The activity of 3- and 7-hydroxyflavones as scavengers of superoxide radical anion generated from photo-excited riboflavin

Abstract

The visible-light irradiation of the system Rivoflavin plus 3-hydroxyflavone or plus 7-hydroxyflavone, under aerobic conditions, produces a series of competitive processes that depend on the relative concentrations of the pigment and the flavones. The picture comprises photochemical mechanisms that potentially operate in nature. They mainly include the quenching of Rf singlet (1Rf*) and triplet (3Rf*) excited states (with bimolecular rate constants in the order of 109 M–1 s–1) and superoxide radical anion-mediated reactions. The participation of the oxidative species singlet molecular oxygen was not detected. The overall result shows chemical transformations in both Rf and 3-hydroxyflavone. No experimental evidence was found indicating any chemical reaction involving 7-hydroxyflavone. The fate of the pigment also depends on the amount of the dissolved flavonoid. At 50 mM concentrations of these compounds or higher, practically no photochemistry occurs, owing to the extensive quenching of 1Rf*. When the concentration of the flavones is in the mM range or lower, 3Rf* is photogenerated. Then, the excited triplet species can be quenched mainly by the flavones through an electron-transfer process, yielding the semireduced pigment. The latter interacts with dissolved oxygen producing O2·–, which reacts with both the pigment and 3-hydroxyflavone. In summary, 3-hydroxyflavone and 7-hydroxyflavone participate in the generation of superoxide ion in an Rf-sensitized process, and simultaneously 3-hydroxyflavone constitutes a degradable quencher of the oxidative species.Key words: flavones, riboflavin, sensitization, singlet molecular oxygen, superoxide radical anion.