Structure-antioxidant activity relationship of methoxy, phenolic hydroxyl, and carboxylic acid groups of phenolic acids

Abstract

The antioxidant activities of 18 typical phenolic acids were investigated using 2, 2'-diphenyl-1-picrylhydrazyl (DPPH) and ferric ion reducing antioxidant power (FRAP) assays. Five thermodynamic parameters involving hydrogen atom transfer (HAT), single-electron transfer followed by proton transfer (SET-PT), and sequential proton-loss electron transfer (SPLET) mechanisms were calculated using density functional theory with the B3LYP/UB3LYP functional and 6-311++G (d, p) basis set and compared in the phenolic acids. Based on the same substituents on the benzene ring, -CH₂COOH and -CH = CHCOOH can enhance the antioxidant activities of phenolic acids, compared with -COOH. Methoxyl (-OCH₃) and phenolic hydroxyl (-OH) groups can also promote the antioxidant activities of phenolic acids. These results relate to the O-H bond dissociation enthalpy of the phenolic hydroxyl group in phenolic acids and the values of proton affinity and electron transfer enthalpy (ETE) involved in the electron donation ability of functional groups. In addition, we speculated that HAT, SET-PT, and SPLET mechanisms may occur in the DPPH reaction system. Whereas SPLET was the main reaction mechanism in the FRAP system, because, except for 4-hydroxyphenyl acid, the ETE values of the phenolic acids in water were consistent with the experimental results.

Figure 1

RSA values of DPPH (A) and TEAC value of FRAP (B) in 18 tested compounds. The data were expressed as mean (±SD) (n = 3). Different lowercase Greek letters represented different phenolic acids with the same methoxy and phenolic hydroxyl groups (p  < 0.05), and different Latin letters represented different phenolic acids with the same carboxylic acid group (p < 0.05).

Figure 2

The energy and distribution of HOMO for18 tested compounds in ethanol.