groups. The second section will answer the question of why social media applications are the perfect platform for the radical voice. Finally, the use of social media and its influence in radicalizing populations in Northern Africa and the Middle East during 2011 will be analyzed and recommendations proposed.

  20. User involvement competence for radical innovation

    DEFF Research Database (Denmark)

    Lettl, Christopher

    2007-01-01

    One important market related capability for firms which seek to develop radical innovations is the competence to involve the 'right' users at the 'right' time in the 'right' form. While former studies have identified a rather passive role of users in the radical innovation process, this paper focuses on the involvement of such users that are in the position to play an active role as inventors and (co)-developers. A multiple case study analysis was conducted in the field of medical technology. Five radical innovation projects within four firms were selected including medical robots and computer-assisted navigation systems. The case study analysis reveals that firms who closely interact with specific users benefit significantly for their radical innovation work. These users have a high motivation toward new solutions, are open to new technologies, possess diverse competencies, and are embedded into a very supportive environment. Udgivelsesdato: MAR-JUN

  1. Fast beam studies of free radical photodissociation

    Energy Technology Data Exchange (ETDEWEB)

    Neumark, D.M. [Lawrence Berkeley Laboratory, CA (United States)

    1993-12-01

    The authors have developed a novel technique for studying the photodissociation spectroscopy and dynamics of free radicals. In these experiments, radicals are generated by laser photodetachment of a fast (6-8 keV) mass-selected negative ion beam. The resulting radicals are photodissociated with a second laser, and the photofragments are collected and detected with high efficiency using a microchannel plate detector. The overall process is: ABC{sup -} {yields} ABC + e{sup -} {yields} A + BC, AB + C. Two types of fragment detection schemes are used. To map out the photodissociation cross-section of the radical, the photodissociation laser is scanned and the total photofragment yield is measured as a function of wavelength. In other experiments, the photodissociation frequency is fixed and the photofragment masses, kinetic energy release, and scattering angle is determined for each photodissociation event.

  2. A mechanochemical switch to control radical intermediates.

    Science.gov (United States)

    Brunk, Elizabeth; Kellett, Whitney F; Richards, Nigel G J; Rothlisberger, Ursula

    2014-06-17

    B??-dependent enzymes employ radical species with exceptional prowess to catalyze some of the most chemically challenging, thermodynamically unfavorable reactions. However, dealing with highly reactive intermediates is an extremely demanding task, requiring sophisticated control strategies to prevent unwanted side reactions. Using hybrid quantum mechanical/molecular mechanical simulations, we follow the full catalytic cycle of an AdoB??-dependent enzyme and present the details of a mechanism that utilizes a highly effective mechanochemical switch. When the switch is "off", the 5'-deoxyadenosyl radical moiety is stabilized by releasing the internal strain of an enzyme-imposed conformation. Turning the switch "on," the enzyme environment becomes the driving force to impose a distinct conformation of the 5'-deoxyadenosyl radical to avoid deleterious radical transfer. This mechanochemical switch illustrates the elaborate way in which enzymes attain selectivity of extremely chemically challenging reactions. PMID:24846280

  3. Radical production in the radiolysis of benzene

    International Nuclear Information System (INIS)

    Complete text of publication follows. Benzene is the prototypical aromatic compound and yet the radiation chemistry of the radicals formed in its radiolysis is not well understood. Temporal information on the yield of phenyl radical, the major radical produced in the radiolysis, is important for understanding the radiation chemistry of many other types of aromatic compounds including some polymers. The effects of track structure on the production of phenyl radicals have been examined using iodine-scavenging techniques. The variation of the yields of iodobenzene and the other major molecular products such as biphenyl as a function of iodine concentration gives a good indication of the competition kinetics occurring in particle tracks. Experimental results of the scavenger experiments will be shown and their implications in the radiolysis of condensed hydrocarbons will be discussed

  4. Radical pancreaticoduodenectomy for benign disease.

    LENUS (Irish Health Repository)

    Kavanagh, D O

    2008-01-01

    Whipple\\'s procedure is the treatment of choice for pancreatic and periampullary malignancies. Preoperative histological confirmation of malignancy is frequently unavailable and some patients will subsequently be found to have benign disease. Here, we review our experience with Whipple\\'s procedure for patients ultimately proven to have benign disease. The medical records of all patients who underwent Whipple\\'s procedure during a 15-year period (1987-2002) were reviewed; 112 patients underwent the procedure for suspected malignancy. In eight cases, the final histology was benign (7.1%). One additional patient was known to have benign disease at resection. The mean age was 50 years (range: 30-75). The major presenting features included jaundice (five), pain (two), gastric outlet obstruction (one), and recurrent gastrointestinal haemorrhage (one). Investigations included ultrasound (eight), computerised tomography (eight), endoscopic retrograde cholangiopancreatography (seven; of these, four patients had a stent inserted and three patients had sampling for cytology), and endoscopic ultrasound (two). The pathological diagnosis included benign biliary stricture (two), chronic pancreatitis (two), choledochal cyst (one), inflammatory pseudotumour (one), cystic duodenal wall dysplasia (one), duodenal angiodysplasia (one), and granular cell neoplasm (one). There was no operative mortality. Morbidity included intra-abdominal collection (one), anastomotic leak (one), liver abscess (one), and myocardial infarction (one). All patients remain alive and well at mean follow-up of 41 months. Despite recent advances in diagnostic imaging, 8% of the patients undergoing Whipple\\'s procedure had benign disease. A range of unusual pathological entities can mimic malignancy. Accurate preoperative histological diagnosis may have allowed a less radical operation to be performed. Endoscopic ultrasound-guided fine needle aspirate (EUS-FNA) may reduce the need for Whipple\\'s operation in benign pancreaticobiliary disease in the future.

  5. Radical radiotherapy for oropharyngeal carcinomas

    Energy Technology Data Exchange (ETDEWEB)

    Kagei, Kenji; Shimizu, Shinichi; Hashimoto, Seiko; Nishioka, Takeshi; Shirato, Hiroki; Honma, Akihiro; Miyasaka, Kazuo [Hokkaido Univ., Sapporo (Japan). School of Medicine; Kaneko, Masanori; Ohmori, Keiichi

    1999-03-01

    The treatment results of 127 previously untreated patients with oropharyngeal carcinomas treated with radical radiotherapy between 1980 and 1995 were evaluated. Almost all patients were treated with external radiotherapy using cobalt gamma rays. The standard treatment schedule was one time per day, four times per week, with 2.5 Gy as the daily dose and 65 or 70 Gy as the total number of tumor doses. From the introduction of a CT simulator in 1988, patients who had an unilateral tumor that did not cross the midline and had no contralateral neck lymph node metastasis were treated by an ipsilateral technique (an anterior oblique and a posterior oblique field with 30 or 45 deg wedges) sparing contralateral parotid gland and excluding the contralateral neck region from the irradiated volume using CT simulator. In 38 patients who were treated by the ipsilateral technique, the treatment results were comparable with those in patients treated by the standard method in opposite fields and there was no contralateral regional failure. Moreover, radiation-induced xerostomia was significantly reduced in these patients. It was suggested that the ipsilateral technique may be indicated in patients with laterally located, not crossing the midline, T1-3, N0-2 tumors of the oropharynx with the help of CT simulator. The treatment results of 29 patients treated with the concomitant administration of radiotherapy and weekly carboplatin and 92 patients treated with radiotherapy without chemotherapy were compared. No significant difference in cause-specific survival, local control and neck control was found between the two groups. (author)

  6. Experimental evidence for a non-OH oxidant produced from the reaction of isoprene with OH radical

    Science.gov (United States)

    Huang, D.; Chen, Z.

    2013-12-01

    The OH radical initiated oxidation of alkenes is of great importance to air quality and atmospheric chemistry. Although the related mechanism is well studied over several decades, several intermediate steps, such as the recycling of OH radical, the reaction of intermediates, and the formation of peroxides, are unresolved. As we known, the traditional mechanism cannot reproduce the high measured OH radical level in the rural forests. Currently, the recycling of OH radical in the isoprene-OH reaction is considered to be a potential candidate for the explanation. Here, alternatively, we intend to know if a non-OH oxidant leads to the discrepancy between the modeled and measured OH radical in the rural forest by reacting with plenty of oxygenated products of hydrocarbon compounds, sharing the 'oxidation responsibility' of OH radical, and consequently saving the OH radical. After mixing the products produced from the isoprene-OH reaction with formaldehyde and acetaldehyde in a flow reactor in the absent of light, we found an immediate increase of the peroxy formic acid and peroxy acetic acid. Control experiment results indicated that these peroxy acids were the products of aldehyde reaction with some non-OH oxidant, which was produced from the isoprene-OH reaction. Unfortunately, we have not identified this unknown oxidant. However, based on the decrement of aldehyde during the process of mixing with isoprene products, we estimate the OH-equivalent concentration of this oxidant to be ~0.2 pptv, which is one fifth of the OH radical in the isoprene-OH reaction. This mechanism may contribute to explaining the maintenance of the oxidation capacity of the troposphere. Additionally, this mechanism might involve in the functionalization of oxygenated organic compounds and the formation of secondary organic aerosols.

  7. Kinetic analysis of the reaction of hydroxyl radical with antioxidants

    International Nuclear Information System (INIS)

    It is well known that main factor of the radiation damage to the living body is the hydroxyl radical (·OH). So, to look for natural substances which scavenge ·OH is important in health science. We have reported the second order reaction rate constants of ·OH with the molecules possessing the partial structures of tea catechins using the rapid flow ESR method and showed a linear relationship between the rate constant and the dissociation energy (BDE) of the bond of the reaction site. In this work, we report the rate constants of (+)-catechin, L-ascorbic acid and (-)-epigallocatechin gallate (EGCg) and the calculated BDEs. The result was discussed from structural point of view. As a ·OH generating system, (Ti3+ + H2O2 ? Ti4+ + ·OH + OH) was used, which was thought to generate free ·OH as radiations. Antioxidants were mixed with ethanol and were reacted with ·OH and the ESR spectra were measured just after the mixing. All the spectra were the superposition of the hydroxyethyl and antioxidant radicals, and the ratio of their intensity was calculated from the doubly-integrated curves. Then, the ratio of the reaction rate constant of ·OH with polyphenol and ethanol, kAO/kEtOH, was obtained using the equation [·OH]/ [CH3C·HOH]=kAO/kEtOH·([AO]/[EtOH]). The bond dissociation energy (BDE) was calculated as the energy difference for the reaction AO-H ? AO· + H·. The geometries of the closed-shell species were optimized at the B3LYP/6-311 + G(2d, 2p) level of theory. For the radicals, a restricted open-shell (ROB3LYP) approach was utilized. The energy of the hydrogen atom is exceptionally set to its exact value, -0.50000 au, Energies of all the species were corrected using unscaled zero-point energies. All the calculations were carried out with the SPARTAN '02 system of programs. It was concluded from the analysis of ESR spectrum that EGCg reacts with ·OH using the central OH group on the Bring (gallyl group). The ratios of the reaction rate constant to that of ethanol were in the order of EGCg (45)>(+)-catechin (20)> pyrogallol (19)> gallic acid (17)> L-ascorbic acid (13)> catechol (11)> phloroglucinol (1.5)> resorcinol (1.2). The value of EGCg was larger than the twice of pyrogallol (model of B ring) or the sum of pyrogallol and gallic acid (model of the galloyl group), suggesting that B ring is not independent of other parts in the molecule. Similar concept has already been reported on the reaction of tea catechin and DPPH radical. This concept was ascertained by the calculation, which elucidated that spin density spreads all over three rings and as a result the structure of catechin radicals is stabilized.

  8. Antioxidant and free radical scavenging activities of some fruits.

    Science.gov (United States)

    Prakash, Dhan; Upadhyay, Garima; Pushpangadan, P; Gupta, Charu

    2011-01-01

    Phenols, a major group of antioxidant phytochemicals, have profound importance due to their biological and free radical scavenging activities. To identify their potential sources extracts of some fruits and their different parts were studied for total phenolic contents (TPC), antioxidant (AOA) and free radical scavenging activities (FRSA). The amount of TPC varied from 10.5 (Carissa carandus, fruit peel) to 343.2 mg/g (Caesalpinia Mexicana, fruits) and AOA from 20.3% (Musa paradisiacal, fruits) to 96.7% (Caesalpinia Mexicana, fruits). Fruits of Caesalpinia Mexicana, Acacia auriculiformis, fruit pericarp green fibres of Cocus nucifera, and fruits of Emblica officinalis were found to have high TPC (73.1-343.2 mg/g) and high AOA (68.5-96.7%). Promising fruits were studied for their FRSA and reducing power (RP) measured by DPPH assay where the fruits of Caesalpinia mexicana, fruit pericarp fibres of Cocus nucifera, fruits of Emblica officinalis showed very low IC50 ranging from 0.009 to 0.016 mg/ml, EC50 from 0.39 to 0.70 mg/mg DPPH and reasonably high values (142.1-256.3) of anti radical power (ARP), indicating their strong FRSA and reducing power (RP) as evident by their low ASE/ml values (0.42-1.08). They also showed better inhibition of lipid peroxidation measured by using ferric thiocyanate assay and by using egg yolk compared to the reference standard quercetin. The ferrous and ferric ion chelating capacity of the promising fruits and their underutilized parts in terms of IC50 varied from 0.12 (Emblica officinalis, fruits) to 2.44 mg/ml (Mangifera indica, Seed kernel) and 0.22 (Caesalpinia Mexicana, fruits) to 2.59 mg/ml (Litchi chinensis, fruit peel) respectively. Fruit pulp, peel and seeds of Litchi chinensis with reasonable amount of phenols (48.3, 43.9, 50.1 mg/ml) showed low ARP (23.5, 38.3, 33.8) and ASE/ml (3.13, 2.18, 2.62) respectively in contrast to Aegle marmelos with comparatively lower phenols (35.1 mg/g) exhibited good ARP (57.4) and RP (1.67 ASE/ml). Extracts (20 ?g/ml) of fruits of Acacia auriculiformis, Caesalpinia Mexicana, Emblica officinalis, fruit pericarp fibres of Cocus nucifera, were found effective in protecting plasmid DNA nicking induced by Fenton’s reagent generated hydroxyl radicals. They were further assayed for their specific phenolic composition through HPLC and MS/MS where the amount of caffeic acid varied from 48.5 to 2231 ?g/g, chlorogenic acid 63.8 to 912.1 ?g/g, ellagic acid 46.4 to 1429.1 ?g/g, ferulic acid 36.7 to 762.9 ?g/g, gallic acid 181.6 to 2831.6 ?g/g, protocatechuic acid 41.7 to 322.8 ?g/g, and quercetin 44.6 to 367.6 ?g/g. PMID:22754941

  9. Free Radicals, Antioxidants in Disease and Health

    OpenAIRE

    Pham-Huy, Lien Ai; HE, HUA; Pham-Huy, Chuong

    2008-01-01

    Free radicals and oxidants play a dual role as both toxic and beneficial compounds, since they can be either harmful or helpful to the body. They are produced either from normal cell metabolisms in situ or from external sources (pollution, cigarette smoke, radiation, medication). When an overload of free radicals cannot gradually be destroyed, their accumulation in the body generates a phenomenon called oxidative stress. This process plays a major part in the development of chronic and degene...

  10. Imágenes para Shehouse: Smiljan Radic, Yuji Harada

    Scientific Electronic Library Online (English)

    Smiljan, Radic.

    2012-04-01

    Full Text Available A medio camino entre la pintura, el collage y el render, las visualizaciones de Radic parecen declarar el imaginario cultural desde el cual se emprende el proyecto, para revelar un campo de referencias y aspiraciones. [...] Abstract in english Radic produces images halfway between painting, collage and rendering. They seem to declare the cultural field where the project stands and reveal a set of references and aspirations. [...

  11. Radical induction theory of ulcerative colitis

    OpenAIRE

    Pravda, Jay

    2005-01-01

    To propose a new pathogenesis called Radical Induction to explain the genesis and progression of ulcerative colitis (UC). UC is an inflammatory bowel disease. Colonic inflammation in UC is mediated by a buildup of white blood cells (WBCs) within the colonic mucosal lining; however, to date there is no answer for why WBCs initially enter the colonic mucosa to begin with. A new pathogenesis termed “Radical Induction Theory” is proposed to explain this and states that excess un-neutralized hydro...

  12. Radical Behaviorism and Buddhism: Complementarities and Conflicts

    OpenAIRE

    Diller, James W.; Lattal, Kennon A.

    2008-01-01

    Comparisons have been made between Buddhism and the philosophy of science in general, but there have been only a few attempts to draw comparisons directly with the philosophy of radical behaviorism. The present review therefore considers heretofore unconsidered points of comparison between Buddhism and radical behaviorism in terms of their respective goals, conceptualization of human beings, and the outcomes of following either philosophy. From these comparisons it is concluded that the commo...

  13. Radicalization and the Use of Social Media

    OpenAIRE

    Robin Thompson

    2011-01-01

    The use of social media tools by individuals and organizations to radicalize individuals for political and social change has become increasingly popular as the Internet penetrates more of the world and mobile computing devices are more accessible. To establish a construct for radicalization,the power and reach of social media will be described so there is common understanding of what social media is and how it is utilized by various individuals and groups. The second section will answer the q...

  14. Formation and stabilization of persistent free radicals

    OpenAIRE

    Dellinger, Barry; Lomnicki, Slawomir; Khachatryan, Lavrent; Maskos, Zofia; Hall, Randall W.; Julien ADOUNKPE; McFerrin, Cheri; TRUONG, HIEU

    2007-01-01

    We demonstrate that stable and relatively unreactive “environmentally persistent free radicals (PFRs)” can be readily formed in the post-flame and cool-zone regions of combustion systems and other thermal processes. These resonance-stabilized radicals, including semiquinones, phenoxyls, and cyclopentadienyls, can be formed by the thermal decomposition of molecular precursors including catechols, hydroquinones and phenols. Association with the surfaces of fine particles imparts additional stab...

  15. Hydroxyl radical induced degradation of salicylates in aerated aqueous solution

    International Nuclear Information System (INIS)

    Ionizing radiation induced degradation of acetylsalicylic acid, its hydrolysis product salicylic acid and a salicylic acid derivative 5-sulpho-salicylic acid, was investigated in dilute aqueous solutions by UV–vis spectrophotometry, HPLC separation and diode-array or MS/MS detection, chemical oxygen demand, total organic carbon content and by Vibrio fischeri toxicity measurements. Hydroxyl radicals were shown to degrade these molecules readily, and first degradation products were hydroxylated derivatives in all cases. Due to the by-products, among them hydrogen peroxide, the toxicity first increased and then decreased with the absorbed dose. With prolonged irradiation complete mineralization was achieved. - Highlights: • In OH induced reactions of salicylates first products are hydroxylated derivatives. • With prolonged irradiation dihydroxy derivatives also form. • In aerated solutions the one-electron oxidant OH induces 3–4 oxidations. • Toxicity first increases and then decreases with dose mainly due to H2O2 formation. • The toxicity in tap water is smaller than in pure water

  16. A comparative study of hydrogen-atom release dynamics in radical-radical reactions

    International Nuclear Information System (INIS)

    This paper presents a comparative study of the atomic hydrogen release dynamics in the oxidation reactions of saturated and unsaturated hydrocarbon radicals. The prototypal radical-radical reactive scattering processes were examined by applying a combination of crossed beams and high-resolution vacuum-ultraviolet laser-induced fluorescence spectroscopy. With the aid of ab initio and statistical calculations, remarkable dynamic features were uncovered in the Doppler profile analysis of the atomic hydrogen products. The difference in the reactivity of saturated and unsaturated hydrocarbon radicals could be rationalized in terms of the characteristic geometry of the transition state and activation barriers along the exit channel on the doublet potential energy surface.

  17. Selective Radical-Radical Cross-Couplings: Design of a Formal ?-Mannich Reaction.

    Science.gov (United States)

    Jeffrey, Jenna L; Petronijevi?, Filip R; MacMillan, David W C

    2015-07-01

    A direct ?-coupling of cyclic ketones with imines has been accomplished via the synergistic combination of photoredox catalysis and organocatalysis. Transient ?-enaminyl radicals derived from ketones via enamine and oxidative photoredox catalysis readily combine with persistent ?-amino radicals in a highly selective hetero radical-radical coupling. This novel pathway to ?-aminoketones is predicated upon the use of DABCO as both a base and an electron transfer agent. This protocol also formally allows for the direct synthesis of ?-Mannich products via a chemoselective three-component coupling of aryl aldehydes, amines, and ketones. PMID:26075347

  18. Indicators of free radical activity in patients developing radiation pneumonitis

    International Nuclear Information System (INIS)

    Purpose: Radiation pneumonitis is thought to occur as the result of excess free radical generation following radiotherapy. Various in vitro studies have shown that large doses of irradiation can cause membrane lipid peroxidation and the oxidation of protein sulphuryl groups. We, therefore, studied two circulating markers of lipid peroxidation and an indicator of 'catalytic iron' (potentially available iron to catalyze the generation of free radicals) in patients undergoing radiotherapy. Methods and Materials: The 9,11 diene conjugate of 9,12 linoleic acid, expressed as their molar ratio (percentage molar ratio (MR)) and thiobarbituric acid reactive acid-substances (TBARS), as well as levels of circulating desferrioxamine-chelatable iron assay, were assayed. Serial blood samples were taken over a 3-month period in 25 patients with inoperable nonsmall cell lung cancer. Results: Ten patients developed radiation pneumonitis. The patients who developed pneumonitis showed a tendency for the serum percentage molar ratio to increase after a week. The change in the percentage molar ratio between Time 0 and 1 week of radiotherapy was significantly higher in the group that subsequently developed pneumonitis compared to the group that did not (p = 0.002). The initial serum TBARS levels in patients were not significantly elevated compared to controls and there was no difference in the serum TBARS levels in the pneumonitis and nonpneumonitis groups throughout the study period. After 1 week of radiotherapy the group that subsequently developed pneumonitis had a significantly higher level of desferrioxamine-chelatable iron (DFx-iron) compared with the nonpneumonitis group (p = 0.05). Conclusion: These data suggest that both the percentage MR and DFx-iron appear to reflect an increased susceptibility to develop radiation pneumonitis and after 1 week of radiotherapy they indicate patients who are likely to subsequently develop pneumonitis. Hence, these indicators could indicate the group of patients that could benefit from intervention therapies with antioxidants

  19. Volatility of secondary organic aerosol during OH radical induced ageing

    Directory of Open Access Journals (Sweden)

    K. Salo

    2011-07-01

    Full Text Available The aim of this study was to investigate oxidation of SOA formed from ozonolysis of ?-pinene and limonene by hydroxyl radicals. This paper focuses on changes of particle volatility, using a Volatility Tandem DMA (VTDMA set-up, in order to explain and elucidate the mechanism behind atmospheric ageing of the organic aerosol. The experiments were conducted at the AIDA chamber facility of KIT in Karlsruhe and at the SAPHIR chamber of FZJ in Jülich. A fresh SOA was produced from ozonolysis of ?-pinene or limonene and then aged by enhanced OH exposure. As an OH-radical source in the AIDA-chamber the ozonolysis of tetramethylethylene (TME was used while in the SAPHIR-chamber the OH was produced by natural light photochemistry. A general feature is that SOA produced from ozonolysis of ?-pinene and limonene initially were rather volatile and becomes less volatile with time in the ozonolysis part of the experiment. Inducing OH chemistry or adding a new portion of precursors made the SOA more volatile due to addition of new semi-volatile material to the aged aerosol. The effect of OH chemistry was less pronounced in high concentration and low temperature experiments when lower relative amounts of semi-volatile material were available in the gas phase. Conclusions drawn from the changes in volatility were confirmed by comparison with the measured and modelled chemical composition of the aerosol phase. Three quantified products from the ?-pinene oxidation; pinonic acid, pinic acid and methylbutanetricarboxylic acid (MBTCA were used to probe the processes influencing aerosol volatility. A major conclusion from the work is that the OH induced ageing can be attributed to gas phase oxidation of products produced in the primary SOA formation process and that there was no indication on significant bulk or surface reactions. The presented results, thus, strongly emphasise the importance of gas phase oxidation of semi- or intermediate-volatile organic compounds (SVOC and IVOC for atmospheric aerosol ageing processing.

  20. Radiolytic oxidation of tamoxifen using the free radicals .OH and (or) HO2

    International Nuclear Information System (INIS)

    Tamoxifen is the most widely used antiestrogen in the treatment of breast cancer. In this work, we have studied its antioxidant properties. We have investigated the ability of tamoxifen to scavenge, in vitro, .OH and (or) HO2. free radicals that are produced by water radiolysis. Aqueous solutions of tamoxifen of concentrations ranging between 10-5 and 2.5 x 10-5 M have been irradiated (? 137Cs) in aerated acidic medium (H3PO4 10-3 M or HCOOH 10-1 M). The results show that tamoxifen reacts quantitatively with .OH free radicals but does not react with HO2. free radicals under our experimental conditions. (author)