Characterization of free and glycosidically bound simple phenols in hybrid grape varieties using liquid chromatography coupled to high resolution mass (q-orbitrap)

Grapevine berries produce thousands of secondary metabolites of diverse chemical nature that have been largely detailed in the past due to their importance for defining wine quality. The wide Vitis vinifera diversity, resulting in thousands of different varieties well detailed in many studies regarding berries, is still not investigated in vegetative organs, leaves in particular. Deepening knowledge related to this aspect could be of great interest for many reasons (for example the possibility of using leaf extract for pharmaceutical, cosmetic and nutrition purposes) but, above all, for understanding the susceptibility of different grapevine varieties to pathogens.

Recent studies have demonstrated the role of certain lactones, particularly 2-nonen-4-olide, and volatile thiols (3-sulfanylhexan-1-ol) in the over ripped aromas of noble rot sweet wines (Stamatopoulos et al. 2014ab). These compounds are partly formed during the maturation and under the activity of B. cinerea on grapes. This research was carried out in the vineyard of Sauternes with aim to better understand their genesis depending on the grape over-ripening on two different soil types during 3 vintages. Thus, the study was conducted, with the Sémillon grape, during vintages 2012, 2014 & 2015, at 4 stages of over-maturation of the grapes (healthy, pourri plein, pourri roti, pourri roti + 15 days) considering two vineyard plots with different soil characteristics (calcosol & peyrosol) planted with the 315 Sémillon clone and grafted on 101-14 rootstock respectively in 1981 and 1980 and cultivated with the same vineyard management. Volatile lactones were assayed by liquid-liquid extraction followed by GC/MS analysis and the precursors of 3-sulfanylhexanol by an adaptation of the method by Capone et al. 2010 (SPE-
UPLC/FTMS).

3-Isobutyl-2-methoxypyrazine (IBMP) is one of the key molecules in wine aroma with a bell pepper aroma and a very low threshold in wine, 1-6 ng/L for white wine and 10-16 ng/L in red wine1. The differences in these thresholds are likely due to IBMP-non volatile matrix interactions. It has indeed been shown that polyphenols may influence the volatility of flavor compounds2. In the present study, we focus on IBMP-polyphenols interactions in relation to volatility and sensory perception in model wine solution. Methods: 1. GC-MS Static Headspace Analysis: Samples were analyzed by Static headspace analysis with an Agilent 7890A gas chromatograph coupled to HP 5975C mass spectrometry detector (Agilent Technologies, Santa Clara, CA, USA).

Chemical studies aiming at assessing how a wine reacts towards oxidation usually focus on the characterization of wine constituents, such as polyphenols, or oxidation products. As an alternative, the key oxidation intermediate hydrogen peroxide H2O2 has never been quantified, although it plays a pivotal role in wine oxidation. H2O2 is obtained from molecular oxygen as the result of a first cascade of oxidation reactions involving metal ions and polyphenols. The produced H2O2 then reacts in a second cascade of oxidation to produce reactive hydroxyl radicals that can attack almost any chemical substrate in wine.

Laboratório de Análisis del Aroma y Enologia (LAAE). Department of Analytical Chemistry, Faculty of Sciences, Universidad de Zaragoza, 50009, Zaragoza, Spain, During alcoholic fermentation, fusel (or Strecker) aldehydes are intermediates in the amino acid catabolism to form fusel alcohols following the Ehrlich Pathway (1). One of the main enzymes involved in this pathway is Alcohol Dehydrogenase (ADH), whose activity is highly strain dependent and determines the rate of conversion of aldehydes into fusel alcohols (2). This enzyme has a Zn2+ catalytic binding site, which suggests that the must Zn2+ levels will most likely influence the rate of reduction of aldehydes into alcohols. On the other hand, SO2 is commonly used in winemaking for its antiseptic and antioxidant properties.