PHOTOINDUCED OXYGEN CONSUMPTION IN MELANIN SYSTEMS. ACTION SPECTRA AND QUANTUM YIELDS FOR EUMELANIN AND SYNTHETIC MELANIN

Abstract— The first quantitative measurements of the wavelength dependence of oxygen consumption in systems containing eumelanin (from bovine eyes) and synthetic DOPA melanin are reported. Consumption of oxygen (considered to be a requirement for immediate pigment darkening) during irradiation of melanins with either visible or ultraviolet light was monitored using a spin probe nitroxide-electron spin resonance spectroscopic approach. From initial rates of oxygen removal, quantum yields have been obtained over a wavelength range from 230 to 600 nm. Eumelanins are moderately effective in promoting oxygen consumption; quantum yields are low for irradiation with visible light, but increase sharply with light of shorter wavelengths. The absolute quantum yield for oxygen consumption is about 0.1% for natural melanin at 320 nm. The action spectrum is similar for both natural and synthetic melanins, indicating that the major chromophore responsible for oxygen consumption is the same for both kinds of material. This chromophore is not the major melanin chromophore responsible for absorption of visible light. The action spectrum also clearly differs from published action spectra for melanogenesis; however, the weak wavelength dependence for visible light is similar to that found for immediate pigment darkening. Catalase decreases the rate of oxygen consumption by 50%, confirming that hydrogen peroxide is the major molecular product of oxygen reduction. A Type I (free-radical) mechanism evidently predominates: D₂O and azide are shown to have only minor effects, ruling out any major contribution from a Type II (singlet-oxygen) process to the overall oxygen consumption.