New acylated flavonols identified in Vitis vinifera grapes and wines

Flavonols are a class of polyphenol compounds whose importance for wine quality has increased as their structures and properties have become better understood. Here, the acetylated and p-coumaroylated derivatives of the flavonol 3-O-glucosides of isorhamnetin, laricitrin and syringetin have been identified for the first time in Vitis vinifera grape skins and wines. First, the MS2 fragmentation patterns of the new flavonol derivatives showed a main signal attributable to the expected flavonol aglycone. In the p-coumaroylated derivatives, the signal corresponding to the intermediate loss of the phenolic acid was also observed. The structures of the aglycones were confirmed by their respective MS3 experiments that matched with those obtained from authentic standards of the aglycones. In addition, the fragmentation signals corresponding to the aglycone radical ions generated through homolytic cleavage assisted identification, and could support future studies of flavonoid compounds by ESI-MS. Using an HPLC-ESI-Q-ToF system, the observed m/z values of the compounds being studied were successfully matched with the expected formula. Surprisingly, just the minority methoxylated flavonol glucosides presented acylation, suggesting a high substrate specificity of the acyltransferases implicated in their synthesis. These findings show higher diversity of grape and wine flavonols. Additional studies and isolation strategies need to be followed to further characterize these metabolites as to test their presence in other grape varieties and it wines. [Display omitted] •New series of acylated flavonols tentatively identified in grapes and wines.•New derivatives were found only for the minority methoxylated flavonols.•Most of putative aglycones fragmented at MS3 as the authentic standards.•Homolytic cleavage of glucosidic bond complicates MS3 spectra of putative aglycones.•The mass accuracy of the new compounds was confirmed by Q-ToF-MS.