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Redox Reaction (redox + reaction)
Selected AbstractsElectronic Structure and Solvation of Copper and Silver Ions: A Theoretical Picture of a Model Aqueous Redox ReactionCHEMINFORM, Issue 23 2004Jochen Blumberger Abstract For Abstract see ChemInform Abstract in Full Text. [source] ChemInform Abstract: Excited State Intramolecular Redox Reaction of 2-(Hydroxymethyl)anthraquinone in Aqueous Solution.CHEMINFORM, Issue 19 2002Matthew Lukeman Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Redox Reactions and Electron Transfer Across the Red Cell MembraneIUBMB LIFE, Issue 7 2003Eleanor Kennett Abstract Plasma membrane electron transport systems appear to be ubiquitous. These systems are implicated in hormone signal transduction, cell growth and differentiation events as well as protection from oxidative stress. The red blood cell is constantly exposed to oxidative stress; protection against the reactive species generated during this process may be the main role of its membrane electron transport systems. Membrane redox activity has been studied for over three-quarters of a century, and yet many questions remain regarding its identity and likely roles: are electron transfers by distinct and specific mechanisms; what are the physiological donors and acceptors; and how do these systems affect metabolism? Current evidence suggests that the human erythrocyte membrane contains a number of distinct electron transfer systems, some of which, at least, involve membrane proteins, and NADH or ascorbate as electron donors. The activity of these systems appears to be closely related to the metabolic state of the cell, suggesting that mediation of reducing equivalents across the plasma membrane allows redox buffering of each environment, intra- and extracellular, by the other. We have decided to study this from a new perspective, NMR spectroscopy the area of our own technical expertise, hence this review is slanted towards this more recent analysis. IUBMB Life, 55: 375-385, 2003 [source] Spontaneous Redox Reactions of Dopaquinone and the Balance between the Eumelanic and Phaeomelanic PathwaysPIGMENT CELL & MELANOMA RESEARCH, Issue 4 2000E.J. LAND Eumelanogenesis and phaeomelanogenesis diverge at an early stage in pigment formation, namely at the point where dopaquinone, the initial product of tyrosine oxidation by tyrosinase, undergoes one of two types of reaction: either (1) a reductive endocyclisation in which a Michael addition of the side-chain amino group takes place; or (2) a reductive addition of cysteine to give cysteinyldopa. In the former case, the product cyclodopa, is known rapidly to undergo a redox exchange reaction with dopaquinone to yield dopachrome, the precursor of the eumelanogenic pathway. In the second instance, cysteinyldopa is regarded as leading to the formation of benzothiazoles, which are characteristic of phaeomelanin. The precursor molecule of the phaeomelanic pathway is cysteinyldopaquinone. We have examined quantitatively the role of dopaquinone in the non-enzymatic oxidation of 5-S-cysteinyldopa using pulse radiolysis and have demonstrated that the redox exchange reaction between dopaquinone and 5-S-cysteinyldopa occurs spontaneously with a rate constant of 8.8×105 M,1 sec,1. This study has also enabled an improved estimate of ,4×107 M,1sec,1 to be obtained for the rate constant of the reaction of dopaquinone with cyclodopa. Calculations utilising these figures and estimates of the rate constants for the other reactions in early melanogenesis, demonstrate that, whilst similar pathways are invoked, the phaeomelanic pathway predominates in the presence of cysteine, irrespective of the availability of dopaquinone and thus independently of the rate of tyrosinase-catalysed oxidation. This suggests that the balance between the formation of eumelanin and phaeomelanin is regulated principally by the availability of cysteine at the site of melanogenesis. [source] Solubility, Complex Formation, and Redox Reactions in the Tl2O3,HCN/CN - ,H2O System.CHEMINFORM, Issue 24 2005Crystal Structures of the Cyano Compounds Tl(CN)3×H2O, K[Tl(CN)4], Na[Tl(CN)4]×3H2O, TlI[TlIII(CN)4], of TlI2C2O4. Abstract For Abstract see ChemInform Abstract in Full Text. [source] Effect of Ultrasound on the Redox Reactions of Iron(II) and (III).CHEMINFORM, Issue 52 2004Pankaj Pankaj Abstract For Abstract see ChemInform Abstract in Full Text. [source] Topochemically Controlled Redox Reactions in the System In/Sn/Cl.CHEMINFORM, Issue 24 2003Horst P. Beck Abstract For Abstract see ChemInform Abstract in Full Text. [source] The Biochemistry of Drug Metabolism , An IntroductionCHEMISTRY & BIODIVERSITY, Issue 10 2006Abstract This paper reviews the general principles and concepts underlying Drug and Xenobiotic Metabolism. Its five Chapters deal with: 1.1. Drugs and Xenobiotics, 1.2. What are Drug Disposition and Metabolism?, 1.3. Where does Drug Metabolism Occur?, 1.4. Consequences of Drug Metabolism -- An Overview, and 1.5. Drug Metabolism and Drug Discovery. This review is the first of seven Parts which will be published at intervals. The subsequent Parts will cover: 2. Redox Reactions and Their Enzymes, 3. Reactions of Hydrolysis and Their Enzymes, 4. Conjugation Reactions and Their Enzymes, 5. Metabolism and Bioactivity, 6. Inter-Individual Factors Affecting Drug Metabolism, and 7. Intra-Individual Factors Affecting Drug Metabolism. [source] Redox reactions of copper(II) upon electrospray ionization in the presence of acridine ligands with an amide side chainJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 3 2009Aura Tintaru Abstract The complexation of copper(II) to acridine derivatives has been studied by means of electrospray ionization (ESI) mass spectrometry. Under soft conditions of ionization, the ESI mass spectra of methanolic solutions of copper(II) chloride and the acridine ligands show abundant signals of the mononuclear complexes formed from the metal and ligand. Depending on the position of the N -benzoylamino substituent in the acridinic heterocycle, however, the copper atom involved in the complexation process adopts different oxidation states in the resulting cations. Hence, the metal is reduced to copper(I) in the monocationic complex with the compound substituted in position 2, whereas it keeps its divalent state in the monocation formed with the compound substituted in position 4. As a consequence, the regioisomers lead to monocations with different masses in the ESI spectra. In order to understand this unusual behavior of two isomeric compounds, additional experiments have been performed with quinoline as a model. Copyright © 2008 John Wiley & Sons, Ltd. [source] CxxS: Fold-independent redox motif revealed by genome-wide searches for thiol/disulfide oxidoreductase functionPROTEIN SCIENCE, Issue 10 2002Dmitri E. Fomenko Abstract Redox reactions involving thiol groups in proteins are major participants in cellular redox regulation and antioxidant defense. Although mechanistically similar, thiol-dependent redox processes are catalyzed by structurally distinct families of enzymes, which are difficult to identify by available protein function prediction programs. Herein, we identified a functional motif, CxxS (cysteine separated from serine by two other residues), that was often conserved in redox enzymes, but rarely in other proteins. Analyses of complete Escherichia coli, Campylobacter jejuni, Methanococcus jannaschii, and Saccharomyces cerevisiae genomes revealed a high proportion of proteins known to use the CxxS motif for redox function. This allowed us to make predictions in regard to redox function and identity of redox groups for several proteins whose function previously was not known. Many proteins containing the CxxS motif had a thioredoxin fold, but other structural folds were also present, and CxxS was often located in these proteins upstream of an ,-helix. Thus, a conserved CxxS sequence followed by an ,-helix is typically indicative of a redox function and corresponds to thiol-dependent redox sites in proteins. The data also indicate a general approach of genome-wide identification of redox proteins by searching for simple conserved motifs within secondary structure patterns. [source] Fabrication and Characterization of DNA/QPVP-Os Redox-Active Multilayer FilmELECTROANALYSIS, Issue 23 2004Jianyun Liu Abstract Calf thymus DNA was immobilized on functionalized glassy carbon, gold and quartz substrates, respectively, by the layer-by-layer (LBL) assembly method with a polycation QPVP-Os, a quaternized poly(4-vinylpyridine) partially complexed with osmium bis(2,2,-bipyridine) as counterions. UV-visible absorption and surface plasmon resonance spectroscopy (SPR) showed that the resulting film was uniform with the average thickness 3.4,nm for one bilayer. Cyclic voltammetry (CV) showed that the total surface coverage of the polycations increases as each QPVP-Os/DNA bilayer added to the electrode surface, but the surface formal potential of Os-centered redox reaction shifts negatively, which is mainly attributed to the intercalation of redox-active complex to DNA chain. The electron transfer kinetics of electroactive QPVP-Os in the multilayer film was investigated by electrochemical impedance experiment for the first time. The permeability of Fe(CN) in the solution into the multilayer film depends on the number of bilayers in the film. It is worth noting that when the multilayer film is up to 4 bilayers, the CV curves of the multilayer films display the typical characteristic of a microelectrode array. The nanoporous structure of the multilayer film was further confirmed by the surface morphology analysis using atomic force microscopy (AFM). [source] Chromate reduction in wastewater at different pH levels using thin iron wires,A laboratory studyENVIRONMENTAL PROGRESS & SUSTAINABLE ENERGY, Issue 3 2005Li-Yang Chang Abstract The effectiveness of using thin zero-valent iron (Fe0) wires in the treatment of wastewater generated from a metal cleaning facility and with a pH in the range of 2 to 10 was examined. It was found that (1) when the sample containing low levels of total chromium (,14 mg/L) was mixed with iron wires at a pH of 3 to 8, 50 to 90% of the total chromium could be reduced in 4 h; (2) the initial reduction efficiency was pH-dependent: the lower the pH, the higher the reduction rate; (3) variations of solution pH, redox electrical potential, and electrical conductivity (EC) in samples were also pH-dependent; (4) the adsorption/reduction efficiency was limited by the diffusion of Cr(VI) from wastewater to the iron surface when the test duration was long; (5) when the initial pH = 3, iron corrosion and redox reaction dominated the reduction process; however, with pH = 8 or 10, corrosion, surface passivation, or metal precipitation could compete with reduction; (6) the used iron wires were still effective in chromium removal in new samples at pH = 3; and (7) some desorption of adsorbed chromium was observed in acidic samples when the test duration was long. Scanning electron microscope images and energy-dispersive X-ray spectra collected from iron samples also indicate that the efficiency of chromium adsorption/reduction is pH-dependent. Our results suggest that using zero-valent iron to polish acidic wastewater containing low contents of chromium and other heavy metals is feasible. © 2005 American Institute of Chemical Engineers Environ Prog, 2005 [source] Probing the access of protons to the K pathway in the Paracoccus denitrificans cytochrome c oxidaseFEBS JOURNAL, Issue 2 2005Oliver-M. In recent studies on heme-copper oxidases a particular glutamate residue in subunit II has been suggested to constitute the entry point of the so-called K pathway. In contrast, mutations of this residue (E78II) in the Paracoccus denitrificans cytochrome c oxidase do not affect its catalytic activity at all (E78IIQ) or reduce it to about 50% (E78IIA); in the latter case, the mutation causes no drastic decrease in heme a3 reduction kinetics under anaerobic conditions, when compared to typical K pathway mutants. Moreover, both mutant enzymes retain full proton-pumping competence. While oxidized-minus-reduced Fourier-transform infrared difference spectroscopy demonstrates that E78II is indeed addressed by the redox state of the enzyme, absence of variations in the spectral range characteristic for protonated aspartic and glutamic acids at ,,1760 to 1710 cm,1 excludes the protonation of E78II in the course of the redox reaction in the studied pH range, although shifts of vibrational modes at 1570 and 1400 cm,1 reflect the reorganization of its deprotonated side chain at pH values greater than 4.8. We therefore conclude that protons do not enter the K channel via E78II in the Paracoccus enzyme. [source] Spectral, kinetic, and redox properties of basic fuchsin in homogeneous aqueous and sodium dodecyl sulfate micellar mediaINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 12 2003N. Ramanathan Effect of anionic surfactant on the optical absorption spectra and redox reaction of basic fuchsin, a cationic dye, has been studied. Increase in the absorbance of the dye band at 546 nm with sodium dodecyl sulfate (SDS) is assigned to the incorporation of the dye in the surfactant micelles with critical micellar concentration (CMC) of 7.3 × 10,3 mol dm,3. At low surfactant concentration (<5 × 10,3 mol dm,3) decrease in the absorbance of the dye band at 546 nm is attributed to the formation of a dye,surfactant complex (1:1). The environment, in terms of dielectric constant, experienced by basic fuchsin inside the surfactant micelles has been estimated. The association constant (KA) for the formation of dye,SDS complex and the binding constant (KB) for the micellization of dye are determined. Stopped-flow studies, in the premicellar region, indicated simultaneous depletion of dye absorption and formation of new band at 490 nm with a distinct isosbestic point at 520 nm and the rate constant for this region increased with increasing SDS concentration. The reaction of hydrated electron with the dye and the decay of the semireduced dye are observed to be slowed down in the presence of SDS. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 629,636, 2003 [source] Micellar catalysis on the redox reaction of glycolic acid with chromium(VI)INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 6 2001Kabir-ud-Din Chromium(VI) oxidation of glycolic acid in the absence and presence of cetyltrimethylammonium bromide (CTAB) and cetylpyridinium bromide (CPB) followed the same mechanism as shown by kinetic study. The reaction followed second-order kinetics, first-order in each reactant. The oxidation is strongly catalyzed by manganese(II) and cationic micelles of CTAB or CPB. The catalytic effect of micelles can be fitted to a model in which the reaction rate depends upon the concentration of both reactants in the micellar pseudophase. Some added inorganic salts (NaCl, NaBr, NaNO3, and Na2SO4) reduce the micellar catalysis by excluding glycolic acid from the reaction site. The reactivity of glycolic acid towards chromium(VI) has been discussed and also compared with those obtained previously for the reaction between chromium(VI) and the reductants oxalic and lactic acids. On the basis of the observed results, probable mechanisms have been proposed. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 377,386, 2001 [source] Theoretical study of the oxidative polymerization of aniline with peroxydisulfate: Tetramer formationINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 2 2008-Marjanovi, Gordana Abstract Semi-empirical quantum chemical study of the oxidative polymerization of aniline with ammonium peroxydisulfate, in aqueous solutions without added acid, has been based on the MNDO-PM3 computations of thermodynamic, redox, and acid,base properties of reactive species and the intermediates, combined with the MM2 molecular mechanics force-field method and conductor-like screening model of solvation. The main reaction routes of aniline tetramerization are proposed. The regioselectivity of the formation of aniline tetramers by redox and electrophilic aromatic substitution reactions is analyzed. It was proved that the linear NC4 coupled tetra-aniline is formed as a dominant product by three different pathways: comproportionation redox reaction between N -phenyl-1,4-benzoquinonediimine and 4-aminodiphenylamine, the one-electron oxidation of aniline with its half-oxidized NC4 coupled trimer, and the electrophilic aromatic substitution reaction of aniline with fully oxidized NC4 coupled trianiline nitrenium cation. The electrophilic aromatic substitution reaction of the NC4 coupled aniline trimer with aniline nitrenium cation, as well as the oxidation of aniline with half-oxidized branched trimer, lead to the branched aniline tetramers. The competing character of different tetramerization routes is highlighted. The oxidative intramolecular cyclization of branched oligoanilines and polyaniline, leading to the generation of substituted phenazine units, has been predicted to accompany the classical routes of the polymerization of aniline. Various molecular (branched vs. linear) oligomeric structures produced at different level of acidity during the course of polymerization and their impact on the formation of supramolecular structures of conducting polyaniline (nanorods and nanotubes vs. granular morphology), are discussed. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] tert -Amino effect at a coumarin and a 2-quinolone system: Synthesis of 1,2 fused 5H -chromeno[4,3- b]pyridin-5-ones and a 6H -benzo[h][1,6]naphthyridin-5-oneJOURNAL OF HETEROCYCLIC CHEMISTRY, Issue 1 2008Ivo C. Ivanov Some novel 1,2-fused 5H -chromeno[4,3- b]pyridin-5-ones (5a,b) and a 6H -benzo[h][1,6]naphthyridin-5-one (5c) have been synthesized starting from the 4-chlorocoumarin-3-carbaldehyde (1a) or its N -methyl-2-quinolone analogue (1b) via subsequent Knoevenagel condensation and ring closure reaction known as the ,tert -amino effect'. These are rare examples of the tert -amino effect occurring at 2-pyrone and 2-pyridone ring. An unusual intramolecular redox reaction of the iminium ion 6, reported earlier, most probably follows analogous mechanism as the tert- amino effect reactions leading to 5. [source] A novel CD4-conjugated ultraviolet light-activated photocatalyst inactivates HIV-1 and SIV efficiently,JOURNAL OF MEDICAL VIROLOGY, Issue 8 2008Koushi Yamaguchi Abstract In this study, we found that the electric potential derived from the redox reaction of ultraviolet (UV)-illuminated CD4-conjugated titanium dioxide (TiO2) inactivated a wide range of high-titered primary HIV-1 isolates, regardless of virus co-receptor usage or genetic clade. In vitro incubation of HIV-1 isolates with CD4-conjugated TiO2 (CD4-TiO2) followed by UV illumination led to inhibition of viral infectivity in both H9 cells and peripheral blood mononuclear cells as well as to the complete inactivation of plasma virions from HIV-1-infected individuals. Treatment with a newly established extra-corporeal circulation system with the photocatalyst in rhesus macaques completely inactivated plasma virus in the system and effectively reduced the infectious plasma viral load. Furthermore, plasma viremia and infectious viral loads were controlled following a second therapeutic photocatalyst treatment during primary SIVmac239 infection of macaques. Our findings suggest that this therapeutic immunophysical strategy may help control human immunodeficiency viral infection in vivo. J. Med. Virol. 80:1322,1331, 2008. © 2008 Wiley-Liss, Inc. [source] Kinetics and mechanism of oxidation of apple pectin by CrVI in aqueous acid medium,JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 12 2008Sebastián E. Bellú Abstract Selective oxidation of galacturonic acid residues of apple pectin by CrVI affords CO2/HCO2H, oxidized pectin, and CrIII as final redox products. The reaction shows first-order kinetics in [pectin], [CrVI], and [H+], at fixed ionic strength and temperature. Kinetic studies show that the redox reaction proceeds through a mechanism combining CrVI,,,CrIV,,,CrII and CrVI,,,CrIV,,,CrIII pathways. The mechanism is supported by the observation of free radicals, CrO (the formation of which implies involvement of CrII and CrIV) and CrV (formed in monoelectronic redox processes) as reaction intermediates. The reduction of CrIV and CrV by pectin was independently studied and found to occur more than 103 times faster than pectin,+,CrVI reaction, in acid medium. At pH 3,5, apple pectin,+,CrVI redox reaction is slow, oxo-chromate(V),pectin species stabilize and remain in solution during several hours. The present results show that these abundant and ubiquitous components of the cell walls of all land plants are able to reduce CrIV,VI or stabilize high-valent chromium depending on pH. Copyright © 2008 John Wiley & Sons, Ltd. [source] Cp2TiCl-catalyzed living radical polymerization of styrene initiated from peroxidesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 3 2006Alexandru D. Asandei Abstract The effects of the reaction conditions and nature of the initiator were investigated in the Cp2Ti(III)Cl-catalyzed living radical polymerization of styrene initiated by benzoyl peroxide (BPO), tert -butyl peroxide (TBPO), tert -butyl peroxybenzoate (TBPOB), dicumyl peroxide (CPO), and tert -butylperoxy 2-ethylhexyl carbonate (TBPOEHC). The reversible termination of the growing chains with Cp2Ti(III)Cl affords a linear dependence of molecular weight on conversion over a wide range of temperatures (60,120 °C) with an optimum in polydispersity (Mw/Mn < 1.2) for St/BPO/Cp2TiCl2/Zn = 100/1/3/6 at 60,90 °C. The similarity of the kinetic parameters from polymerizations initiated by peroxides with vastly different half-life times (t = 1 h, t = 543 h) and the minimum peroxide/Ti = 1/2 ratio required for a living process indicate that initiation occurs primarily by the redox reaction of the peroxide with Cp2Ti(III)Cl rather than peroxide thermal decomposition. This is consistent with one Ti equivalent consumed in the redox initiation and the second one utilized in the reversible termination of the growing chains. Qualitatively, based on the livingness of the process, these initiators ranked as BPO > TBPOB , TBPO > CPO > TBPOEHC. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1106,1116, 2006 [source] Atom transfer radical polymerization initiated by N -bromosuccinimideJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 22 2004Jianguo Jiang Abstract N -Bromosuccinimide (NBS) was used as the initiator in the atom transfer radical polymerizations of styrene (St) and methyl methacrylate (MMA). The NBS/CuBr/bipyridine (bpy) system shows good controllability for both polymerizations and yields polymers with polydispersity indexes ranging from 1.18 to 1.25 for St and 1.14 to 1.41 for MMA, depending on the conditions used. The end-group analysis of poly(MMA) and polystyrene indicated the polymerization is initiated by the succinimidyl radicals formed from the redox reaction of NBS with CuBr/bpy. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5811,5816, 2004 [source] A fluorimetric method for the determination of trace pentachlorophenol, based on its inhibitory effect on the redox reaction between the improved Fenton reagent and rhodamine BLUMINESCENCE: THE JOURNAL OF BIOLOGICAL AND CHEMICAL LUMINESCENCE, Issue 5 2007Huiqin Guo Abstract A sensitive fluorimetric method is presented and discussed for the determination of pentachlorophenol in aqueous solutions. This method is based on the inhibitory effect of pentachlorophenol on the reaction of conventional Fenton [Fe(III) + H2O2] reagent with rhodamine B in the medium of perchloric acid, which results in the fluorescence quenching of rhodamine B. It was further found that the sensitivity for the determination was improved significantly when the molecular ligand EDTA was added. This improved system was therefore presented for the determination of pentachlorophenol. The characteristics of the excitation and emission spectra, optimization of the experimental conditions, the stability of the system and the influence of foreign matter have all been investigated. Under optimal conditions, the linear range for the determination of pentachlorophenol is 12,480 ng/mL with a 3, limit of detection of 0.96 ng/mL. Compared with the conventional Fenton system, the improved system shows obvious advantages in both sensitivity and selectivity. By combination with the pretreatment of samples using ion exchange resins and XDA-1 absorption resin, the improved Fenton method was used for the first time for the determination of pentachlorophenol in synthetic samples and natural water samples, and satisfactory results, in agreement with those of the HPLC method, were achieved. The possible mechanism of the reactions has also been discussed. Copyright © 2007 John Wiley & Sons, Ltd. [source] Facile Synthesis of Polyaniline-Polypyrrole Nanofibers for Application in Chemical Deposition of Metal NanoparticlesMACROMOLECULAR RAPID COMMUNICATIONS, Issue 16 2008Ping Xu Abstract Polyaniline-polypyrrole (PANI-PPy) nanofibers with high aspect ratios have been synthesized by a one-step, surfactant-assisted chemical oxidative polymerization from mixtures of aniline (An) and pyrrole (Py) monomers. PANI-PPy nanofibers synthesized with an excess of either PANI or PPy show similar spectral (UV-vis and FT-IR) characteristics as the individual homopolymers, whereas nanofibers from an equimolar mixture of An and Py display unique spectral characteristics. PANI-PPy nanofibers undergo a spontaneous redox reaction with metal ions to produce metal nanoparticles with various morphologies and/or sizes. These findings may open new opportunities for synthesizing functional polymer nanofibers and metal nanoparticles with controllable sizes and/or morphologies. [source] Degradation of anilinopyrimidine fungicides photoinduced by iron(III),polycarboxylate complexesPEST MANAGEMENT SCIENCE (FORMERLY: PESTICIDE SCIENCE), Issue 9 2006Laura Anfossi Abstract The photoinduced degradation of three anilinopyrimidine fungicides (cyprodinil, pyrimethanil and mepanipyrim) by Fe(III),polycarboxylate complexes in aqueous solution was investigated. A photochemical redox reaction of Fe(III) complexes of oxalate and citrate occurs during irradiation (simulating sunlight) and is an important source of Fe(II) and a series of oxidants such as H2O2 and O radicals. The mechanism involves the formation of polycarboxylate radicals and/or carbon-centred radicals derived from decarboxylation, whereas the contribution of Fe(OH)2+ to O radical formation is negligible. The attack of O radicals on the fungicide molecules produces numerous photodegradation products, which were identified by means of LC-ES-MS and turned out to be mono- or dihydroxylated derivatives of the active ingredients, except for 2-amino-4,6-dimethylpyrimidine, which is only formed by pyrimethanil. The half-lives of the active ingredients, when submitted to irradiation in the presence of iron(III),polycarboxylate complexes, were estimated to vary between 28 and 79 min (photodegradation rates in the same conditions: mepanipyrim > cyprodinil > pyrimethanil), and photodegradation is slower in citrate than in oxalate solutions. Photoproducts and their kinetics of formation are very similar for the three fungicides. The OH substitution involves the aromatic and the heterocyclic ring and the nitrogen bridge between the two rings, except for mepanipyrim when the hydroxylation also involves the propynylic side chain. Copyright © 2006 Society of Chemical Industry [source] Conductive thin film formation onto radiation grafted polymeric surfaces using electroless plating techniquePOLYMERS FOR ADVANCED TECHNOLOGIES, Issue 9 2009Amr El-Hag Ali Abstract Surface modification of polypropylene films (PP) was carried out via radiation induced graft copolymerization of 4-vinyl pyridine (4VP) and acrylamide (AAm) to enhance the adhesion ability of the PP surface for electroless deposition of copper. Factors affecting the grafting process such as suitable solvent, comonomer composition and concentration and irradiation dose were optimized. The grafted films produced were characterized by studying their Fourier-transform infrared (FTIR) spectra and thermal stability. The grafted films were copper-plated by electroless deposition using Pd as the catalyst to initiate the redox reaction. The influence of catalytic activation method parameters on the plating rate were studied. Scanning electron microscopy revealed a dense and void-free copper deposited film. The adhesion of the deposited copper film to the modified PP films was determined by measuring the tensile strength of the copper plated films. The electrical characteristics of the copper plated films in comparison with grafted films were studied. The results showed the high adhesion of the deposited copper film to the grafted PP film as well as the high electrical conductivity. Copyright © 2008 John Wiley & Sons, Ltd. [source] Can radical cations of the constituents of nucleic acids be formed in the gas phase using ternary transition metal complexes?,RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 13 2005Sheena Wee Electrospray ionization (ESI) tandem mass spectrometry (MS/MS) of ternary transition metal complexes of [M(L3)(N)]2+ (where M,=,copper(II) or platinum(II); L3,=,diethylenetriamine (dien) or 2,2,:6,,2,-terpyridine (tpy); N,=,the nucleobases: adenine, guanine, thymine and cytosine; the nucleosides: 2,deoxyadenosine, 2,deoxyguanosine, 2,deoxythymine, 2,deoxycytidine; the nucleotides: 2,deoxyadenosine 5,-monophosphate, 2,deoxyguanosine 5,-monophosphate, 2,deoxythymine 5,-monophosphate, 2,deoxycytidine 5,-monophosphate) was examined as a means of forming radical cations of the constituents of nucleic acids in the gas phase. In general, sufficient quantities of the ternary complexes [M(L3)(N)]2+ could be formed for MS/MS studies by subjecting methanolic solutions of mixtures of a metal salt [M(L3)X2] (where M,=,Cu(II) or Pt(II); L3,=,dien or tpy; X,=,Cl or NO3) and N to ESI. The only exceptions were thymine and its derivatives, which failed to form sufficient abundances of [M(L3)(N)]2+ ions when: (a) M,=,Pt(II) and L3,=,dien or tpy; (b) M,=,Cu(II) and L3,=,dien. In some instances higher oligomeric complexes were formed; e.g., [Pt(tpy)(dG)n]2+ (n,=,1,13). Each of the ternary complexes [M(L3)(N)]2+ was mass-selected and then subjected to collision-induced dissociation (CID) in a quadrupole ion trap. The types of fragmentation reactions observed for these complexes depend on the nature of all three components (metal, auxiliary ligand and nucleic acid constituent) and can be classified into: (i) a redox reaction which results in the formation of the radical cation of the nucleic acid constituent, N+.; (ii) loss of the nucleic acid constituent in its protonated form; and (iii) fragmentation of the nucleic acid constituent. Only the copper complexes yielded radical cations of the nucleic acid constituent, with [Cu(tpy)(N)]2+ being the preferred complex due to suppression, in this case, of the loss of the nucleobase in its protonated form. The yields of the radical cations of the nucleobases from the copper complexes follow the order of their ionization potentials (IPs): G (lowest IP),>,A,>,C,>,T (highest IP). Sufficient yields of the radical cations of each of the nucleobases allowed their CID reactions (in MS3 experiments) to be compared to their even-electron counterparts. Copyright © 2005 John Wiley & Sons, Ltd. [source] Investigation of reduction of Cu(II) complexes in positive-ion mode electrospray mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 23 2001Luca Gianelli The electrospray ionization mass spectrometry (ESI-MS) behavior of seven Cu(II) complexes with tetradentate ligands has been studied. An unexpected reduction process, in positive ion mode, of the Cu oxidation state was observed, and shown to be due to charge transfer between the metal complex and the solvent molecules in the gas phase. Ion trap collision-induced dissociation experiments and deuterated solvents were used to support the proposed mechanism that is not a common electrochemical redox reaction at the ESI tip, but a gas-phase process. A series of solvents (acetonitrile, methanol, ethanol, propanol and iso -butanol) were tested, and a correlation between ionization energy (IE) and the amount of Cu(I) produced in ESI has been demonstrated for the alcohols, although some other solvent properties should also be taken into account. The electrochemical reduction potential of the complexes in solution is also an important parameter, since complexes more easily reduced in solution are also easier to reduce in the gas phase. Copyright © 2001 John Wiley & Sons, Ltd. [source] Facile synthesis of functional polyperoxides by radical alternating copolymerization of 1,3-dienes with oxygenTHE CHEMICAL RECORD, Issue 5 2009Eriko Sato Abstract We have developed a facile synthesis of degradable polyperoxides by the radical alternating copolymerization of 1,3-diene monomers with molecular oxygen at an atmospheric pressure. In this review, the synthesis, the degradation behavior, and the applications of functional polyperoxides are summarized. The alkyl sorbates as the conjugated 1,3-dienes gave a regiospecific alternating copolymer by exclusive 5,4-addition during polymerization and the resulting polyperoxides decomposed by the homolysis of a peroxy linkage followed by successive , -scissions. The preference of 5,4-addition was well rationalized by theoretical calculations. The degradation of the polyperoxides occurred with various stimuli, such as heating, UV irradiation, a redox reaction with amines, and an enzyme reaction. The various functional polyperoxides were synthesized by following two methods, one is the direct copolymerization of functional 1,3-dienes, and the other is the functionalization of the precursor polyperoxides. Water soluble polyperoxides were also prepared, and the LCST behavior and the application to a drug carrier in the drug delivery system were investigated. In order to design various types of degradable polymers and gels we developed a method for the introduction of dienyl groups into the precursor polymers. The resulting dienyl-functionalized polymers were used for the degradable gels. The degradable branched copolymers showed a microphase-separated structure, which changed owing to the degradation of the polyperoxide segments. © 2009 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 9: 000,000; 2009: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.200900009 [source] Structure of NADP-dependent glyceraldehyde-3-phosphate dehydrogenase from Synechococcus PCC7942 complexed with NADPACTA CRYSTALLOGRAPHICA SECTION F (ELECTRONIC), Issue 4 2006Kei Wada The crystal structure of NADP-dependent glyceraldehyde-3-phosphate dehydrogenase (NADP-GAPDH) from Synechococcus PCC 7942 (S. 7942) in complex with NADP was solved by molecular replacement and refined to an R factor of 19.1% and a free R factor of 24.0% at 2.5,Å resolution. The overall structure of NADP-GAPDH from S. 7942 was quite similar to those of other bacterial and eukaryotic GAPDHs. The nicotinamide ring of NADP, which is involved in the redox reaction, was oriented toward the catalytic site. The 2,-phosphate O atoms of NADP exhibited hydrogen bonds to the hydroxyl groups of Ser194 belonging to the S-loop and Thr37. These residues are therefore considered to be essential in the discrimination between NADP and NAD molecules. The C-terminal region was estimated to have an extremely flexible conformation and to play an important role in the formation of the supramolecular complex phosphoribulokinase (PRK),regulatory peptide (CP12),GAPDH, which regulates enzyme activities. [source] Expression, purification and crystallization of Trypanosoma cruzi dihydroorotate dehydrogenase complexed with orotateACTA CRYSTALLOGRAPHICA SECTION F (ELECTRONIC), Issue 10 2005Daniel Ken Inaoka Dihydroorotate dehydrogenase (DHOD) catalyzes the oxidation of dihydroorotate to orotate, the fourth step and the only redox reaction in the de novo biosynthesis of pyrimidine. DHOD from Trypanosoma cruzi (TcDHOD) has been expressed as a recombinant protein in Escherichia coli and purified to homogeneity. Crystals of the TcDHOD,orotate complex were grown at 277,K by the sitting-drop vapour-diffusion technique using polyethylene glycol 3350 as a precipitant. The crystals diffract to better than 1.8,Å resolution using synchrotron radiation (, = 0.900,Å). X-ray diffraction data were collected at 100,K and processed to 1.9,Å resolution with 98.2% completeness and an overall Rmerge of 7.8%. The TcDHOD crystals belong to the orthorhombic space group P212121, with unit-cell parameters a = 67.87, b = 71.89, c = 123.27,Å. The presence of two molecules in the asymmetric unit (2 × 34,kDa) gives a crystal volume per protein weight (VM) of 2.2,Å3,Da,1 and a solvent content of 44%. [source] | ||||||||||||||||||||||||||||||||||||||||