Dynamics of lipid peroxidation and antioxidion of alpha-tocopherol in membranes.

The dynamics of initiation and inhibition of lipid peroxidation by alpha-tocopherol (alpha-Toc) in membranes were investigated under biological conditions using phosphatidylcholine liposomes. First, I examined how superoxide generated in the bulk water phase is able to induce lipid peroxidation in the inner hydrophobic region of the membrane. Second, I studied the localization of the antioxidant OH group of alpha-Toc in membranes and its lipid radical-trapping dynamics. Third, I investigated how alpha-Toc that is oxidized during radical trapping in membranes is recycled by ascorbic acid (AsA) in the bulk water phase. Finally, I studied the deactivation by alpha-Toc of singlet oxygen ((1)O(2)), which was generated by photoirradiation at the membrane surface, in the hydrophobic membrane inner region, and in bulk water, and measured the (1)O(2) deactivating rate constant of alpha-Toc in membranes considering: the concentration and mobility of alpha-Toc molecule in membranes, especially those of its active OH moiety located at the membrane domains, such as the membrane surface polar zone, inner hydrogen belt, and hydrophobic core, and the dielectric constant reflecting the reactivity of the OH moiety and (1)O(2) in the membrane domains where they interact.