Acetylation of Malvidin-3-O-glucoside Impedes Intermolecular Copigmentation: Experimental and Theoretical Investigations.

Abstract

Malvidin-3-O-(6-O-acetyl)-glucoside is usually the most abundant acylated anthocyanin in red wines. In this work, intermolecular copigmentation of malvidin-3-O-(6-O-acetyl)-glucoside and malvidin-3-O-glucoside with three phenolic copigments was carried out in model wine solutions, and the influence of the acetylation group was evaluated emphatically using experimental and theoretical approaches. This study found that there was no distinct coloring difference in the two anthocyanins themselves; however, the hyperchromic effects were smaller in malvidin-3-O-(6-O-acetyl)-glucoside solutions with the existence of insufficient copigments. Thermodynamic analysis confirmed that malvidin-3-O-(6-O-acetyl)-glucoside showed weaker affinity (smaller K values) toward the three copigments compared with its non-acylated form. Theoretical analysis also indicated that the existence of the acetylation group changed the spatial conformations and non-covalent interactions (hydrogen bonds and van der Waals forces) of the copigmentation complexes, which might be due to the potential steric hindrance effect. In conclusion, the results revealed that the acetylation group on anthocyanin glycosyl could impede intermolecular copigmentation.