Naslov
DFT Study of the Direct Radical Scavenging Potency of Two Natural Catecholic Compounds

Autori
Amić, Ana ; Mastiľák Cagardová, Denisa

Izvornik
International Journal of Molecular Sciences, Special Issue (1422-0067) 23 (2022); 14497, 15

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
quercetin ; rooperol ; peroxyl radicals ; density functional theory ; kinetics ; tunnelling

Sažetak
To ascertain quercetin’s and rooperol’s potency of H-atom donation to CH3OO• and HOO•, thermodynamics, kinetics and tunnelling, three forms of chemical reaction control, were theo- retically examined. In lipid media, H-atom donation from quercetin’s catecholic OH groups via the proton-coupled electron transfer (PCET) mechanism, is more relevant than from C-ring enolic moiety. Amongst rooperol’s two catecholic moieties, H-atom donation from A-ring OH groups is favored. Allylic hydrogens of rooperol are poorly abstractable via the hydrogen atom transfer (HAT) mechanism. Kinetic analysis including tunnelling enables a more reliable predic-tion of the H-atom donation potency of quercetin and rooperol, avoiding the pitfalls of a solely thermodynamic approach. Obtained results contradict the increasing number of misleading statements about the high impact of C–H bond breaking on polyphenols’ antioxidant potency. In an aqueous environment at pH = 7.4, the 3-O− phenoxide anion of quercetin and rooperol’s 4′-O− phenoxide anion are preferred sites for CH3OO• and HOO• inactivation via the single electron transfer (SET) mechanism.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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