• Ponnusamy Sami

      Articles written in Journal of Chemical Sciences

    • Studies on electron transfer reactions of Keggin-type mixed addenda heteropolytungstovanadophosphates with NADH

      Ponnusamy Sami Kasi Rajasekaran

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      The coenzyme nicotinamide adenine dinucleotide (NADH) undergoes facile electron transfer reaction with vanadium (V) substituted Keggin-type heteropolyanions (HPA) [PVVW11O40]4- (PV1) and [PV$^V_2$W10O40]5- (PV2) in aqueous phosphate buffer of pH 6 at ambient temperature. Electrochemical and optical studies show that the stoichiometry of the reaction is 1 : 2 (NADH : HPA). EPR and optical studies show that HPA act as one electron acceptor and the products of electron transfer reactions are one electron reduced heteropoly blues (HPB), viz. [PVIVW11O40]5- and [PVIVVVW10O40]6-. Oxygraph measurements show that there is no uptake of molecular oxygen during the course of reaction. The reaction proceeds through multi-step electron-proton-electron transfer mechanism, with rate limiting initial one electron transfer from NADH to HPA by outer sphere electron transfer process. Bimolecular rate constant for electron transfer reaction between NADH and PV2 in phosphate buffer of pH = 6 has been determined spectrophotometrically.

    • Studies on electron transfer reactions: Reduction of heteropoly 10-tungstodivanadophosphate by thioglycolic acid in aqueous medium

      Ponnusamy Sami Natarajan Mariselvi Kandasamy Venkateshwari Arunachalam Sarathi Kasi Rajasekaran

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      Rates of electron transfer reaction of thioglycolic acid with vanadium(V) substituted Keggintype heteropolyanion, [PVVVVW10O40]5-, in acetate-acetic acid buffers have been measured spectrophotometrically at 25°C. The order of the reaction with respect to substrate and oxidant is unity. The reaction shows simple second order kinetics at constant pH. The rate of the reaction increases with increase of pH of the medium. The mono-anion HSCH2COO- and di-anion -SCH2COO- are found to be the reactive species. Rate constants for mono-anion and di-anion are evaluated from rate law derived from the mechanism. By applying Rehm-Weller relationship, self exchange rate constant for the -SCH2COO-/S$^{\bullet}$ CH2COO- couple was evaluated as $3.3 \times 10^3$ dm3 mol-1 s-1 at 25°C.

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