Subtle distinction in molecular structure of flavonoids leads to vastly different coating efficiency and mechanism of metal-polyphenol networks with excellent antioxidant activities

• Published in: Colloids and surfaces, B, Biointerfaces Vol. 229; p. 113454
• Main Authors: Li, Na, Shou, Zeyu, Yang, Siyun, Cheng, Xinxiu, Chen, Chun, Zheng, Shengwu, Shi, Yelu, Tang, Hongli
• Format: Journal Article
• Language: English
• Published: Netherlands Elsevier B.V 01.09.2023
• Subjects: Antioxidation; Coating technique; Flavonoid; Metal-polyphenol networks; MPN formation mechanism; Metal-polyphenol networks; MPN formation mechanism; Antioxidation; Flavonoid; Coating technique
• ISSN: 0927-7765; 1873-4367
• DOI: 10.1016/j.colsurfb.2023.113454

Metal-polyphenol networks (MPNs) are of immense scientific interest because of their simple and rapid process to deposit on various substrates or particles with different shapes. However, there are rare reports on the effect of polyphenol molecular structure on coating efficiency and mechanism of MPNs. Herein, three typical flavonoid polyphenols, catechin (Cat), epigallocatechin (EGC) and procyanidin (PC), with the same skeleton (C6-C3-C6) but subtle distinction in molecular structure, were selected to build MPN coatings with ferric ions (Fe3+). And various techniques combined with the density functional theory (DFT) were applied to deeply reveal the roles of coordinative phenolic hydroxyl groups as well as noncovalent interactions (hydrogen bonding and π − π stacking) in the formation of flavonoid-based MPNs. We found that more accessible numbers of coordinative phenolic hydroxyl groups, the higher coating efficiency. In these flavonoid-based MPNs, the single-complex is the predominant during the coordinative modes between phenolic hydroxyl and Fe3+, not the previously reported mono-complex, bis-complex and/or tris-complex. Besides coordinative interaction, noncovalent interactions also contribute to MPNs formation, and hydrogen bonds prevail in the noncovalent interaction compared with π-π stacking. And these engineered MPN coatings can endow the substrate with excellent antioxidant activities. This study contributes to in-depth understanding the building mechanism of flavonoid-based MPNs, and increasing coating efficiency by choosing proper polyphenols. [Display omitted] •Minor molecular structural differences affect MPN coating process and properties.•Flavonoid MPN binding mode is mainly based on coordination between monophenol hydroxyl and Fe3+.•Hydrogen bonds dominate the noncovalent interaction, π-π stacking is not the key factor.•Faster MPN growth is due to easier aggregate formation between flavonoids and Fe3+.•Flavonoid-based MPN shows remarkable antioxidant activity and potential for bio applications.