Comparative analysis of molecular properties and reactions with oxidants for quercetin, catechin, and naringenin

Flavonoids, a large group of secondary plant phenolic metabolites, are important natural antioxidants and regulators of cellular redox balance. The present study addressed evaluation of the electronic properties of some flavonoids belonging to different classes such as quercetin (flavonols), catechin (flavanols), and naringenin (flavanones) and their interactions with oxidants in model systems of DPPH reduction, flavonoid autoxidation, and chlorination. According to our ab initio calculations, the high net negative excess charges of the C rings and the small positive excess charges of the B rings of quercetin, catechin, and naringenin make these parts of flavonoid molecules attractive for electrophilic attack. The 3′-OH group of the B ring of quercetin has the highest excess negative charge and the lowest energy of hydrogen atom abstraction for the flavonoids studied. The apparent reaction rate constants (s(−1), 20 °C) and the activation energies (kJ/mol) of DPPH reduction were 0.34 ± 0.06 and 23.0 ± 2.5 in the case of quercetin, 0.09 ± 0.02 and 32.5 ± 2.5 in the case of catechin, respectively. The stoichiometry of the DPPH–flavonoid reaction was 1:1. The activation energies (kJ/mol) of quercetin and catechin autoxidations were 50.8 ± 6.1 and 58.1 ± 7.2, respectively. Naringenin was not oxidized by the DPPH radical and air oxygen (autoxidation) and the flavonoids studied effectively prevented HOCl-induced hemolysis due to direct scavenging of hypochlorous acid (flavonoid chlorination). The best antioxidant quercetin had the highest value of HOMO energy, a planar structure and optimal electron orbital delocalization on all the phenolic rings due to the C2=C3 double bond in the C ring (absent in catechin and naringenin).