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02 13, 2020;10 (1): 2611.

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

Jinxiang Chen, Jing Yang, Lanlan Ma, Jun Li, Nasir Shahzad, Chan Kyung Kim
Author Information
  1. Jinxiang Chen: School of Chemical Engineering and Technology, North University of China, Taiyuan, 030051, China.
  2. Jing Yang: School of Chemical Engineering and Technology, North University of China, Taiyuan, 030051, China. yangjing5152@163.com. ORCID
  3. Lanlan Ma: School of Chemical Engineering and Technology, North University of China, Taiyuan, 030051, China.
  4. Jun Li: School of Chemical Engineering and Technology, North University of China, Taiyuan, 030051, China.
  5. Nasir Shahzad: Department of Chemistry and Chemical Engineering, Inha University, Incheon, 22212, Korea.
  6. Chan Kyung Kim: Department of Chemistry and Chemical Engineering, Inha University, Incheon, 22212, Korea. kckyung@inha.ac.kr.
PMID: 32054964 DOI: 10.1038/s41598-020-59451-z

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, -CHCOOH and -CH = CHCOOH can enhance the antioxidant activities of phenolic acids, compared with -COOH. Methoxyl (-OCH) 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.

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