Petrolomics-derived data interpretation to study acetaldehyde-epicatechin condensation reactions

Tannin, anthocyanins and their reaction products play a major role in the quality of red wines. They contribute to their sensory characteristics, particularly colour and astringency. Grape tannins and anthocyanins are extracted during red wine fermentation. However, their concentration and composition change over time, due to their strong chemical reactivity1. It is also well known that yeasts influence the wine phenolic content, either through the release of metabolites involved in the formation of derived pigments1, or through polyphenol adsorption2,3.

Tyrosol (TYR) and hydroxytyrosol (HYT) are bioactive phenols present in olive oil and wine, basic elements of the Mediterranean diet. TYR is reported in the literature for its interesting antioxidant, cardioprotective and anti-inflammatory properties. In wine, its concentration can reach values as high as about 40 mg/L
[Pour Nikfardjam et al. 2007] but, more frequently, this phenol – derived from yeast metabolism of tyrosine during fermentation – is present at lower levels, generally higher in red wines compared to whites. HYT was measured for the first time by Di Tommaso et al. [1998] in Italian wines – with maximum values of 4.20 mg/L and 1.92 mg/L for red and white wines, respectively – while definitely lower concentrations have been found later in Greek samples.

With climate change, it is progressively more often to obtain grapes with an acceptable content in sugars or acids but with immature tannins described as green, aggressive or hard (noted as GAH onwards). During winemaking, the oenologist has to make decisions related to the elaboration of such grapes based mainly on empirical experience, given the lack of objective criteria to this concern. An increase in the chemical and sensory knowledge of immature tannins would allow managing this GAH character of grapes with the maximum possible efficiency during winemaking processes. The present work aims at isolating and identifying the group of compounds responsible for the GAH character present in wines.

Proteins constitute one of the three main components of grape juice and white wine, phenolic compounds and polysaccharides being the others. A specific group of the total grape-derived proteins resists degradation or adsorption during the winemaking process and remains in finished wine if not removed by the commonplace commercial practice of bentonite fining. While bentonite is effective in removing the problematic proteins, it is claimed to adversely affect the quality of the treated wine under certain conditions, through the removal of colour, flavor and texture compounds. A number of studies have indicated that different protein fractions require distinct bentonite concentrations for protein removal and consequent heat stabilization.

A method of suspect screening analysis to study grape metabolomics, was developed [1]. By performing ultra-high performance liquid chromatography (UHPLC) – high-resolution mass spectrometry (HRMS) analysis of the grape extract, averaging 320-450 putative grape compounds are identified which include mainly polyphenols. Identification of metabolites is performed by a new HRMS-database of putative grape and wine compounds expressly constructed (GrapeMetabolomics) which currently includes around 1,100 entries.