The photoreactive free radical in eumelanin

Melanin is the primary photoprotecting pigment in humans as well as being implicated in the development of deadly melanoma. The material also conducts electricity and has thus become a bioelectronic model for proton-to-electron transduction. Central to these phenomena are its spin properties—notably two linked species derived from carbon-centered and semiquinone radicals. Using a novel in situ photoinduced electron paramagnetic resonance technique with simultaneous electrical measurements, we have elucidated for the first time the distinct photoreactivity of the two different radical species. We find that the production of the semiquinone is light- and water-driven, explaining the electrical properties and revealing biologically relevant photoreactivity.