Flavanol glycosides in grapes and wines : the key missing molecular intermediates in condensed tannin biosynthesis ?

The phenolic profiles of little known red grape cultivars, namely Garnacho, Moribel and Tinto Fragoso, which are autochthonous from the Spanish region of La Mancha (ca. 600,000 ha of vineyards) have been studied over the consecutive seasons of years 2013 and 2014. The study was separately performed over the skins, the pulp and the seeds, and comprised the following phenolic types: anthocyanins, flavonols, hydroxycinnamic acid derivatives (HCADs), total proanthocyanidins (PAs) and their structural features. The selected grape cultivars belong to the Vine Germplasm Bank created in this region in order to preserve the great diversity of genotypes grown in La Mancha.

Phenolic compounds are important quality indicators in red wine. A large number of polyphenols play an important role in wine development, contributing to the colour and the sensory perception of the wines. Anthocyanins are the pigments responsible for the colour in young red wines while tannins are the principal contributors to the bitterness and the astringency of the wines. Wine polyphenols are considered more complex molecules than grape phenolics, due to the enormous number of chemical reactions which take place during the entire winemaking process and storage, forming more stable compounds.

The assessment of red wine mouthfeel relies primarily on the sensory description of its tannic properties. This evaluation could be improved by gaining a better understanding of the physicochemical properties of these tannins. Hence, the objectives of the present study were threefold: (1) to gain an insight into the sensory properties of subpopulations of proanthocyanidic tannins of different molecular sizes obtained through several ultrafiltration steps, (2) to quantify the kinetics of haze formation of these proanthocyanidic tannins in a dynamic polyvinylpyrrolidone (PVP) precipitation test, (3) to determine whether a correlation exists between the sensory and the precipitation data.

Tannin and polysaccharide concentration and composition is important in defining the texture of red wines, but can vary due to factors such as cultivar, region, grape ripeness, viticultural practices and winemaking techniques. However, the concentration and composition of these macromolecules is dependent not only on grape tannin and polysaccharide concentration and composition, but also their extractability and, in the case of polysaccharides, their formation by yeast. Through studies into the influence of grape maturity, winemaking and sensory impacts of red grape polysaccharides, seed and skin tannins, recent research in our laboratory has shown that the processes involved in the extraction of these macromolecules from grapes and their retention in wine are very complex.

Among red wines ethyl esters, those from short hydroxylated and branched-chain aliphatic acids constitute a family with a particular behavior and sensory importance. They have been previously discussed in the literature [1] and recent studies have established that some of them were strongly involved in of red wines’ fruity aroma [2]. As some among them have an asymmetrical carbon atom, it seemed important to separate their different enantiomers to obtain an accurate assessment of their organoleptic impact. Three chiral esters have been identified, presenting alkyl and/or hydroxyle substituants: ethyl 2-hydroxy-4-methylpentanoate, ethyl 2-methylbutanoate, and ethyl 3-hydroxybutanoate.