Examination of the chemical behavior of the quercetin radical cation towards some bases

It has been generally accepted that, due to high ionization potential values, single electron transfer followed by proton transfer (SET-PT) is not a plausible mechanism of antioxidant action in flavonoids. In this paper the SET-PT mechanism of quercetin (Q) was examined by revealing possible reaction paths of the once formed quercetin radical cation (Q(+center dot)) at the M0-52X/6311+G(d,p) level of theory. The deprotonation of Q(+center dot) was simulated by examining its chemical behavior in the presence of three bases: methylamine (representative of neutral bases), the MeS anion (CH3S-) and the hydroxide anion (representative of anionic bases). It was found that Q(+center dot) will spontaneously be transformed into Q in the presence of bases whose HOMO energies are higher than the SOMO energy of Q(+center dot) in a given medium, implying that Q cannot undergo the SET-PT mechanism in such an environment. In the reaction with the MeS anion in both gaseous and aqueous phases and the hydroxide anion in the gaseous phase Q(+center dot) accepts an electron from the base, and so-formed Q undergoes the hydrogen atom transfer mechanism. On the other hand, SET-PT is a plausible mechanism of Q in the presence of bases whose HOMO energies are lower than the SOMO energy of Q(+center dot) in a given medium. In such cases Q(+center dot) spontaneously donates a proton to the base, with energetic stabilization of the system. Our investigation showed that Q conforms to the SET-PT mechanism in the presence of methylamine, in both gaseous and aqueous phases, and in the presence of the hydroxide anion, in the aqueous solution.