Despite being an important pigment in skin, hair, the eye and the brain, melanin remains one of the most enigmatic of
pigments. Although the main constituents of melanin are known to be dihydroxyindoles, its photophysics is complex and
its detailed structure remains unknown. In this work we have arrested prior to completion the usual synthesis of
eumelanin formed via auto-oxidation of 3, 4-dihydroxy-L-phenylalanine (L-DOPA), by the addition of copper ions.
Using fluorescence techniques we report how copper modifies the self assembly of eumelanin by reducing the time to the
onset of aggregation at pH 10 and yet produces simplified photophysics in terms of a clearly-defined fluorescence
spectrum and a fluorescence decay that is described well by a dominant single lifetime of ~ 6ns. This behavior is
consistent with copper inducing an enhanced abundance of 5,5-dihydroxyindole-2-carboxylic acid (DHICA). Metal ion
binding to melanin is of particular importance to neurology and has potential applications in optoelectronics.
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