Large carbon isotope fractionation associated with oxidation of methyl halides by methylotrophic bacteria

The largest biological fractionations of stable carbon isotopes observed in nature occur during production of methane by methanogenic archaea. These fractionations result in substantial (as much as 70) shifts in 13C relative to the initial substrate. We now report that a stable carbon isotopic fractionation of comparable magnitude (up to 70) occurs during oxidation of methyl halides by methylotrophic bacteria. We have demonstrated biological fractionation with whole cells of three methylotrophs (strain IMB-1, strain CC495, and strain MB2) and, to a lesser extent, with the purified cobalamin-dependent methyltransferase enzyme obtained from strain CC495. Thus, the genetic similarities recently reported between methylotrophs, and methanogens with respect to their pathways for C1-unit metabolism are also reflected in the carbon isotopic fractionations achieved by these organisms. We found that only part of the observed fractionation of carbon isotopes could be accounted for by the activity of the corrinoid methyltransferase enzyme, suggesting fractionation by enzymes further along the degradation pathway. These observations are of potential biogeochemical significance in the application of stable carbon isotope ratios to constrain the tropospheric budgets for the ozone-depleting halocarbons, methyl bromide and methyl chloride.

Catalytic Role of Metal Oxides in Gold-Based Catalysts: A First Principles Study of CO Oxidation on TiO2 Supported Au

CO oxidation on TiO2 supported Au has been studied using density functional theory calculations. Important catalytic roles of the oxide have been identified: (i) CO oxidation occurs at the interface between Au and the oxide with a very small barrier; and (ii) O-2 adsorption at the interface is the key step in the reaction. The physical origin of the oxide promotion effect has been further investigated: The oxide enhances electron transfer from the Au to the antibonding states of O-2, giving rise to (i) strong ionic bonding between the adsorbed O-2, Au, and the Ti cation; and (ii) a significant activation of O-2 towards CO oxidation.

Dioxygenase-catalysed oxidation of alkylaryl sulfides: sulfoxidation versus cis-dihydrodiol formation

Toluene- and naphthalene-dioxygenase-catalysed sulfoxidation of nine disubstituted methylphenyl sulfides, using whole cells of Pseudomonas putida, consistently gave the corresponding enantioenriched sulfoxides. Using the P. putida UV4 mutant strain, and these substrates, differing proportions of the corresponding cis-dihydrodiol sulfides were also isolated. Evidence was found for the concomitant dioxygenase-catalysed cis-dihydroxylation and sulfoxidation of methyl paratolyl sulfide. A simultaneous stereoselective reductase-catalysed deoxygenation of (S)-methyl para-tolyl sulfoxide, led to an increase in the proportion of the corresponding cis-dihydrodiol sulfide. The enantiopurity values and absolute configurations of the corresponding cis-dihydrodiol metabolites from methyl ortho-and para-substituted phenyl sulfides were determined by different methods, including chemoenzymatic syntheses from the cis-dihydrodiol metabolites of para-substituted iodobenzenes. Further evidence was provided to support the validity of an empirical model to predict, (i) the stereochemistry of cis-dihydroxylation of para-substituted benzene substrates, and (ii) the regiochemistry of cis-dihydroxylation reactions of ortho-substituted benzenes, each using toluene dioxygenase as biocatalyst.

Electrochemical reduction of benzoic acid and substituted benzoic acids in some room temperature ionic liquids

Using cyclic voltammetry, the electrochemical reduction of benzoic acid (BZA) has been studied at Pt and Au microelectrodes (10 and 2 mu m diameter) in six room temperature ionic liquids (RTILs), namely [C(2)mim][NTf2], [C(4)mim][NTf2], [C(4)mpyrr][NTf2], [C(4)mim][BF4], [C(4)mim][NO3], and [C(4)mim][PF6] (where [C(n)mim](+) = 1-alkyl-3-methylimidazolium, [NTf2](-) = bis(trifluoromethylsulfonyl)imide, [C(4)mpyrr](+) = N-butyl-N-methylpyrrolidinium, [BF4](-) = tetrafluoroborate, [NO3](-) = nitrate, and [PF6](-) = hexafluorophosphate). In all cases, a main reduction peak was observed, assigned to the reduction of BZA in a CE mechanism, where dissociation of the acid takes place before electron transfer to the dissociated proton. One anodic peak was observed on the reverse sweep, assigned to the oxidation of adsorbed hydrogen, and a reductive