DFT Study of the Direct Radical Scavenging Potency of Two Natural Catecholic Compounds
| Autor: | Ana Amić, Denisa Mastiľák Cagardová |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2022 |
| Předmět: |
Anions
Organic Chemistry quercetin rooperol peroxyl radicals density functional theory kinetics tunnelling Free Radical Scavengers General Medicine Catalysis Computer Science Applications Inorganic Chemistry Kinetics Quercetin Protons Physical and Theoretical Chemistry Molecular Biology Spectroscopy Hydrogen |
| Zdroj: | International Journal of Molecular Sciences; Volume 23; Issue 22; Pages: 14497 |
| Popis: | 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 theoretically 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 prediction 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. |
| Databáze: | OpenAIRE |
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