Untargeted voltammetric approaches for characterization of oxidation patterns in white wines.

Chemical and electrochemical changes associated with controlled oxidation were measured in thirteen commercial white wines, in order to evaluate the potential of linear sweep voltammetry to provide relevant information on the oxidative behavior of individual wines. For a given amount of oxygen consumed, substantial diversity of oxidative behaviors was observed. A good correlation (R2 = 0.69) was observed between the rate of O2 consumption of individual wines and the total charged passed during linear sweep voltammetry, but not with their Folin-Ciocalteu values. Onset potential of anodic oxidation was also related to oxygen consumption capacity of wine, indicating an important contribution of easily oxidizable substrates. Subtraction of voltammograms of oxidized wines from their corresponding non-oxidized controls generated new voltammograms representative of the global changes induced by oxidation. These new voltammograms contained several features related to oxygen consumption rates of each wine, and could be considered as a 'wine oxidation signature'.

Influence of closure, phenolic levels and microoxygenation on Cabernet Sauvignon wine composition after 5 years' bottle storage.

BACKGROUND: Wine aging is generally limited by the amount of oxidation, which is dependent on the amount of oxygen entering via the closure. Cabernet Sauvignon wine is well known for its high concentration of tannin, making it an ideal red wine for aging. The impact of closure type after 5 years' bottle aging has been investigated on a 2007 Cabernet Sauvignon red wine, treated with or without polyvinylpolypyrrolidone (PVPP) and micro-oxygenation (Mox). Two oxygen transfer rate (OTR) conditions (16 and 5 µg per day) into 375 mL bottles were obtained by using different synthetic stoppers. RESULTS: Color was evaluated by UV-visible spectrophotometry, carbonyls by 2,4-dinitrophenylhydrazine derivatization, phenolics by high-performance liquid chromatography and sulfur dioxide by the aspiration method. Closure type strongly influenced color parameters involving SO2 bleaching and some phenolics, particularly quercetin, were affected, but there was little effect on carbonyls other than acetaldehyde. PVPP treatment afforded wines with the lowest levels of phenolics and color density, but highest acetaldehyde. Few effects of Mox could be detected. CONCLUSIONS: Closure OTR strongly affects sulfur dioxide levels - the primary antioxidant in wine - in aged wine, but phenolic levels substantially alter the secondary reactions of oxidative aging.

Oxygen consumption and development of volatile sulfur compounds during bottle aging of two Shiraz wines. Influence of pre- and postbottling controlled oxygen exposure.

The evolution of different volatile sulfur compounds (VSCs) during bottle maturation of two Shiraz wines submitted to controlled oxygen exposure prior to bottling (through micro-oxygenation, MOX) and postbottling (through the closure) was investigated. H(2)S, methyl mercaptan (MeSH), and dimethyl sulfide (DMS) were found to increase during aging. Lower postbottling oxygen exposure, as obtained by different degrees of oxygen ingress through the closure, resulted in increased H(2)S and methyl mercaptan. In one wine MOX increased the concentration of H(2)S and methyl mercaptan during maturation. Dimethyl disulfide and DMS were not affected by any form of oxygen exposure. Overall, postbottling oxygen had a stronger influence than MOX on the evolution of VSCs. Data suggest that dimethyl disulfide was not a precursor to methyl mercaptan during bottle maturation. For the two wines studied, a consumption of oxygen of 5 mg/L over 12 months was the most effective oxygen exposure regimen to decrease accumulation of MeSH and H(2)S during bottle aging.

Evolution of 3-mercaptohexanol, hydrogen sulfide, and methyl mercaptan during bottle storage of Sauvignon blanc wines. Effect of glutathione, copper, oxygen exposure, and closure-derived oxygen.

The effects of wine composition and postbottling oxygen exposure on 3-mercaptohexanol (3-MH), hydrogen sulfide (H2S), and methyl mercaptan (MeSH) were investigated. A Sauvignon blanc wine with initial copper concentration of 0.1 mg/L was treated with copper sulfate and/or glutathione (GSH) prior to bottling to give final concentrations of 0.3 and 20 mg/L, respectively. The wines were bottled with a synthetic closure previously stored in either ambient air or nitrogen to study the effect of the oxygen normally present in the closure. Bottled wines were stored for 6 months in either air or nitrogen to study the effect of oxygen ingress through the closure. Copper addition resulted in a rapid initial decrease in 3-MH. During storage, a further decrease of 3-MH was observed, which was lower with GSH addition and lowered oxygen exposure. H2S accumulated largely during the second 3 months of bottle storage, with the highest concentrations attained in the wines treated with GSH and copper. Lower oxygen from and through the closure promoted H2S accumulation. The concentration of MeSH was virtually not affected by the experimental variables at 6 months, although differences were observed after 3 months of storage. The implications for wine quality are discussed.

Sensory characteristics changes of red Grenache wines submitted to different oxygen exposures pre and post bottling.

It is widely accepted that oxygen contributes to wine development by impacting its colour, aromatic bouquet, and mouth-feel properties. The wine industry can now also take advantage of engineered solutions to deliver known amounts of oxygen into bottles through the closures. This study was aimed at monitoring the influence of oxygen pick-up, before (micro-oxygenation, Mox) and after (nano-oxygenation) bottling, on wine sensory evolution. Red Grenache wines were prepared either by flash release (FR) or traditional soaking (Trad) and with or without Mox during elevage (FR+noMox, FR+Mox, Trad+noMox, Trad+Mox). The rate of nano oxygenation was controlled by combining consistent oxygen transfer rate (OTR) closures and different oxygen controlled storage conditions. Wine sensory characteristics were analyzed by sensory profile, at bottling (T0) and after 5 and 10 months of ageing, by a panel of trained judges. Effects of winemaking techniques and OTR were analyzed by multivariate analysis (principal component analysis and agglomerative hierarchical clustering) and analysis of variance. Results showed that, at bottling, Trad wines were perceived more animal and FR wines more bitter and astringent. Mox wines showed more orange shade. At 5 and 10 months, visual and olfactory differences were observed according to the OTR levels: modalities with higher oxygen ingress were darker and fruitier but also perceived significantly less animal than modalities with lower oxygen. Along the 10 months of ageing, the influence of OTR became more important as shown by increased significance levels of the observed differences. As the mouth-feel properties of the wines were mainly dictated by winemaking techniques, OTR had only little impact on "in mouth" attributes.

Mass spectrometric evidence for the existence of oligomeric anthocyanins in grape skins.

The fractionation of a grape skin extract by multilayer countercurrent chromatography coupled with step gradient elution allowed the preparation of a fraction almost devoid of free anthocyanins. This fraction appeared to be almost exclusively polymeric, as judged by liquid chromatographic-mass spectrometric (LC-MS) analysis, color-bleaching tests with sulfur dioxide, and thiolysis. Electrospray mass spectrometric analysis indicated that the pigmented material in this fraction was chiefly composed of direct condensation products of anthocyanin extending up to trimers. With regard to their linkages, the anthocyanin units in the oligomers were possibly linked by either an A-type (by both carbon-carbon and ether bonds) or B-type (by carbon-carbon bond) linkage, like proanthocyanidins. The terminal anthocyanin unit of the oligomers is consistently in the flavylium form but the extension units are in the flavan form for the A-type oligomers and in the flavene form for the B-type oligomers. Although their linkages still need to be defined rigorously, this is the first mass spectrometric evidence confirming the existence of anthocyanin oligomers in the grape skin extract.

Fractionation of grape anthocyanin classes using multilayer coil countercurrent chromatography with step gradient elution.

Grape anthocyanins from rosé wine pomace and grape skins were fractionated by multilayer coil countercurrent chromatography (MLCCC). Tert-butyl methyl ether/n-butanol/acetonitrile/water acidified with trifluoroacetic acid (2/2/x/5) was chosen as the solvent system because of its demonstrated efficiency in separating anthocyanins. A method combining MLCCC and step gradient elution has been developed. This method enabled the fractionation of anthocyanins as series of glucosides, and the corresponding acetylated, coumaroylated, and caffeoylated derivatives. The different anthocyanins were identified on the basis of their UV spectra, their elution time on reversed-phase HPLC as well as by mass spectrometry. A polar-colored fraction free of anthocyanin monomers and corresponding to the material remaining in the stationary phase after the completion of the gradient was recovered.

Characterization of proanthocyanidins in grape seeds using electrospray mass spectrometry.

Two proanthocyanidin (PA) fractions, one (Sdp3) with the mean degree of polymerization (mDP) of 3 and the other (Sdp9) with mDP of 9, were obtained from a Vitis vinifera cv. Shiraz grape seed extract. The PA fractions were directly analyzed by electrospray ionization mass spectrometry (ES-MS) and negative ion mass spectra were recorded. The mass spectrum of Sdp3 exhibited only singly charged ions corresponding to the molecular mass of PA with a degree of polymerization (DP) up to 9 (nonamers). In contrast, Sdp9 yielded rather complex mass spectra featuring ions with single [M - H](-), double [M - 2H](2-) and triple [M - 3H](3-) charge representing the molecular masses of PAs up to a DP of 28. In addition, the degree of galloylation per procyanidin (DG) was observed to be up to 5 (pentagallates) in Sdp3 and 8 (octagallates) in the Sdp9. This is the first evidence obtained by mass spectrometry for the distribution of grape seed PAs with such a high degree of polymerization and a broad diversity of galloylation. ES-MS data together with the complementary information provided by acid hydrolysis provides a detailed picture of the composition of grape seed PAs.

Changes in proanthocyanidin chain length in winelike model solutions.

Reactions of seed and skin proanthocyanidins in the presence or absence of (-)-epicatechin were followed in winelike solutions over 53 days at 30 degrees C. Proanthocyanidins were separated from flavanol monomers by sequential elution from a Sep Pak cartridge, and changes in proanthocyanidin composition were monitored by thiolysis analysis of the proanthocyanidin fraction. In solutions containing no free (-)-epicatechin, trace amounts of monomers were released and important losses of proanthocyanidins were measured, but their average composition and mean degree of polymerization (mDP) were hardly modified. In the presence of (-)-epicatechin, the mDP value decreased and oligomeric proanthocyanidins accumulated throughout the incubation while losses of total units were dramatically reduced. Our data indicate that interflavanic bond cleavage of proanthocyanidins occurred under mild acidic conditions such as encountered in wine and that the resulting carbocation proceeded to unknown species. The latter reaction did not take place in the presence of (-)-epicatechin. Epicatechin added to the intermediate carbocation, thus being incorporated as the end unit of a shorter proanthocyanidin chain. The results of this study are discussed in relation to the loss of astringency reported during wine aging.