Synthesis and polymerization studies of organic-soluble eumelanins

The isolation, structure determination and chemical characterization of eumelanins has been plagued by their very low solubility in organic solvents. To gain insights into the structure and reactivity of these unusual and important biologic macromolecules and to pave the way for their use in electronics, we have prepared soluble melanins via the synthesis of monomeric precursors containing lipophilic substituents. Two such monomers derived from 5,6-dihydroxyindole-2-carboxytic acid (DHICA) were prepared, namely the benzyl and octyl ester derivatives. Both benzyl and octyl ester monomers were oxidatively polymerized to yield dark, melanin-like pigments. These polymerization processes were followed by UV-visible, fluorescence and NMR spectroscopy. These studies showed that the polymerizations proceeded by cross-linking at the 4- and 7-positions of the indole nucleus and led to highly heterogeneous polymeric products. Incorporation of a lipophilic benzyl or octyl group resulted in enhanced solubility of the pigments in a wide range of organic solvents. The UV-visible spectra of the organically soluble synthetic melanins were essentially identical to that of natural eumelanin.