Ascorbate Reacts with Singlet Oxygen to Produce Hydrogen Peroxide

Abstract

Singlet oxygen is a highly reactive electrophilic species that reacts rapidly with electron-rich moieties, such as the double bonds of lipids, thiols, and ascorbate (AscH-). The reaction of ascorbate with singlet oxygen is rapid (k = 3 × 108 M-1 s-1). Here we have investigated the stoichiometry of this reaction. Using electrodes to make simultaneous, real-time measurements of oxygen and hydrogen peroxide concentrations, we have investigated the products of this reaction. We have demonstrated that hydrogen peroxide is a product of this reaction. The stoichiometry for the reactants of the reaction (1 1O2 + 1AscH- → 1H2O2 + 1dehydroacorbic) is 1:1. The formation of H2O2 results in a very different oxidant that has a longer lifetime and much greater diffusion distance. Thus, locally produced singlet oxygen with a half-life of 1 ns - 1 μs in a biological setting is changed to an oxidant that has a much longer lifetime and thus can diffuse to distant targets to initiate biological oxidations.