Oxidation of catechol in plants : III. Purification and properties of the diphenylene dioxide 2,3-quinone-forming enzyme system from Tecoma leaves

In attempting to determine the nature of the enzyme system mediating the conversion of catechol to diphenylenedioxide 2,3-quinone, in Tecoma leaves, further purification of the enzyme was undertaken. The crude enzyme from Tecoma leaves was processed further by protamine sulfate precipitation, positive adsorption on tricalcium phosphate gel, and elution and chromatography on DEAE-Sephadex. This procedure yielded a 120-fold purified enzyme which stoichiometrically converted catechol to diphenylenedioxide 2,3-quinone. The purity of the enzyme system was assessed by polyacrylamide gel electrophoresis. The approximate molecular weight of the enzyme was assessed as 200,000 by gel filtration on Sephadex G-150. The enzyme functioned optimally at pH 7.1 and at 35 °C. The Km for catechol was determined as 4 × 10−4 Image . The enzyme did not oxidize o-dihydric phenols other than catechol and it did not exhibit any activity toward monohydric and trihydric phenols and flavonoids. Copper-chelating agents did not inhibit the enzyme activity. Copper could not be detected in the purified enzyme preparations. The purified enzyme was not affected by extensive dialysis against copper-complexing agents. It did not show any peroxidase activity and it was not inhibited by catalase. Hydrogen peroxide formation could not be detected during the catalytic reaction. The enzymatic conversion of catechol to diphenylenedioxide 2,3-quinone by the purified Tecoma leaf enzyme was suppressed by such reducing agents as GSH and cysteamine. The purified enzyme was not sensitive to carbon monoxide. It was not inhibited by thiol inhibitors. The Tecoma leaf was found to be localized in the soluble fraction of the cell. Treatment of the purified enzyme with acid, alkali, and urea led to the progressive denaturation of the enzyme.

Electro-Oxidation of Borohydride on Rhodium, Iridium, and Rhodium-Iridium Bimetallic Nanoparticles with Implications to Direct Borohydride Fuel Cells

Electrochemical oxidation of borohydride is studied on nanosized rhodium, iridium, and bimetallic rhodium-iridium catalysts supported onto Vulcan XC72R carbon. The catalysts are characterized by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy in conjunction with cyclic voltammetry and polarization studies. The studies reveal that a 20 wt % bimetallic Rh-Ir catalyst supported onto carbon (Rh-Ir/C) is quite effective for the oxidation of borohydride. Direct borohydride fuel cell with Rh-Ir/C as the anode catalyst and Pt/C as the cathode catalyst exhibits a peak power density of 270 mW/cm(2) at a load current density of 290 mA/cm(2) as against 200 mW/cm(2) at 225 mA/cm(2) for Rh/C and 140 mW/cm(2) at 165 mA/cm(2) for Ir/C while operating at 80 degrees C. The synergistic catalytic activity for the bimetallic Rh-Ir nanoparticles toward borohydride oxidation is corroborated by density-functional theory calculations using electron-localization function. (C) 2010 The Electrochemical Society. [DOI:10.1149/1.3442372] All rights reserved.

Quinone studies. Part III. Metal ion-catalysed oxidation of halophenols and halonaphthols by peroxidisulphate

Oxidation of representative halophenols and halonaphthols by peroxidisulphate has been examined. The influence of metallic ions, viz. Cu2+, Fe3+, Ag+, on the above reaction has been studied. Cu2+ ion-catalyzed oxidation gives halo-1, 4-quinones in excellent yield. Potassium bis(biureto)cuprate(III) complex also oxidises halophenols to halo-1, 4-quinones.

A kinetic study of liquid-phase catalytic oxidation of styrene to benzaldehyde with Wilkinson complex

Liquid-phase homogeneous catalytic oxidation of styrene with Wilkinson complex by molecular oxygen in toluene medium gave selectively benzaldehyde and formaldehyde as the primary products. Higher temperatures and styrene conversions eventually led to acid formation due to co-oxidation of aldehyde.A reaction induction period and an initiation period, typical of free-radical reactions, characterized the oxidation process. The effects of temperature and catalyst and styrene concentrations on the conversion of styrene to benzaldehyde and acid formation have been studied. The optimum reaction parameters have been determined as a styrene-to-solvent mole ratio of 0.5, a catalyst-to-styrene mole ratio of 5.0 X lo4, and a reaction temperature of 75 "C. A reaction scheme based upon free-radical mechanism yielded a pseudo-first-order model which agreed well with the observed kinetic data in the absence of co-oxidation of aldehyde. A second-order model was found to fit the experimental data better in the case of aldehyde conversion to acid.

NO reduction, CO and hydrocarbon oxidation over combustion synthesized Ag/CeO2 catalyst

The combustion technique produces ionically dispersed Ag on a nano-crystalline CeO2 surface. The catalysts thus produced were characterized by X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy. Catalytic properties towards NO reduction, CO and hydrocarbon oxidation have been investigated using the temperature programmed reaction technique in a packed bed tubular reactor. These results are compared with alpha-Al2O3 supported finely divided Ag metal particles synthesized by the same method. Both oxidation and reduction reactions over Ag/CeO2 have been observed to occur at lower temperatures compared to Ag/Al2O3. The rate and turnover frequency of the NO+CO reaction over 1% Ag/CeO2 are 56.3 mu mol g(-1) s(-1) and 0.97 s(-1) at 225 degrees C respectively. Activation energy (E-a) values are 71 and 67 kJ mol(-1) for CO+O-2 and NO+CO reactions, respectively, over 1% Ag/CeO2 catalyst.

1,2-Shift in the anodic oxidation of aromatic compounds

The 1,2-shift observed during oxidation of organic substrates can arise by involvement of cation radicals.

Growth of titanium oxide overlayers by thermal oxidation of titanium

This paper describes a theoretical model for the growth of titanium oxide by thermal oxidation of titanium. It is shown that this model can explain the formation of layers of different oxides of titanium and the changes in these layers with variations in the conditions of oxidation. Some experimental X-ray diffraction results which support the model are also given.

Identification of corona discharge-induced SF6 oxidation mechanisms using SF6/18O2/H216O and SF6/16O2/H218O gas mixtures

The absolute yields of gaseous oxyfluorides SOF2, SO2F2, and SOF4 from negative, point-plane corona discharges in pressurized gas mixtures of SF6 with O2 and H2O enriched with18O2 and H2 18O have been measured using a gas chromatograph-mass spectrometer. The predominant SF6 oxidation mechanisms have been revealed from a determination of the relative18O and16O isotope content of the observed oxyfluoride by-product. The results are consistent with previously proposed production mechanisms and indicate that SOF2 and SO2F2 derive oxygen predominantly from H2O and O2, respectively, in slow, gas-phase reactions involving SF4, SF3, and SF2 that occur outside of the discharge region. The species SOF4 derives oxygen from both H2O and O2 through fast reactions in the active discharge region involving free radicals or ions such as OH and O, with SF5 and SF4.

Vapor phase oxidation of p-xylene

The kinetics of the vapor phase oxidation of p-xylene over ferric molybdate catalyst were studied in an isothermal, differential, tubular flow reactor in the temperature range of 360 to 420° C. The major product obtained was p-tolualdehyde with small amounts of maleic anhydride and p-toluic acid. No terephthalic acid or CO2 were observed. The reaction rate data collected fit the redox model given by Equation 1. The values of activation energies Ex, Eo and frequency factors Ax, Ao obtained are 72, 63 kJ/mol and 0.64, 2.89 m3/kg catalyst s respectively. The reaction mechanism was established by studying the oxidation of p-tolualdehyde, toluic and terephthalic acids. It is concluded that the reaction follows a parallel-consecutive scheme. On a étudié la cinétique de l'oxydation, en phase gazeuse, du para-xylène sur un catalyseur consistant en molybdate ferrique; cette oxydation s'est faite dans un réacteur à écoulement tubulaire, isothermique et différentiel, dans une échelle de températures comprises entre 360°C et 420°C. Le produit principal obtenu a été le para-tolualdéhyde; on a aussi trouvé de faibles quantités d'anhydride maléique et d'acide para-toluique, mais on n'a pas noté la présence d'acide téréphtalique ni d'anhydride carbonique (CO2). Les résultats obtenus en ce qui a trait à la vitesse de réaction concordent bien avec les données du modèle redox indiquées par l'équation 1. Les valeurs des énergies d'activation Ex et Eo ainsi que des facteurs de fréquence Ax et Ao obtenus sont respectivement 72 et 63 kilojoules/mol. et 0.64 × 103 et 2.89 m3/kg de catalyseur. On a établi le mécanisme de la réaction en étudiant l'oxydation du para-tolualdéhyde et des acides toluique et téréphtalique. On conclut que la réaction se fait d'une manière parallèle et consécutive.

A bifunctional approach towards the mild oxidation of organic halides: 2-dimethylamino-N,N-dimethylaniline N-oxide

The titled reagent incorporates an oxygen-centred nucleophile and a basic moiety�in a suitably mutual orientation�in the same molecule. It oxidises various primary benzylic bromides to the corresponding aromatic aldehydes under relatively mild conditions (MeCN/rt�50°C/6�24 h) in high yields (83�97%), and is thus a useful alternative to the Kornblum procedure.

Hemin-mediated oxidation of dithiothreitol reduces oxygen to H2O

Hemin catalyses the oxidation of dithiothreitol. One mole of oxygen is consumed for every 2 moles of dithiothreitol oxidized and the product is shown by spectral studies to be the intramolecular disulphide. The reaction shows a specificity for dithiol and for free heme moieties. Hemin molecules exhibit cooperativity in oxygen reduction. Oxygen radicals do not seem to be involved. H2O2 is not required for this oxidation of dithiothreitol and does not appear to be an intermediate in the reduction of O2 to H2O. However, an independent minor reaction involving a 2-electron transfer with the formation of H2O2 also occurs. These studies on the hemin-catalyzed oxidation of dithiothreitol provide a chemical model for a direct 4-electron reduction of O2 to H2O.