Acetaldehyde anthocyanin-tannin condensation

Other studies have described similar results to those found in our research, that is, that ellagitannins are more abundant in French oak (26) and therefore, in wines matured in French oak barrels. So, the presence of ellagitannins enhances the color of wine and increases absorbance at 620 nm by fevoring anthocyanin-procyanidin type tannin condensations with acetaldehyde (purple pigments) and that foct also helps to explain the higher PVPP index values of wines fix)m new French oak barrels. They also prevent the development of brick-yellow color by preventing the oxidation of phenolic compounds (24). 

Thiolysis also proved useful for the analysis of derived tannins. Methylmethine-linked tannin-like compounds resulting from acetaldehyde-mediated condensation of flavanols (see Section 5.5.S.2) yielded several adducts when submitted to acid-catalyzed cleavage in the presence of ethanethiol, providing information on the position of linkages in the original ethyl-linked compounds. " Thiolysis of red wine extracts released benzylthioether derivatives of several anthocyanin-flavanol adducts, indicating that such structures were initially linked to proanthocyanidins. However, some of the flavonoid derivatives present in wine (e.g., flavanol-anthocyanins ) are resistant to thiolysis, while others (e.g., flavanol-ethyl anthocyanins) were only partly cleaved. Thiolysis, thus, appears as a rather simple, sensitive, and powerful tool for quantification and characterization of proanthocyanidins, but provides mostly qualitative data for their reaction products. 

According to some studies, the compounds form as reaction by-products between anthocyanins and flavan-3-ols, such as catechins and proanthocyanidins (condensed tannins). These reactions may also involve other molecules such as acetaldehyde, pyruvic acid, acetoacetic acid, vinylphenol, vinylguaiacol, vinylcatechol, and dimerization of anthocyanins (Asenstorfer et ah, 2001 Atanasova et al., 2002 Bakker and Timberlake, 1997 Brouillard and Dangles, 1994 Fulcrand et ah, 1996, 1998 He et al., 2006 Liao et ah, 1992 Remy et ah, 2000 Salas et ah, 2004 Schwarz et al., 2003 Timberlake and Bridle, 1976). 

Acetaldehyde plays an important role during red wine fermentation in which it can react directly with anthocyanins pigments to form vinyl adducts (pyroan-thocyanins) (Fulcrand et al. 1998), and can participate in the condensation of proanthocyanidins (tannins) and anthocyanins to form ethyl-bridge linked dimers... 

While the identity of the relevant yeast metabolites in the fermented medium sampled at day 2 needs to be clarified, previously published data have provided some evidence about the role of acetaldehyde-mediated condensation of catechin with MSG (13-20). We therefore aimed to extend these model studies and to confirm chemical formation of pigmented polymers from condensed tannins, which are commercially used in red winemaking, and anthocyanins. The model reactions were conducted with vatying concentrations of acetaldehyde and SO2 as shown in Table 2 and analysed by HPLC after 2, 4 and 7 days. After 7 days visible precipitation of unidentified material started to occur in presence of acetaldehyde and the reactions were discontinued. 

The reaction mechanism proposed by Timberlake and Bridle (1976), suggests that acetaldehyde, in the form of a carbo-cation, reacts with flavanol (tarmin) at position C-6 or C-8 (Figure 1 (1)). This, via several condensation reactions, gives rise to tannin-ethyl-anthocyanin derivatives (Figure 1 (2)) such as malvidin-3-glucoside-ethyl-(epi)catechin and malvidin-3-(6-/7-coumaroyl)-glucoside-ethyl-(epi)catechin. 

One of the first reactions described in red wines was the polymerization reaction between anthocyanins and flavanols (catechins and condensed tannins) mediated by acetaldehyde (Timberlake Bridle, 1976). This reaction involves the protonation of the aldehyde, followed by addition of the respective carbocation to the nucleophilic position C-8 and less likely C-6 of the phloroglucinol ring of the flavanol (see Fig. 3.6). Further dehydration and a nucleophilic attack from the anthocyanin give rise to the formation of two new pigments that differ in the stereochemistry of the asymmetric carbon of the interflavonoid linkage [catechin-HC (CH3)-anthocyanin], as demonstrated by several authors (Rivas-Gonzalo etal, 1995 Escribano-Bailonefa/., 1996 Lee etal, 2004). 

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