Electron-nuclear double resonance (ENDOR) signals from matrix protons interacting with the stable free radicals of "A"- and "B"-type melanins have been observed as a function of pH. In all samples the single line is similar in width and unusually narrow. The ENDOR reduction varies by more than a factor of 10, indicating a large sensitivity of relaxation properties of melanin to sample type. Signals were observed over a wide range of experimental conditions with good signal-to-noise ratio, establishing feasibility for further more detailed ENDOR studies. Incubation in D2O resulted in little change, indicating that the free radical is well buried or protected. No resolved hyperfine structure was seen, consistent with the generally accepted view that melanin is a heterogeneous polymer.
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