Formation of Vitisins and Anthocyanin–Flavanol Adducts during Red Grape Drying

• Published in: Journal of agricultural and food chemistry 2012-07, Vol.60 (27), p.6866-6874
• Main Authors: Marquez, Ana, Dueñas, Montserrat, Serratosa, María P, Merida, Julieta
• Format: Article
• Language: English
• Subjects: Acetaldehyde - chemistry; Anthocyanins - chemistry; Biological and medical sciences; Desiccation; Fermented food industries; Flavanones - chemistry; Food engineering; Food industries; Fruit - chemistry; Fundamental and applied biological sciences. Psychology; General aspects; Mass Spectrometry; Pyruvic Acid - chemistry; Vitis - chemistry; Wine - analysis; Wines and vinegars
• ISSN: 0021-8561; 1520-5118
• DOI: 10.1021/jf300998p

This study evaluated the formation of anthocyanin-derived compounds during the production of sweet red wines from Merlot and Syrah grapes previously chamber-dried under controlled-temperature conditions. The musts from both grape varieties were found to contain pelargonidin-3-glucoside throughout the vinification process. Besides, HPLC-DAD-MS revealed the presence of pyranoanthocyanins in unfermented musts from the raisins. These compounds are adducts resulting from the cycloaddition of pyruvic acid (type A vitisins) and acetaldehyde (type B vitisins) to anthocyanin molecules. The analyses additionally revealed the presence of products of the condensation via a methylmethine bridge between anthocyanins and (epi)catechin, which requires the presence of acetaldehyde. The absence of pyruvic acid, acetaldehyde, and ethanol in the musts from fresh grapes and their presence in those from dried grapes support the idea that these compounds result from enzymatic transformations because the vinification of the musts involves no alcoholic fermentation. The drying process alters the permeability of grape membranes by the lipoxygenase activation effect (LOX), a switch to an anaerobic metabolism and the resulting triggering of the alcohol dehydrogenase enzyme (ADH). The activation of these and several other enzymes confirmed the occurrence of enzymatic transformations and the formation of vitisin A, acetylvitisin A, and the B vitisins of malvidin-3-glucoside, peonidin-3-glucoside, peonidin-3-acetylglucoside, and malvidin-3-acetylglucoside, as well as the adducts Pn-3-glc-methylmethine(epi)catechin, Mv-3-glc-methylmethine(epi) catechin, and Mv-3-acetylmethylmethine(epi)catechin.