Laser access to quercetin radicals and their repair by co-antioxidants

We have demonstrated the feasibility and ease of producing quercetin radicals by photoionization with a pulsed 355nm laser. A conversion efficiency into radicals of 0.4 is routinely achieved throughout the pH range investigated (pH 2-pH 9), and the radical generation is completed within a few ns. No precursor other than the parent compound is needed, and the ionization by-products do not interfere with the further fate of the radicals. With this generation method, we have characterized the quercetin radicals and studied the kinetics of their repairs by co-antioxidants such as ascorbate and 4-aminophenol. Bell-shaped pH dependences of the observed rate constants reflect opposite trends in the availability of the reacting protonation forms of radical and co-antioxidant and even at their maxima mask the much higher true rate constants. Kinetic isotope effects identify the repairs as proton-coupled electron transfers. An examination of which co-antioxidants are capable of repairing the quercetin radicals and which are not confines the bond dissociation energies of quercetin and its monoanion experimentally to 75-77 kcal/mol and 72-75 kcal/mol, a much narrower interval in the case of the former than previously estimated by theoretical calculations.

Keywords: Antioxidants; kinetics; laser chemistry; photoionization.