Titrimetric method based on potentiometric titration to evaluate redox couples in wine and polyphenols

Polyphenols are electroactive compounds, each molecule having reductive (Rd) and oxidative forms (Ox) due to the presence of several phenolic hydroxyls. Direct study of Rd/Ox forms was conducted using potentiometric titration in two steps: First, a complete reduction of the polyphenol Rd/Ox couples by titanium III chloride TiCl3 (100 % Rd), and then, oxidative titration by dichlorophenolindophenol DCPIP (100 % Ox). The second curve represents the totality of polyphenol couples titration with, for each couple, a characteristic E0 point representing the equilibrium between the concentration of Rd and Ox forms (Rd/Ox = 1). This value was typical for each polyphenol. We conducted several preliminary experiments with a model polyphenol (catechin) to establish the analysis conditions. The titration solution concentration was N/10 in HCl N and N/20 in water for TiCl3 and DCPIP respectively. The concentration of this solution diminished very rapidly, i.e. within 24 h for TiCl3 and DCPIP (under nitrogen and in darkness) and regularly needed a fresh preparation. To control the consistency and precision of the method we performed a few tests on pure products (e.g. hydroquinone/quihydrone, Fe III, Fe II, Cu II) permitting comparison between theoretical and experimental E0 values. Our result indicated less than 5 % variation and curves with a high reproducibility.

Influence de SO2 et de l'acide ascorbique sur l'activité antiradicalaire des tanins, mesurée sur l'anion superoxyde. Application aux vins rouges

Pour des concentrations habituellement utilisées en oenologie, le SO2 ne presente pas d'activité antiradicalaire à l'égard de l'anion superoxyde. L'acide ascorbique est un antiradicalaire dont les performances sont fonction de sa concentration. Les différents tanins testés présentent tous de très importantes activités antiradicalaires. Dans les vins rouges, ce sont donc pour l'essentiel les procyanidines qui captent les radicaux libres superoxydes. Influence of SO2 and ascorbic acid on the scavenger effect of tannins, measured on superoxide anion. Application to red wines At usual oenological concentrations SO2 does not have a scavenger effect on superoxide anion. Ascorbic acid is an antiradical the effect of which varies with concentration. Different tannins, e.g. castalagin, pentagalloylglucose, procyanidins B2 and B4, (+)-catechin and garlic acid, are shown to have significant antiradical effects. In red wines in particular procyanidins have a scavenger effect on free superoxide radicals

Formation of Flavanol-aldehyde Adducts in Barrel-aged White Wine – Possible Contribution of These Products to Colour

This paper describes the formation and diversity of new compounds resulting from the polymerisation of furanic andphenolic flavanol-aldehydes with HPLC‑DAD and LC‑ES/MS analysis. Polymerisation, resulting from nucleophilicreactions, formed dimers, trimers, soluble and insoluble polymers. Reactions in hydroalcoholic solution with purealdehydes (phenolic and furanic) and flavanols (catechin) were studied. The study was repeated with differentaldehydes in white wine. This research focused particularly on the colour properties of the released products and theirpotential impact on the colour of white wine. Some products were purified and isolated; these were mainly catechinfurfuraldehyde,catechin-methyl-5-furfuraldehyde, catechin-hydroxymethyl-furfuraldehyde,catechin-vanillin, andcatechin-syringaldehyde dimers. The most powerful coloured products resulted from furanic aldehydes. Over thecourse of the experiment, the reaction produced dimers, trimers and oligomers. After 50 to 60 days, the colour of thesolution was mainly due to soluble polymeric forms. In addition, the role of SO2, generally used during vinificationand ageing, was studied. The influence of SO2 on the kinetics of the reaction was limited

Occurrence and specificity of glucose oxidase (E.C: 1.1.3.4) in botrytized sweet white wine. Comparison with laccase (E.C: 1.10.3.2), considered as the main responsible factor for oxidation in this type of wine

Two types of oxidizing enzymes are present in botrytized white grapes and wines: laccase (PPO) and glucose oxidase (GOX). The evolution of these two enzymes is similar both during the over-ripening of grapes and during wine making. Yet, PPO is severely inhibited by the addition of SO2 following the alcoholic fermentation, and shows a marked instability in both the must and wine environments. GOX, however, remains free and active in solution and helps develop the main characteristics of the wine. In particular, as is to be expected from its activity, GOX oxidizes tartaric acid, ethanol and glycerol, the major components of must and wine, respectively to glyoxylic acid, acetaldehyde and glyceraldehyde. And then, by nucleophilic additions under acidic conditions, these products react with catechins and proanthocyanidins to form several new compounds, some of which appear in a colored form. These reactions can have an impact on the visual quality of the wine.

Formation of Flavanol-aldehyde Adducts in Barrel-aged White Wine - Possible Contribution of These Products to Colour

[EN] This paper describes the formation and diversity of new compounds resulting from the polymerisation of furanic and phenolic flavanol-aldehydes with HPLC¿DAD and LC¿ES/MS analysis. Polymerisation, resulting from nucleophilic reactions, formed dimers, trimers, soluble and insoluble polymers. Reactions in hydroalcoholic solution with pure aldehydes (phenolic and furanic) and flavanols (catechin) were studied. The study was repeated with different aldehydes in white wine. This research focused particularly on the colour properties of the released products and their potential impact on the colour of white wine. Some products were purified and isolated; these were mainly catechinfurfuraldehyde, catechin-methyl-5-furfuraldehyde, catechin-hydroxymethyl-furfuraldehyde, catechin-vanillin, and catechin-syringaldehyde dimers. The most powerful coloured products resulted from furanic aldehydes. Over the course of the experiment, the reaction produced dimers, trimers and oligomers. After 50 to 60 days, the colour of the solution was mainly due to soluble polymeric forms. In addition, the role of SO2 , generally used during vinification and ageing, was studied. The influence of SO2 on the kinetics of the reaction was limited.Vivas, N.; Nonier, MFB.; Absalon, C.; Lizama Abad, V.; Jamet, F.; De Gaulejac, NV.; Vitry, C.... (2008). Formation of Flavanol-aldehyde Adducts in Barrel-aged White Wine - Possible Contribution of These Products to Colour. South African journal of enology and viticulture. 29(2):98-108. http://hdl.handle.net/10251/105310S9810829

Étude structurale de lignines extraites de cour de bois de chêne

Dans ce travail les auteurs présentent la structure de deux types de lignines extraites du bois de cœur de Q. robur. Il s'agit de LE, lignine extraite en milieu hydroalcoolique acide (PM 23 kDa) et de LD extraite à chaud par le dioxane acidifié (PM 45 kDa). L'analyse des spectres 2D de type TOCSY et HMQC confirme que les deux lignines contiennent principalement des noyaux phénoliques monométhoxylés (Gaïacyles) et diméthoxylés (Syringyles) reliés par des liaisons β–O–4 aryl-ether prépondérantes. LD se distingue de LE par une proportion plus importante de noyaux G.