Multiple free radical scavenging reactions of flavonoids. (February 2022)

• Record Type: Journal Article
• Authors: Zheng, Yan-Zhen; Deng, Geng; Zhang, Yu-Cang
• Is Part Of: Dyes and pigments. Volume 198(2022)
• Publication Date: 2022-02
• Subjects: Flavonoids -- Density functional theory -- Antioxidant activity -- Multiple H+/e‒ processes; Dyes and dyeing -- Periodicals; Pigments -- Periodicals; 667.2
• DOI: 10.1016/j.dyepig.2021.109877
• Languages: English
• ISSNs: 0143-7208

Abstract

Abstract: The multiple free radical scavenging reactions of flavonoids have been studied considering the gas, benzene, and water phases by applying density functional theory (DFT). Intramolecular hydrogen-bonds are found in all the most stable geometries of flavonoids and can reduce the antioxidant activity of hydroxyl groups, acting as hydrogen-bond donors (5−OH, 3−OH and 3'−OH), while enhancing the antioxidant activity of hydroxyl groups, acting as hydrogen-bond acceptors (4'−OH). In the gas and benzene phases, all of the flavonoids first prefer performing continuous di-hydrogen atom transfer (HAT) reaction from the B ring OH groups to trap two free radicals with the formation of stable quinones for ampelopsin, taxifolin, dihydro orobol and eriodictyol and benzodioxole for hesperetin. They would trap the third free radical via the HAT in the gas phase. In the benzene phase, ampelopsin also favours to apply HAT to trap the third free radical, and the other flavonoids would use the sequential proton loss electron transfer (SPLET) mechanism. In the water phase, the investigated flavonoids would first perform consecutive proton loss (PL) reactions from all of the OH groups with the formation of polyanions. The multiple PL reactions begin from the 7−OH group. The second PL reaction prefers performing in the OH groups on the B benzene ring due to the better delocalization of the negative charge via conjugation over the entire skeleton. The polyanions of the investigated flavonoids scavenge three free radicals via three consecutive ET reactions. Highlights: The antioxidative mechanisms of the five flavonoids are analysed. Intramolecular hydrogen-bonds can affect the hydrogen atom loss sequence. Flavonoids can perform multiple H + /e ‒ processes. The preferred mechanisms vary among the different phases.