title: Radiative relaxation in synthetic pheomelanin.
abstract: We report a detailed photoluminescence study of cysteinyldopa-melanin (CDM), the synthetic analogue of pheomelanin. Emission spectra are shown to be a far more sensitive probe of CDM's spectroscopic behavior than are absorption spectra. Although CDM and dopa-melanin (DM, the synthetic analogue of eumelanin) have very similar absorption spectra, we find that they have very different excitation and emission characteristics; CDM has two distinct photoluminescence peaks that do not shift with excitation wavelength. Additionally, our data suggest that the radiative quantum yield of CDM is excitation energy dependent, an unusual property among biomolecules that is indicative of a chemically disordered system. Finally, we find that the radiative quantum yield for CDM is approximately 0.2%, twice that of DM, although still extremely low. This means that 99.8% of the energy absorbed by CDM is dissipated via nonradiative pathways, consistent with its role as a pigmentary photoprotectant.
authors.affiliation: Soft Condensed Matter Physics Group and Centre for Biophotonics and Laser Science, School of Physical Sciences, University of Queensland, St. Lucia, Brisbane, Queensland 4072, Australia. riesz@physics.uq.edu.au
authors.forename: Jennifer
authors.initials: J
authors.lastname: Riesz
authors.forename: Tadeusz
authors.initials: T
authors.lastname: Sarna
authors.forename: Paul
authors.initials: P
authors.lastname: Meredith
mesh_terms: D003548:Cysteinyldopa / Q000031:analogs & derivatives* / Q000737:chemistry; D049449:Luminescence; D008543:Melanins / Q000138:chemical synthesis / Q000737:chemistry*; D010777:Photochemistry
chemical_list: D008543:Melanins; C523049:cysteinyldopa-melanin; C018362:pheomelanin; D003548:Cysteinyldopa