Abstract
The spectroscopic behaviour of lumiflavin (7,8,10-trimethyl-isoalloxazine, oxidized form LFox) in aqueous solutions of pH range -1.08 to 14.6 is studied. Absorption spectra, fluorescence quantum distributions, quantum yields and lifetimes are determined. The ionization stage of ground-state LFox changes from cationic (LFoxH2+) at low pH (pK(c) approximate to 0.38) via neutral (LFoxH) to anionic ...
Abstract
The spectroscopic behaviour of lumiflavin (7,8,10-trimethyl-isoalloxazine, oxidized form LFox) in aqueous solutions of pH range -1.08 to 14.6 is studied. Absorption spectra, fluorescence quantum distributions, quantum yields and lifetimes are determined. The ionization stage of ground-state LFox changes from cationic (LFoxH2+) at low pH (pK(c) approximate to 0.38) via neutral (LFoxH) to anionic (LFox-) at high pH (pK(a) approximate to 10.8). The cationic, neutral, and anionic forms are identified by their different absorption spectra. LFox H in neutral aqueous solution is reasonably fluorescent (fluorescence quantum yield OF 0.29, fluorescence lifetime tau(F)approximate to 5.2 ns), while LFox- is weakly fluorescent (phi(F)approximate to 0.0042, tau(F)approximate to 90 ps), and LFoxH2+ is nearly non-fluorescent (phi(F)approximate to 3.6 x 10(-5), tau(F)approximate to 0.4 ps). A theory of the pH dependent equilibration of cationic, neutral and anionic molecules in the ground state and their dynamics in the excited state is developed. For lumiflavin in aqueous solution in the excited state no equilibrium distributions are reached between the cationic, neutral, and anionic forms. Some neutral excited lumiflavin transforms to the cationic ground-state form at low pH by intermolecular photo-induced proton transfer from H3O+ to LFoxH*. At high pH no photo-induced intermolecular proton transfer takes place. (C) 2010 Elsevier B.V. All rights reserved.
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