RESUMO
Naturally occurring flavonoids, delphinidin, pelargonidin and malvin, were investigated experimentally and theoretically for their ability to scavenge hydroxyl and nitric oxide radicals. Electron spin resonance (ESR) spectroscopy was used to determine antiradical activity of the selected compounds and M05-2X/6-311+G(d,p) level of theory for the calculation of reaction enthalpies related to three possible mechanisms of free radical scavenging activity, namely HAT, SET-PT and SPLET. The results obtained show that the molecules investigated reacted with hydroxyl radical via both HAT and SPLET in the solvents investigated. These results point to HAT as implausible for the reaction with nitric oxide radical in all the solvents investigated. SET-PT also proved to be thermodynamically unfavourable for all three molecules in the solvents considered.
Assuntos
Antocianinas/farmacologia , Sequestradores de Radicais Livres/farmacologia , Glucosídeos/farmacologia , Espectroscopia de Ressonância de Spin Eletrônica , Radical Hidroxila/metabolismo , Óxido Nítrico/metabolismo , TermodinâmicaRESUMO
The M05-2X/6-311++G(d,p) and B3LYP-D2/6-311++G(d,p) models are used to evaluate scavenging potency of gallic acid. The hydrogen atom transfer (HAT), sequential proton loss electron transfer (SPLET), and single electron transfer followed by proton transfer (SET-PT) mechanisms of gallic acid with some radicals ((â¢)OO(-), (â¢)OH, and CH3OO(â¢)) were investigated using the corresponding thermodynamic quantities: bond dissociation enthalpy (BDE), ionization potential (IP), and proton affinity (PA). Namely, the ΔHBDE, ΔHIP, and ΔHPA values of the corresponding reactions in some solvents (water, DMSO, pentylethanoate, and benzene) are investigated using an implicit solvation model (SMD). An approach based on the reactions enthalpies related to the examined mechanisms is applied. This approach shows that a thermodynamically favored mechanism depends on the polarity of reaction media and properties of free radical reactive species. The most acidic 4-OH group of gallic acid is the active site for radical inactivation. The results of this investigation indicate that the SPLET mechanism can be a favored reaction pathway for all three radicals in all solvents, except for (â¢)OH in the aqueous solution. In water, gallic acid can inactivate (â¢)OH by the HAT mechanism.
Assuntos
Sequestradores de Radicais Livres/química , Radicais Livres/química , Ácido Gálico/química , Simulação por Computador , Elétrons , Sequestradores de Radicais Livres/farmacologia , Ácido Gálico/farmacologia , Hidrogênio , Ligação de Hidrogênio , Modelos Químicos , Estrutura Molecular , Prótons , Solventes/química , Relação Estrutura-Atividade , TermodinâmicaRESUMO
The mechanisms of the carboxylations of lithium, potassium, rubidium, and cesium phenoxides are investigated by means of the DFT method with the LANL2DZ basis set. It is shown that the reactions of all alkali metal phenoxides with carbon dioxide occur via very similar reaction mechanisms. The reactions can proceed in the ortho and para positions. The exception is lithium phenoxide which yields only salicylic acid in the Kolbe-Schmitt reaction. It is found that the yield of the para substituted product increases with increasing the ionic radius of the alkali metal used. An explanation for this experimental and theoretical observation is proposed.