Identification, amounts, and kinetics of extraction of C-glucosidic ellagitannins during wine aging in oak barrels or in stainless steel tanks with oak chips

The research began with an investigation of tannins from traditional medicinal plants and resulted in isolation and structure determination of hundreds of ellagitannins and dehydroellagitannins, as well as their oligomers and oxidized derivatives with various structures specific to each plant species. These polyphenols have been classified according to the stage of oxidative structural transformation and oligomerization, into types I-IV and I+ to IV+, etc. Parallels were found between their oxidative transformations and plant evolution. They were also classified by the linkage units between the monomers, into DOG, GOD, GOG and DOGOD types (D=Diphenoyl, G=Galloyl, O=Oxygen), etc. Besides their fundamental activities, e.g., reduction and anti-peroxidation properties, remarkable biological and pharmacological activities of various potencies have also been found, including, amongst others, inhibition of lipid-peroxidation, mutagenicity of carcinogens and tumor promotion, host-mediated antitumor effects specific to particular tannin structures, antiviral activity and potentiation of antibacterial activity.

Aimed at increasing our knowledge on the sensory-active nonvolatiles migrating from oak wood into alcoholic beverages upon cooperaging, an aqueous ethanolic extract prepared from oak wood chips (Quercus alba L.) was screened for its key taste compounds by application of the taste dilution analysis. Purification of the compounds perceived with the highest sensory impacts, followed by liquid chromatography/mass spectrometry as well as one-dimensional and two-dimensional NMR experiments, revealed the ellagitannins vescalagin, castalagin, and grandinin, the roburins A-E, and 33-deoxy-33-carboxyvescalagin as the key molecules imparting an astringent oral sensation. To the best of our knowledge, 33-deoxy-33-carboxyvescalagin has as yet not been reported as a phytochemical in Q. alba L. In addition, the sensory activity of these ellagitannins was determined for the first time on the basis of their human threshold concentrations and dose/response functions. Furthermore, the ellagitannins have been quantitatively determined in extracts prepared from Q. alba L. and Quercus robur L., respectively, as well as in bourbon whiskey and oak-matured red wines, and the sensory contribution of the individual compounds has been evaluated for the first time on the basis of dose/activity considerations.

Polyphenolic nonahydroxyterphenoyl-containing C-glycosidic oak ellagitannins are found in wine as a result of the aging of this beverage in oak-made barrels. Once in the slightly acidic wine (pH approximately 3-4), some of these complex natural products such as (-)-vescalagin (1), but not its C-1 epimer (-)-castalagin (2), can capture grape-derived nucleophilic entities such as ethanol, the flavanols catechin (10a) and epicatechin (10b), the anthocyanin oenin (13b), and the thiolic glutathione (16) to furnish condensation products with retention of configuration at the C-1 locus. A computer-aided rationale of this high diastereoselectivity is given. These condensation products can contribute to the modulation of organoleptic properties of the wine, as evidenced by the 23 nm bathochromic shift color absorbance observed with the novel oenin-based anthocyano-ellagitannin (15b). Hydrolysis of 1 under solvolytic conditions furnished another novel compound that we refer to as vescalene (21), in addition to the known (-)-vescalin (18). Of pharmacological importance is the fact that most of these found-in-wine water-soluble ellagitannin derivatives are much more potent than etoposide (VP-16) at inhibiting top2-mediated DNA decatenation in vitro (top2=topoisomerase II)). The known (-)-vescalin (18) and the novel vescalene (21) fully inhibited top2 at 10 microM concentration!