Mechanism of lipid radical formation following exposure of epidermal homogenate to ultraviolet light.

It has been suggested that oxygen free radicals are important mediators of lipid peroxidation in the epidermis exposed to ultraviolet (UV) light. However, it is not clear whether it is the superoxide anion radical (O2-.) or the hydroxyl radical (.OH) that plays the major role in producing the lipid radicals (L.) following UV exposure. In this study, we used electron spin resonance (ESR) technique with the spin trap (5,5-dimethyl-1-pyrroline-N-oxide [DMPO]) to determine which active oxygen species is involved in the UV-induced lipid radical formation (DMPO-L.: aN = 15.5 G, aH = 22.7 G). In the presence of superoxide dismutase or the metal-chelating agent, the DMPO-spin adduct spectrum of lipid radicals was reduced remarkably. The lipid radicals were formed by the hydroxyl radical generation system, not the superoxide anion generation system. The hydroxyl radical was found to be the direct active oxygen species that can generate lipid radicals as a result of .OH-mediated hydrogen atom abstraction. Superoxide anion radical stimulated the generation of hydroxyl radical via the iron-catalyzed reaction.