Antioxidant activity and mechanism of dihydrochalcone C-glycosides: Effects of C-glycosylation and hydroxyl groups. (November 2020)

• Record Type: Journal Article
• Authors: Xue, Yunsheng; Liu, Yunping; Xie, Yuxin; Cong, Chunxue; Wang, Guirong; An, Lin; Teng, Yangxin; Chen, Mohan; Zhang, Ling
• Is Part Of: Phytochemistry. Volume 179(2020)
• Publication Date: 2020-11
• Subjects: Dihydrochalcones -- C-Glycosylation -- Radical scavenging activity -- Antioxidative mechanism -- Density functional theory; Botanical chemistry -- Periodicals; Biochemistry -- Periodicals; Botany -- Periodicals; Chimie végétale -- Périodiques; 572.2
• DOI: 10.1016/j.phytochem.2020.112393
• Languages: English
• ISSNs: 0031-9422

Abstract

Abstract: Dihydrochalcones (DHCs), an important subgroup of flavonoids, have recently received much attention due to their diverse biological activities. In contrast to their O -glycosides, understanding of the antioxidant property and mechanism of DHC C-glycosides remains limited. Herein, the free radical scavenging activity and mechanism of two representative C -glycosyl DHCs, aspalathin (ASP) and nothofagin (NOT) as well as their aglycones, 3-hydroxyphloretin (HPHL) and phloretin (PHL) were evaluated using the density functional theory (DFT) calculations. The results revealed the crucial role of sugar moiety on the conformation and the activity. The o -dihydroxyl in the B-ring and the 2′, 6′-dihydroxyacetophenone moiety were found significant in determining the activity. Our results showed that hydrogen atom transfer (HAT) is the dominant mechanism for radical-trapping in the gas and benzene phases, while the sequential proton loss electron transfer (SPLET) is more preferable in the polar environments. Also, the results revealed the feasibility of the double HAT and double SPLET as well as the SPLHAT mechanisms, which provide alternative pathways to trap radical for the studied DHCs. These results could deepen the understanding of the antiradical activity and mechanism of DHCs, which will facilitate the design of novel efficient antioxidants. Graphical abstract: DFT calculations reveal the antioxidant mechanism and the effect of C-glycosylation on the activity of two representative C -glycosyl dihydrochalcones. Image 1 Highlights: Antioxidant activity of dihydrochalcone C-glycosides was evaluated by DFT method. Results revealed the crucial role of C-glycosylation on the activity. Catechol group and 2′, 6′-di-OH moiety were found significant for the activity. HAT is dominant pathway in the gas phase, while SPLET is more favored in polar media. Double HAT and double SPLET mechanisms as well as SPLHAT are alternative pathways.