Sequential Proton-Coupled Electron Transfer Mediates Excited-State Deactivation of a Eumelanin Building Block

Juan J. Nogueira, Alice Corani, Amal El Nahhas, Alessandro Pezzella, Marco D’Ischia, Leticia González, Villy Sundström

Forskningsoutput: TidskriftsbidragArtikel i vetenskaplig tidskriftPeer review

18 Citeringar (SciVal)

Sammanfattning

Skin photoprotection is commonly believed to rely on the photochemistry of 5,6-dihydroxyindole (DHI)- and 5,6-dihydroxyindole-2-carboxylic acid (DHICA)-based eumelanin building blocks. Attempts to elucidate the underlying excited-state relaxation mechanisms have been partly unsuccessful due to the marked instability to oxidation. We report a study of the excited-state deactivation of DHI using steady-state and time-resolved fluorescence accompanied by high-level quantum-chemistry calculations including solvent effects. Spectroscopic data show that deactivation of the lowest excited state of DHI in aqueous buffer proceeds on the 100 ps time scale and is 20 times faster than in methanol. Quantum-chemical calculations reveal that the excited-state decay mechanism is a sequential proton-coupled electron transfer, which involves the initial formation of a solvated electron from DHI, followed by the transfer of a proton to the solvent. This unexpected finding would prompt a revision of current notions about eumelanin photophysics and photobiology.

Originalspråkengelska
Sidor (från-till)1004-1008
Antal sidor5
TidskriftThe Journal of Physical Chemistry Letters
Volym8
Utgåva5
DOI
StatusPublished - 2017 mar 2

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