Effect of ethanol on the sorption of four targeted wine volatile compounds in a polyethylene film.

The objectives of this study were to demonstrate that the presence of ethanol in a solution containing two esters and two aromatic alcohols has several consequences on the sorption of these compounds into polyethylene (PE) film. First, sorption of ethanol into the PE film occurred at the same time as water and reached 8 kg m(-3) using 12% v/v of ethanol. This sorption was associated with an increase in PE crystallinity, which may have prevented the sorption of volatile compounds despite their strong affinity with PE film, as evaluated by Hansen solubility parameters. Moreover, increasing the ethanol concentration increased the solubility of the four volatile compounds. In the case of aromatic alcohols, the sorption was decreased in the presence of ethanol as expected. In the case of esters, as their hydrolysis was substantial in the presence of water, the consequence was a higher sorption into the PE film in the presence of ethanol than in its absence. Nevertheless, the sorption also depended on the concentration of ethanol and the heterogeneity of the ethanol-water mixture as well as the presence of other volatile compounds, as in the case of 4-ethylphenol. In conditions simulating wine packaging, losses of volatile compound by sorption and by permeation estimated after only 5 days of contact varied between 0.08 and 25% for 2-phenylethanol and ethyl hexanoate, respectively.

Changes in polysaccharide and protein composition of cell walls in grape berry skin (Cv. Shiraz) during ripening and over-ripening.

Polysaccharide modification is the most fundamental factor that affects firmness of fruit during ripening. In grape, because of the lack of information on the modifications occurring in cell wall polysaccharides in skins, but also because this tissue contains large amounts of organoleptic compounds for winemaking, a study was performed on the evolution and extractability of polysaccharides from grape skins of Shiraz cultivar throughout ripening. A HEPES/phenol extraction technique was used to analyze Shiraz grape cell wall material isolated from skins of berries harvested from one to ten weeks after veraison. Total amounts in cell wall polysaccharides remained constant during ripening (4.2 mg/berry). A slight decrease in galactose content of insoluble polysaccharides was observed, as well as a significant de-esterification of methoxylated uronic acids, indicating that some modifications occur in cell wall polysaccharides. The water-soluble fraction represented a very small fraction of the whole polysaccharides, but its amounts increased more than 2-fold between the first and the last sample. Isolated cell walls were also analyzed for their protein composition. Last, hydroalcoholic extractions in model-wine solution were also performed on fresh skins. This extracted fraction was very similar to the water-soluble one, and increased during the entire period. By comparison with polysaccharide modifications described in flesh cell wall in previous works, it can be assumed that the moderate skin polysaccharide degradation highlights the protective role of that tissue.

Accumulation and extractability of grape skin tannins and anthocyanins at different advanced physiological stages.

Quantitative and qualitative modifications of tannins and anthocyanins in grape skin were investigated at different dates of harvest, from berries sorted on the basis of their density. Free anthocyanins accumulated until 170 g/L of sugars in pulp before undergoing a slight decrease. Changes in anthocyanin composition were observed with increasing sugar levels in the pulp that reflected structural differences between classes of anthocyanins. The proportion of methoxylated anthocyanins continued to increase in the skin as sugar accumulated while the proportion of coumaroylated anthocyanins initially increased (up to 200 g/L of sugars in the pulp) and then rapidly decreased. In comparison, no major quantitative nor qualitative change was observed for tannins, except for a slight increase of the mean degree of polymerization. Whatever the physiological stage of the pulp, the extraction yield of skin phenolics into hydroalcoholic solution for 5 h was lower than 77% for anthocyanins and 38% for proanthocyanidins. For both classes of compounds, no clear evolution in these extraction yields could be observed as sugars accumulated in pulp (from 162.6 to 275.0 g/L). Nevertheless, some structural features within each family of compounds significantly influenced extractability, for example, a lower extraction yield for coumaroylated anthocyanins and for tannins with a high degree of polymerization. Finally, no direct relationship could be found in extraction media between the amounts of all red pigments (measured in acidic conditions) and the color intensity at 520 nm (measured in wine-like model solutions).

Role of aldehydic derivatives in the condensation of phenolic compounds with emphasis on the sensorial properties of fruit-derived foods.

The reactions between (epi)catechin, mavidin 3-O-glucoside, and some aldehydes were investigated by LC/DAD and LC/ESI-MS analysis. The obtained results showed that the acetaldehyde-mediated condensation occurred more generally and glyoxylic acid, furfural, and 5-(hydroxymethyl)furfural (HMF) react in the same way in the first stages of the reactions. In terms of reactivity, reactions were faster with acetaldehyde than with glyoxylic acid, furfural, or HMF, where the reactions were slower. In the case of acetaldehyde, the obtained purple derivatives were more predominant and stable than the colorless adducts and no xanthylium salt was detected. Interactions involving glyoxylic acid yield purple adducts, which were obtained in small amount compared to the colorless ones. The latter were shown to proceed to more polymerized and yellowish derivatives. Finally, in the case of furfural and HMF, purple compounds involving flavanol and anthocyanin units were detected, and colorless compounds were shown to be predominant and to yield yellowish xanthylium salts.

Interactions between cyanidin 3-O-glucoside and furfural derivatives and their impact on food color changes.

The reaction between (+)-catechin and cyanidin 3-O-glucoside was investigated in the presence of furfural and 5-(hydroxymethyl)furfural using LC/DAD and LC/MS analysis, and the obtained results were compared with those recorded with malvidin 3-O-glucoside. The appearance of colorless and red and yellow compounds was observed showing that the two polyphenols competed in the condensation process with a predominant formation of the reddish adducts. The colored compounds formed in the case of cyanidin 3-O-glucoside seemed to be more stable than those formed when the reaction was conducted with malvidin 3-O-glucoside. The detection of these reddish and yellowish compounds constitutes a new support for the contribution of this kind of reaction in the color evolution of fruit-derived beverages. In addition, other unidentified compounds were also detected, showing the occurrence of other interaction pathways in addition to the polymerization process yielding oligomeric bridged derivatives and opening perspectives of further investigations of these model solutions.

First confirmation in red wine of products resulting from direct anthocyanin-tannin reactions.

Analysis of wine fractions before and after thiolysis confirmed the occurrence in red wine of direct reactions between anthocyanins and tannins established earlier in model solutions. Results showed the presence of two types of structures differing in the linkage position of the anthocyanin moiety. On one hand, detection of malvidin-3-glucoside (Mv3g) among thiolysis products revealed the presence of anthocyanin-derived pigments in which Mv3g is linked by its C-6 or C-8 top. On the other hand, LC/MS analysis allowed the detection of two derivatives tentatively identified as flavenes or a bicyclic condensation products yielded by the reaction of a flavanol monomer (C-6 or C-8 top) with malvidin-3-glucoside (C-4 position). The presence of the corresponding benzylthioethers after thiolysis of the polymeric fractions confirmed that procyanidins are similarly involved in the latter reaction. Besides, MS also allowed the detection of new benzylthioethers of catechin derivatives released after thiolysis of the wine fractions, indicating that in addition to the postulated processes other types of reactions take place in wines. © 2000 Society of Chemical Industry.