Effects of Long-Term Bottle Storage on Red and Rosé Wines Sealed with Different Types of Closures.

Volatile and non-volatile chemical profiles, free and total SO2 and dissolved oxygen content were studied in three red (Merlot, Lagrein red, St. Magdalener) and one rosé (Lagrein rosé) wine after 30 months of storage in bottles. Each wine was sealed with closures made of a 'blend' (B) of natural cork microgranules and polymers without glue and was compared with wines closed with other types of corks (C; a technical cork 1 + 1, or an agglomerated natural cork or a natural one-piece cork). Glutathionyl caftaric acid (GRP) was inversely correlated with total SO2 content and was higher in all three red wines closed with B compared to C, whereas epicatechin was higher in three wines closed with C compared to B. Three volatile compounds formed by fermentation (ethyl butanoate, isoamyl lactate, and octanol) were inversely correlated with both free and total SO2. In terms of their volatile profiles, ethyl octanoate and 2,3-butanediol were significantly higher in the Lagrein red wines closed with C closures, whereas no significant difference was observed in Merlot, Lagrein rosé and St. Magdalener wines. Small differences in some phenolic compounds due to the type of closure were found: GRP, syringic acid, (+)-catechin, and (-)-epicatechin differentiated the Merlot wines closed with B from the C closures. Protocatechuic acid and GRP levels differentiated the Lagrein red wines according to their closure type, whereas only (-)-epicatechin differentiated the Lagrein rosé wines. GRP, caffeic acid, (-)-epicatechin, and anthocyanin content differentiated the St. Magdalener wines according to their closure type. Even though St. Magdalener and Lagrein rosé closed with C could be distinguished from those closed with B by using the (sensory) triangle test (α = 0.05), these differences appeared to be relative as it did not include all the wines in a systematic manner.

Impact of Different Stoppers on the Composition of Red and Rosé Lagrein, Schiava (Vernatsch) and Merlot Wines Stored in Bottle.

Different technical cork stoppers (blend of natural cork microgranules, one-piece natural cork, agglomerated natural cork, technical cork 1+1) were compared to evaluate the effects on the phenolic, volatile profiles and dissolved oxygen in three red (Merlot, Lagrein red, St. Magdalener) and one rosé (Lagrein rosé) wines, which were stored in bottles for 12 months. Gallic acid, caffeic acid, p-coumaric acid, trans-resveratrol, glutahionyl caftaric acid and protocatechuic acid did not vary remarkably during the first three months, whereas at six months a net increase was reported, followed by a clear decrease at 12 months. The same trend was observed in Lagrein rosé, but only for gallic acid. The total anthocyanins content decreased during the storage period in the four wines. Isopentyl acetate, 1-hexanol, ethyl hexanoate, 2-phenylethyl alcohol, diethyl succinate, ethyl octanoate and ethyl decanoate were the main volatile compounds. The sum of alcohols decreased in all four of the wines. The esters decreased in Merlot; however, they increased in Lagrein rosé, Lagrein red and St. Magdalener during the storage. Univariate and multivariate statistics and a sensory discriminant triangle test displayed similar influences of the different stoppers on the phenolic and volatile compounds during the whole storage duration. The changes detected in the phenolic and volatile concentrations were presumably due to the non-oxygen-mediated reactions occurring during 12 months of storage in bottle.

Distribution of crown hexameric procyanidin and its tetrameric and pentameric congeners in red and white wines.

Nineteen red and white wines were screened for the presence of crown (oligomeric cyclic) procyanidins with 4, 5 or 6 (epi)catechin monomers by means of HPLC-HRMS/MS. For the first time, the distribution of crown procyanidins in wines obtained from several grape varieties was discussed including white wines. The ratios between crown and non-cyclic procyanidins allowed the samples to be discriminated by grape variety. The crown hexameric procyanidin was present in the red wines and absent in the white wines analyzed. The crown pentameric procyanidin was absent in Gewürztraminer. In Chardonnay and Sauvignon Blanc, the pentameric procyanidin was present only in the cyclic form. Less oxidized high quality red wines displayed a higher fraction of crown to non-cyclic procyanidins than the other wines. These compounds are proposed as potential complement markers of wine quality and authenticity.

Relative abundances of novel cyclic prodelphinidins in wine depending on the grape variety.

The identification of cyclic B-type procyanidins in grape and wine was recently disclosed. Some of these were also found in berries of totally different vegetal species (eg, Vaccinium sp.). However, presence of a wider class of these cyclic condensed tannin compounds with variably substituted monomers has never been addressed so far. Here, an extended list of oligomeric cyclic proanthocyanidins (PAC) bearing variable substitution patterns on the main flavan-3-ol unit has been searched in wines. Nearly 7600 theoretical structures were calculated and searched in red and white wine samples made from different grape varieties. Moreover, a hydrogen/deuterium exchange approach (already applied to a cyclic tetrameric procyanidin) coupled to high-resolution mass spectrometry was applied to confirm their cyclic B-type structure rather than a non cyclic A-type structure, otherwise isomeric and undistinguishable by LC-MS alone. The main group of novel cyclic PAC observed is shown to contain (epi)gallocatechin beside (epi)catechin as the constituent monomers.

Disambiguation of Isomeric Procyanidins with Cyclic B-Type and Non-cyclic A-Type Structures from Wine and Peanut Skin with HPLC-HDX-HRMS/MS.

Hydrogen/deuterium exchange coupled with high-resolution mass spectrometry was successfully applied for the identification of A-type tetrameric, pentameric, and hexameric procyanidins in peanut skin. This extended a previous study on isomeric cyclic B-type unconventional tetramer, pentamer, and hexamer procyanidins found in wine and cranberries. Not only had the method successfully identified the procyanidins with a single A-linkage (e.g., tetrameric m/z 1153.2608) by means of distinguishing them from their isomeric cyclic B-type analogues, but this method also worked for procyanidins with two or more A-linkages (such as the tetrameric m/z 1151.2452). As a further consequence, B-type cyclic pentamers and hexamers in wine have been elucidated with hydrogen/deuterium exchange (HDX) for the first time. Graphical Abstract ᅟ.

Selective binding of potassium and calcium ions to novel cyclic proanthocyanidins in wine by HPLC-HRMS.

RATIONALE: Cyclic B-type (referred also as crown) proanthocyanidins were recently identified in wines. An HPLC-HRMS/MS method was applied to study the binding of cyclic and non-cyclic PAC to potassium and calcium ions, which affect the chemico-physical stability of wines. Different binding affinities suggest that cyclic and non-cyclic analogues, despite the equal number of monomer units, influence the colloidal stability of wine and are related to the grape variety or winemaking conditions. METHODS: Nineteen red and white wines were analysed by HPLC high resolution tandem mass spectrometry with positive electrospray ionization to investigate the distribution of novel cyclic proanthocyanidins and their calcium, potassium and sodium adducts. Principal Component Analysis was used to study the distribution of the wines and the relationships among proanthocyanidins with and without cation complexes. RESULTS: A dependence on specific isomers (and conformations) was found for the non-cyclic procyanidin (PC) trimer whereas the cyclic tetrameric PAC were shown to bind better to potassium than their non-cyclic analogues. The binding to these metals appeared to be influenced not only be the number of monomer units but also by the conformation assumed by the molecules. Statistical analysis evidenced that the adducts distribution in different wines is less influenced by the grape variety used for winemaking than their associated [M+H]+ species studied earlier. CONCLUSIONS: Wines from 19 grape varieties were investigated in order to identify potassium and calcium complexes of non- and cyclic B-type proanthocyanidins that were recently discovered. The results showed a dependence of the distribution of metal complexes according to the cyclic or non cyclic geometry of proanthocyanidins. The multivariate analysis of the mass spectrometric results showed a relationship with the grape variety, however not so straightforward as evidenced for the non-complexed species.

Volatile, phenolic, and sensory profiles of in-amphorae Chardonnay wine by mass spectrometry and chemometric analysis.

The sensory properties, the phenolic composition, and the volatile profile of Chardonnay wine made in amphorae were compared with the wine obtained in large wooden barrels (2000 L) and small toasted barrels (225 L). Hierarchical cluster analysis and principal component analysis built on the phenolics and volatiles variables allowed to group effectively the samples according to the winemaking material used. In-amphorae wines showed more abundant catechin and caffeic acid and less abundant caftaric acid and trans-coutaric acid. Condensation reactions proceeded in the wood containers leading to esterification of organic acids with ethanol and alcohols, whereas in-amphorae wines were characterized by a higher content of free phenolic acids and higher volatile alcohols. Among the volatile compounds, ramified ethyl esters contributed mostly in samples made in small toasted barrels, whereas nonbranched ethyl esters contributed more for the samples made in large wooden tanks; higher alcohols contributed more for the in-amphorae wine. The sensory analysis showed negligible differences induced by the in-amphorae vinification with respect to the wooden one. Four variables could distinguish wines made in-amphorae compared with the other containers: solvent and acetone (SA), astringent/pungency (AP), fruity (FR), and color intensity (CI). The overall approach proposed here is promising for future developments of innovative types of Chardonnay wine blends.

Isotopic Exchange HPLC-HRMS/MS Applied to Cyclic Proanthocyanidins in Wine and Cranberries.

Cyclic B-type proanthocyanidins in red wines and grapes have been discovered recently. However, proanthocyanidins of a different chemical structure (non-cyclic A-type proanthocyanidins) already known to be present in cranberries and wine possess an identical theoretical mass. As a matter of fact, the retention times and the MS/MS fragmentations found for the proposed novel cyclic B-type tetrameric proanthocyanidin in red wine and the known tetrameric proanthocyanidin in a cranberry extract are herein shown to be identical. Thus, hydrogen/deuterium (H/D) exchange was applied to HPLC-HRMS/MS to confirm the actual chemical structure of the new oligomeric proanthocyanidins. The comparison of the results in water and deuterium oxide and between wine and cranberry extract indicates that the cyclic B-type tetrameric proanthocyanidin is the actual constituent of the recently proposed novel tetrameric species ([C60H49O24]+, m/z 1153.2608). Surprisingly, the same compound was also identified as the main tetrameric proanthocyanidin in cranberries. Finally, a totally new cyclic B-type hexameric proanthocyanidin ([C90H73O36]+, m/z 1729.3876) belonging to this novel class was identified for the first time in red wine. Graphical Abstract ᅟ.