Abstract

The oxidation of the antioxidants dihydrolipoate and lipoamide by triplet duroquinone (3DQ) has been studied by laser flash photolysis and time-resolved resonance Raman (TR3) spectroscopy. Reaction of3DQ with lipoamide by electron transfer [k(H2O)/k(D2O ∼ 1] was more rapid than with dihydrolipoate, in which a proton is also involved [k(H2O)/k(D2O ∼ 2]. For dihydrolipoate at neutral pH the undeprotonated form was the major reactive species with k ∼ 109dm3mol−1s−1. At higher pH values the reaction of ionised (thiolate) forms was observed with k ≥ 4 × 109dm3mol−1s−1. The electron transfer mechanism of reaction between3DQ and lipoamide was confirmed by TR3spectra in which formation of the durosemiquinone radical anion and lipoamide disulfide radical cation (RSS+•) was observed.

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