Zusammenfassung
The absorption and emission spectroscopic behavior of alloxazine is studied in aqueous solutions at pH 4 (10(-4)M HCl) and pH 10 (10(-4)M NaOH). At pH 4 only the pure form of alloxazine is present, while at pH 10 about 9% of alloxazine is present in its tautomeric form of isoalloxazine. Absorption cross-section spectra, fluorescence emission quantum distributions, fluorescence excitation quantum ...
Zusammenfassung
The absorption and emission spectroscopic behavior of alloxazine is studied in aqueous solutions at pH 4 (10(-4)M HCl) and pH 10 (10(-4)M NaOH). At pH 4 only the pure form of alloxazine is present, while at pH 10 about 9% of alloxazine is present in its tautomeric form of isoalloxazine. Absorption cross-section spectra, fluorescence emission quantum distributions, fluorescence excitation quantum distributions, excitation wavelength dependent fluorescence quantum yields, fluorescence lifetimes, and radiative lifetimes are determined. The spectroscopic behavior of alloxazine at pH 4 and pH 10 is compared with that of 7,8-dimethyl-alloxazine (lumichrome) at pH 4 and pH 10. Photo-induced (excited-state) tautomerization of alloxazine to isoalloxazine is observed which does not occur for lumichrome. In the case of alloxazine the highest occupied molecular n orbital (n-HOMO) is energetically well below the highest occupied molecular pi orbital (pi-HOMO) giving non-degenerate ground-state to first excited-state (pi pi*) transition. For isoalloxazine, lumichrome, and lumichrome-10H-tautomer n-HOMO is only slightly below pi-HOMO causing photo-induced ground-state n -> pi electron transfer with elongation of fluorescence lifetime and radiative lifetime. (C) 2015 Elsevier B.V. All rights reserved.
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