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

(-)-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.

Viura is a synonym for Macabeo and currently it is the most widely planted white grape variety in D.O.Ca. Rioja, with 3,569 ha, representing 84% of the white grape cultivated area. It is a generous-yielding grape, presenting low values of titratable acidity and with large and compact clusters which makes it susceptible to Botrytis cinerea. Thus, this variety not always satisfies the wine grower’s prospects. Nowadays, the available plant material is scarce, moreover, it was selected on the basis of other quality criteria, not currently requested.

Oligosaccharides have only recently been characterized in wine, and the information on composition and content is still limited. In wine, these molecules are mainly natural byproducts of the degradation of grape berry cell wall polysaccharides. Wine oligosaccharides present several physicochemical properties, being one relevant factor linked to the astringency perception of wines (1,2). A terroir can be defined as a grouping of homogeneous environmental units based on the typicality of the products obtained. This notion is particularly associated with wine, being the climate and the soil two of the major elements of terroir concept.

Adrenaline (epinephrine) belongs to catecholamine class. It is a neurotransmitter and both a hormone which is released by the sympathetic nervous system and adrenal medulla in response to a range of stresses in order to regulate blood pressure, cardiac stimulation, relaxation of smooth muscles and other physiological processes. Adrenaline exhibits an effective antioxidant capacity (1). However, adrenalin is capable to auto-oxidation and in this case it generates toxic reactive oxygen intermediates and adrenochrome. Under in vitro conditions, auto-oxidation of adrenaline occurs in an alkaline medium (2).

Bacterial malolactic fermentation (MLF) has a considerable impact on wine quality. The yeast strain used for primary fermentation can consistently stimulate (MLF+ phenotype) or inhibit (MLF- phenotype) malolactic bacteria and the MLF process as a function of numerous winemaking practices, but the molecular evidence behind still remains a mystery. In this study, such evidence was elucidated by the direct comparison of extracellular metabolic profiles of MLF+ and MLF- yeast phenotypes. Untargeted metabolomics combining ultrahigh-resolution FT-ICR-MS analysis, powerful machine learning methods and a comprehensive wine metabolite database, discovered around 800 putative biomarkers and 2500 unknown masses involved in phenotypic distinction.