title: Detailed Investigation of the OH Radical Quenching by Natural Antioxidant Caffeic Acid Studied by Quantum Mechanical Models.
abstract: The effectiveness of naturally occurring antioxidant caffeic acid in the inactivation of the very damaging hydroxyl radical has been theoretically investigated by means of hybrid density functional theory. Three possible pathways by which caffeic acid may inactivate free radicals were analyzed: hydrogen abstraction from all available hydrogen atoms, hydroxyl radical addition to all carbon atoms in the molecule, and single electron transfer. The reaction paths were traced independently, and the respective thermal rate constants were calculated using variational transition-state theory including the contribution of tunneling. The more reactive sites in caffeic acid are the C4OH phenolic group and the C4 carbon atom, for the hydrogen abstraction and radical addition, respectively. The single electron transfer process seems to be thermodynamically unfavored, in both polar and nonpolar media. Both hydrogen abstraction and radical addition are very feasible, with a slight preference for the latter, with a rate constant of 7.29 × 10(10) M(-1) s(-1) at 300 K. Tunnel effects are found to be quite unimportant in both cases. Results indicate caffeic acid as a potent natural antioxidant in trapping and scavenging hydroxyl radicals.
authors.affiliation: Dipartimento di Chimica and Centro di Calcolo ad Alte Prestazioni per Elaborazioni Parallele e Distribuite-Centro d'Eccellenza MIUR, Università della Calabria , I-87030 Arcavacata di Rende (CS), Italy.
authors.forename: Monica
authors.initials: M
authors.lastname: Leopoldini
authors.affiliation: Dipartimento di Chimica and Centro di Calcolo ad Alte Prestazioni per Elaborazioni Parallele e Distribuite-Centro d'Eccellenza MIUR, Università della Calabria , I-87030 Arcavacata di Rende (CS), Italy.
authors.forename: Sandro G
authors.initials: SG
authors.lastname: Chiodo
authors.affiliation: Dipartimento di Chimica and Centro di Calcolo ad Alte Prestazioni per Elaborazioni Parallele e Distribuite-Centro d'Eccellenza MIUR, Università della Calabria , I-87030 Arcavacata di Rende (CS), Italy.
authors.forename: Nino
authors.initials: N
authors.lastname: Russo
authors.affiliation: Dipartimento di Chimica and Centro di Calcolo ad Alte Prestazioni per Elaborazioni Parallele e Distribuite-Centro d'Eccellenza MIUR, Università della Calabria , I-87030 Arcavacata di Rende (CS), Italy.
authors.forename: Marirosa
authors.initials: M
authors.lastname: Toscano