Identification and Quantification of Flavanol Glycosides in Vitis vinifera Grape Seeds and Skins during Ripening

Abstract

Monomeric and dimeric flavanol glycosides were analyzed in Vitis vinifera grapes and seeds during ripening. An analytical method using ultra-high performance liquid chromatography coupled with a triple quadrupole mass spectrometry (UHPLC-ESI-QQQ-MS/MS) in multiple reaction monitoring (MRM) mode was employed. Three grape varieties (Merlot, Syrah and Tannat) were chosen and grape berries were sampled at different stages of development. Ten monoglycosylated and six diglycosylated flavanol monomers were detected. Twelve monoglycosylated and three diglycosylated flavanol dimers were also detected for all three grape varieties. All diglycosides were detected for the first time in Vitis vinifera grapes, though some of these compounds were only detected in skins or seeds. Furthermore, the evolution of all these compounds was studied, and a decrease in monomeric (epi) catechin monoglycosides was observed during ripening for Tannat, Merlot and Syrah grape skins. The dimers would appear to accumulate in skin tissues up to mid-summer (after veraison) and decrease when grape berries reached maturity.

Evolution of Flavanol Glycosides during Red Grape Fermentation

“…This study reports the kinetics of extraction of monomeric and dimeric flavanols of mono- and diglycosides in GRE and SYR grape berries, and for the first time, in wine during fermentation. Data were obtained for a total of 22 isomers using a new UHPL-MS technique described in previous work [21].…”

“…(+)-catechin was purchased from Sigma Chemical Company (St Louis, MO, USA). The (+)-catechin 4′- O -β-glucoside (C4′OG) was hemi-synthesized as described previously [21].…”

“…MS/MS experiments were carried out using the Shimadzu UHPLC system described above coupled with a Shimadzu LCMS-8050 triple quadrupole mass spectrometer using the multiple reaction monitoring (MRM) technique operating in negative ion mode. All UHPLC and MS/MS parameters were identical, as previously described [21]. The average and standard deviations of the chemical analyses were performed on Excel 2013.…”

Potential of grape byproducts as functional ingredients in baked goods and pasta

“…Flavanols are bioactive secondary metabolites found in skins and seeds and can be found as monomers, polymers, or as glycosylated hexoside forms (Pérez-Navarro, Cazals, et al, 2019;Popov, Hejtmánková, Kotíková, Střalková, & Lachman, 2017;Zerbib, Cazals, & Enjalbal, 2018). Pérez-Navarro, Cazals, et al (2019) studied the flavanol glycoside profiles of three white (Airén, Albillo Dorado, and Montonera del Casar) and three red (Moribel, Tempranillo, and Tinto Fragoso) grape seeds and peels and revealed Abbreviations: GAE, gallic acid equivalents; TAE, tannic acid equivalents; TE, trolox equivalents; IC 50 , DPPH inhibition percent; TEAC, trolox equivalent antioxidant capacity; ORAC, oxygen radical absorbance capacity; ND, not determined; LD, detection limit.…”

“…Higher monomeric flavanol diglycosides amounts were found in seeds, whereas monoglycosylated dimmers were identified only in peels. Greater quantities of glycosylated flavanols were found in red varieties compared to the white ones, suggesting the dependence of flavanol glycoside profiles on the variety, grape maturity, and environmental conditions (Pérez-Navarro, Cazals, et al, 2019;Zerbib et al, 2018). The particle size of grape byproducts also influences the phenolic content as Beres et al (2016) and Zhao et al (2015) showed.…”