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Spectroscopy and Photoreactivity of Trichochromes: Molecular Components of Pheomelanins

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  • This paper is part of a special issue dedicated to Professor J. C. (Tito) Scaiano on the occasion of his 60th birthday.

ABSTRACT

The trichochromes are a class of small molecules present in pheomelanin (the red melanin) and absent in eumelanin (the black melanin). Herein trichochrome F (TF) and decarboxy-trichochrome C (dTC) are examined. Both trichochromes are characterized by a visible absorption band, which is shown to be the result of overlapping transitions of the cis and trans isomers. The temperature dependence of the absorption spectrum of dTC suggests the additional presence of equilibrium between the enol and keto forms of the molecule. These conclusions are supported by ground-state energies of these isomers obtained using a continuum solvation model. Near-infrared emission measurements were not able to detect photoproduction of 1O2, and spin-trapping experiments revealed formation of O2*-. DNA nicking assays also revealed a low level of light-induced aerobic activity of dTC, suggesting a quantum efficiency of at most 5 × 10-6 for the photo-generation of O2*-. These results are consistent with pump-probe optical experiments, which reveal efficient and nearly complete ground-state recovery within a few picoseconds of excitation. Both trichochromes are efficient quenchers of 1O2, exhibiting a bimolecular rate constant comparable with vitamin C. These results suggest that trichochromes could serve a protective role in pheomelanin pigments.

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