Mass spectrometry in the study of anthocyanins and their derivatives: differentiation of Vitis vinifera and hybrid grapes by liquid chromatography/electrospray ionization mass spectrometry and tandem mass spectrometry

A mass spectrometric‐based procedure for anthocyanin profiling was set up to distinguish authentic Vitis vinifera from hybrid red grapevine cultivars. 3‐O‐Monoglucoside and the related acetyl‐, p‐coumaryl‐ and caffeoyl‐monoglucoside anthocyanins occurred only in Vitis vinifera, whereas 3,5‐O‐diglucoside and the substituted acetyl‐, p‐coumaryl‐, feruloyl‐ and caffeoyl‐diglucoside anthocyanins were the additional pigments in hybrid grapevines. The procedure was applied expressly to identify red grape cultivars based on the anthocyanin chemo‐type determination. In particular, a red grape cultivar, having 3,5‐O‐diglucoside anthocyanins and a novel class of anthocyanin monoglucosides, such as cyanidin‐3‐O‐, cyanidin‐3‐O‐(6‐O‐acetyl)‐ and cyanidin‐3‐O‐(6‐O‐p‐coumaryl)pentoside, was classified as hybrid. A second vine cultivar, characterized exclusively by 3‐O‐monoglucoside anthocyanins, was included among the Vitis vinifera species. Anthocyanin profiling by mass spectrometry could represent the core of a chemotaxonomic procedure for distinguishing American and European grapevines based on the identification of post‐synthetic anthocyanidin modification. Copyright © 2004 John Wiley & Sons, Ltd.