Abstract
Flavan-3-ols belong to a group of polyphenols present in a wide variety of plants, and particularly in grapeberries. They play an important role in defense mechanisms in plants, have a significant impact on wine organoleptic properties; and their beneficial effects on human health may help to protect against chronic diseases such as atherosclerosis. The sequence of common flavanol monomer biosynthesis is widely described in the literature, but the formation mechanisms of proanthocyanidins (PA) remain unknown. Studies show that flavanol glycosides are potential intermediates in PA polymerization and have transporter roles of monomeric units from cytoplasm to vacuole in cell, where polymerization takes place. Global screening of grapeberry flavanol glycosides were carried out at three stages of grape development and in wines of different varieties; skin and seeds were measured separately using an UPLC-DAD-ESI-MS method. The composition of the target isomers depends on different parameters such as tissue type or stage of development. The presence epi catechin monoglycoside is reported here for the first time in grapes. Using (+)-catechin 4’-O--glucoside and 7-O--glucoside hemisynthesis, several monomers were shown to -glucosides. Quantitative analysis demonstrates the evolution of flavanol glycosides in both skin and seeds during the development of three grapevine varieties. For the first time monomeric and dimeric (epi) catechin diglycosides were revealed and shown accumulate only in grape seeds during ripening. A reduction in the concentration of monomeric (epi) catechin monoglycoside was observed during grape skin development. Dimeric (epi) catechin monoglycosides accumulate after veraison and then decrease at the end of grape ripening. The extraction profiles of flavanol glycosides during red grape fermentation showed similar evolution patterns for both varieties used. The total concentration of different compound families increases during winemaking, and then decreases at the end of fermentation. Degradation of specific compounds was observed at the end of fermentation which may be explained by the activity of glycosidases from grape extracts released during fermentation and pressing.