Photochemical Oxidation of Water by 2-Methyl-1,4-benzoquinone: Evidence against the Formation of Free Hydroxyl Radical

Photolysis of 2-methyl-1,4-benzoquinone (toluquinone) in aqueous solution results in the oxidation of water to create either hydroxyl radical or some species capable of transferring a hydroxyl radical. Trapping of the latter with dimethyl sulfoxide (DMSO) creates a methyl radical which in turn can be trapped by the stable radical 3-amino-2,2,5,5-tetramethyl-1-pyrrolidinyloxy. Competitive trapping studies using DMSO and either nitrite anion or salicylate anion show that the hydroxylating species is much more selective in its reactions than free hydroxyl radical. Laser flash photolysis experiments on toluquinone in aqueous solution show formation of a transient species immediately (<150 ns) following the excitation pulse that had previously been assigned to the excited triplet state of the quinone. This spectrum differs from the authentic triplet state spectrum generated in less reactive organic solvents (carbon tetrachloride and acetonitrile). The same intermediate is shown to react with the hydroxyl radic...