Excited-State Proton-Transfer Processes of DHICA Resolved: From Sub-Picoseconds to Nanoseconds
Alice Corani1, Alessandro Pezzella2, Torbjörn Pascher1
1†Department of Chemical Physics, Lund University, Box 124, 22100 Lund, Sweden.
Abstract:
Excited-state proton transfer has been hypothesized as a mechanism for UV energy dissipation in eumelanin skin pigments. By using time-resolved fluorescence spectroscopy, we show that the previously proposed, but unresolved, excited-state intramolecular proton transfer (ESIPT) of the eumelanin building block 5,6-dihydroxyindole-2-carboxylic acid (DHICA) occurs with a time constant of 300 fs in aqueous solution but completely stops in methanol. The previously disputed excited-state proton transfer involving the 5- or 6-OH groups of the DHICA anion is now found to occur from the 6-OH group to aqueous solvent with a rate constant of 4.0 × 10(8) s(-1).
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