Solid-state cross-polarization magic angle spinning 13C and 15N NMR characterization of Sepia melanin, Sepia melanin free acid and Human hair melanin in comparison with several model compounds

This paper presents the high-resolution C-13 and N-15 cross-polarization magic angle spinning (CP/MAS) NMR spectra of three natural melanin solids: Sepia officinalis melanin, Sepia officinalis melanin free acid (MFA) and Human hair melanin. The functional group characterization of Human hair melanin by NMR is the first to date and the C-13 CP/MAS NMR spectra reported here show improved resolution of chemically inequivalent sites. The observed spectral regions of the solid melanin samples can be assigned to the postulated structural unit of the polymer chain of Sepia MFA derived from solution-state NMR studies. To assist in the assignment of functional groups in the spectra, the solid-state CP/MAS NMR spectra are compared with high-resolution C-13 and N-15 CP/MAS spectra of four model compounds, L-dopa, dopamine, 2-methoxycarbonyl-3-ethoxycarbonyl-4-methylpyrrole and ethyl 5,6-dimethoxyindole-2-carboxylate. To aid further in the assignment of protonated and non-protonated carbon atoms, CP contact time dependence and non-quaternary carbon suppression (NQS) experiments were performed on the melanin samples. The N-15 CP/MAS spectra of the melanin samples confirm the presence of indole and pyrrole units in the melanin polymer chain. The NMR peaks observed in all of the melanin samples are relatively broad, presumably owing to the presence of free radicals. Electron spin resonance (ESR) data shows that all three melanin samples contain localized free radicals (g = 2.007), with the Sepia melanin containing a 10-fold higher free radical density than Human hair melanin. Copyright (C) 2003 John Wiley Sons, Ltd.