Supramolecular approaches to the study of the astringency elicited by wine phenolic compounds

(-)-Rotundone, an oxygenated sesquiterpene, is a potent odorant molecule with a characteristic spicy aroma existing in various plants including grapes1. It is considered as a significant compound notably in wines and grapes because of its low sensory threshold (16 ng L-1 in red wine, 8 ng L-1 in water) and aroma properties. (-)-Rotundone was first identified in red wine made from the grape cultivar Syrah (regionally called Shiraz) in Australia1, and then it was found in several grape varieties such as Duras, Grüner Veltliner, Schioppettino and Vespolina from Europe2, 3. Several environmental factors affecting the accumulation of (-)-Rotundone during the grape maturation, were reported such as ambient temperature4, soil properties and topography5, soil moisture from irrigation and light exposure in the bunch zone by leaf removal2.

The chemical composition of wines depends on series of variables such as the type of grape, edaphoclimatic conditions, and viticulture and winemaking practices employed during production. Metallic elements play a significant role during winemaking (e.g. as catalysts of oxidation reactions) and have been previously employed for the classification of wines according to provenance. In this work, we focused on the analysis of metallic elements (K, Na, Ca, Zn, Cu, Fe, Mg, Mn, Ni, Cr, Al, Pb, Cd, Hg, Se, Co, Sn and As) in 145 Chilean wine samples (102 reds and 43 white wines), of seven grape varieties, and five of the major wine producing regions in Chile.

The use of glutathione (GSH) in winemaking has been legitimated recently, according to OIV resolutions OENO 445-2015 and OENO 446-2015 a maximum dose of 20 mg/L is now allowed to use in must and wine. Several studies have proven the benefits of GSH, predominantly in Sauvignon blanc. Thus, oxidative coloration of must and wine is limited, aroma compounds such as volatile thiols are preserved, and the development of ageing flavors such as sotolon and 2-aminoacetophenone is impeded. The protective effect may be explained by the high affinity of GSH to bind o-quinones which are formed during phenolic oxidation and which are known to initiate browning and other oxidative changes. Some researchers have proposed the hydroxycinnamic acid to GSH ratio (HGR) as an indicator of oxidation susceptibility of must and could show that lower ratios yielded lighter musts.

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.

For characterization, sensory designing and authentication rapid analytical technologies have become available. Some, like Proton Transfer Reaction Mass Spectrometry allow a rapid spectrum of the volatile compounds of wines. Combined with chemometrics wines can be characterized. The same approach can be used to calculate the results of virtual mixtures and allow formulation of constant quality blends. Other new techniques and portable devices based on spectroscopy allow measurements on production sites and in grocery stores, even for the smart consumer. We will present some examples of the application of these techniques for authentication of wines, both in the laboratory and on site.