Density functional computations of the energetic and spectroscopic parameters of quercetin and its radicals in the gas phase and in solvent
Università della Calabria, Rende, Calabria, ItalyTheoretical Chemistry Accounts (Impact Factor: 2.23). 02/2004; 111(2):210-216. DOI: 10.1007/s00214-003-0544-1
Quercetin and its radicals were investigated at the B3LYP density functional level with the aim of determining the energetic and spectroscopic parameters and the factors that influence their antioxidant activity in the gas phase and in aqueous solution. The results indicated that the antioxidant ability of quercetin is mainly due to the orthodiphenolic moiety but also to the presence of the C=C double bond of the pyrone ring. Differences in the stability order of the isomers of quercetins radicals were found in going from vacuum to solvent. Hyperfine coupling constants were computed to help the interpretation of the intricate ESR spectrum of quercetin.
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[Show abstract] [Hide abstract] ABSTRACT: We present a computational study on two flavonols that were recently isolated from Loranthaceae family plant extracts: kaempferol 3-O-α-L-arabinofuranosyl-(1 → 3)-α-L-rhamnoside and quercetin 3-O-α-L-arabinofuranosyl-(1 → 3)-α-L-rhamnoside. Their structures and energetics have been investigated at the density functional level of theory, up to B3LYP/6-31+G(d,p), incorporating solvent effects with polarizable continuum models. In addition, their potential antioxidant activities were probed through the computation of the (i) bond dissociation enthalpies (BDEs), which are related to the hydrogen-atom transfer mechanism (HAT), and (ii) ionization potentials (IPs), which are related to the single-electron transfer mechanism (SET). The BDEs were determined in water to be 83.23 kcal/mol for kaempferol 3-O-α-L-arabinofuranosyl-(1 → 3)-α-L-rhamnoside and 77.49 kcal/mol for quercetin 3-O-α-L-arabinofuranosyl-(1 → 3)-α-L-rhamnoside. The corresponding IPs were obtained for both compounds as 133.38 and 130.99 kcal/mol, respectively. The BDEs and IPs are comparable to those probed for their parental molecules kaempferol and quercetin; this is in marked contrast to previous studies where glycosylation at the 3-position increases the corresponding BDEs, and, hence, decreases subsequent antioxidant activity. The BDEs and IPs obtained suggest both compounds are promising for antioxidant activity and thus further experimental tests are encouraged.
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