Macrowine 2021
IVES 9 IVES Conference Series 9 Crown procyanidin: a new procyanidin sub-family with unusual cyclic skeleton in wine

Crown procyanidin: a new procyanidin sub-family with unusual cyclic skeleton in wine

Abstract

Condensed tannins (also called proanthocyanidins) are a widely distributed throughout in plants kingdom and are one of the most important classes of secondary metabolites, in addition, they are part of the human diet. In wine, they are extracted during the winemaking process from grape skins and seeds. These compounds play an important role in red wine organoleptic characteristics such as color, bitterness and astringency. Condensed tannins in red wine are oligomers and polymers of flavan-3-ols unit such as catechin, epicatechin, epigallocatechin and epicatechin-3-O-gallate. The monomeric units can be linked among them with direct interflavanoid linkage or mediated by aldehydes. During our investigation on red wine condensed tannins, three surprisingly polar tannins oligomers (one tetramer and two pentamers) were detected by HPLC-UV-MS (Tof) and their concentrations remained stable during wine aging. The objective of this study was (1) to develop a purification method for these three oligomers of condensed tannins observed in red wine, (2) to determine their structures by high resolution mass spectrometry, chemical depolymerization strategy, as well as NMR, (3) to quantify them in various red wine and to estimate their organoleptic properties. The new procyanidin tetramer and the two new procyanidin pentamers have been purified by a “three steps-two gels” strategy with the first step of C-18 Solid Phase Extraction, the second step of TSK-40S Gel Filtration Chromatography and the last step of C-18 HPLC semi-preparative. Their fragmentation pattern obtained by MS/MS analysis using a high resolution mass spectrometry revealed that these three compounds belong to the procyanidin family. Moreover the inter-flavanoid linkages, sub-units information as well as overall configuration of the tetramer were established by 1D and 2D NMR. The structure of the tetramer have been determined to be a symmetric procyanidin with four sub-units of (−)-epicatechin link together by B-type interflavanoid linkage in the following sequence of Unit 1-(4-8)-Unit 2-(4-6)-Unit 3-(4-8)-Unit 4 (4-6)-Unit 1 with the first unit linked with the last unit via the forth interflavanoid linkage C6-C4 to form the macrocyclic structure. Since such carbon skeleton has never been reported before for procyanidins in wine, neither in plants kingdom, we decide to name this new group of procyanidins “crown procyanidins”. This new procyanidin sub-family has been quantified in three different red wines (merlot, cabernet sauvignon and shiraz) with various vintages (from 1991 to 2011). The concentration of the crown procyanidin remains stable in wine during ageing and their concentration shows higher stability than linear B-type procyanidins which their content decrease during aging. Moreover, a strong correlation between these new procyanidin and the red wine astringency level has been observed.

Publication date: May 17, 2024

Issue: Macrowine 2016

Type: Article

Authors

Michael Jourdes*, Liming Zeng, Pere Pons-Mercadé, Pierre-Louis Teissedre, Stéphanie Krisa, Tristan Richard

*UMR 1219 OEnologie

Contact the author

Tags

IVES Conference Series | Macrowine | Macrowine 2016

Citation

Related articles…

WineMetrics: A new approach to unveil the “wine-like aroma” chemical feature

“The Human being has an excellent ability to detect and discriminate odors but typically has great difficulty in identifying specific odorants”(1). Furthermore, “from a cognitive point of view the mechanism used to judge wines is closer to pattern recognition than descriptive analysis.” Therefore, when one wants to reveal the volatile “wine-like feature” pattern recognition techniques are required. Sensomics is one of the most recent “omics”, i.e. a holistic perspective of a complex system, which deals with the description of substances originated from microorganism metabolism that are “active” to human senses (2). Depicting the relevant volatile fraction in wines has been an ongoing task in recent decades to which several research groups have allocated important resources. The most common strategy has been the “target approach” in order to identify the “key odorants” for a given wine varietal.

Effects of bottle closure type on sensory characteristics of Chasselas wines

Several winemaking operations, such as filtration, pumping, and racking, are known to potentially facilitate the incorporation of atmospheric O2 into the wine. Control of grape must oxidation is one key aspect in the management of white wine aroma expression, color stability and shelf-life extension. On the one hand, controlled must oxidation may help to remove highly reactive phenolic compounds, which otherwise could contribute to premature oxidation. And on the other hand, in certain cases of extreme protection of the must from O2 (e.g. pressing under inert atmosphere), it can help to preserve varietal aromas and natural must antioxidants.

Micro-meteorological, compositional and transcriptional study of corvina grape color during ripening

Grape anthocyanin content and composition could affect the quality and the production strategies of red wines. Differences in the pigment composition modify the color properties in terms of hue, extractability and stability. Thus, for the production of a highly qualitative wine such as “Amarone”, variations in the pigment composition are not negligible. The aim of this work was the investigation of the anthocyanin profile changes during ripening in Corvina grapes, the main cultivar for the “Amarone” production. The experiment took place in 2015, in two vineyards located in Valpollicella (Italy).

Estimation of chemical age of red wines with the use of Fourier transform infrared spectroscopy (FT-IR) and chemometrics

The color of a red wine is one of the most important parameters of its quality, giving much information on its status, such as the grape variety used or the winemaking style. As the result of a complex equilibrium between different forms of anthocyanins and polymerization reactions which occur over the course of time, color can also serve as an indication of a wines’ age. For this purpose the “chemical age” i and ii indexes have been introduced by Somers in 1977. The chemical age index i measures the color absorbance after the addition of acetaldehyde while chemical index ii provides an indication of how much of the total red pigments are resistant to SO2 bleaching.

Defining the mechanisms and impact of winemaking treatments on tannin and polysaccharides in red wine: recent progress in creating diverse styles

Tannin and polysaccharide concentration and composition is important in defining the texture of red wines, but can vary due to factors such as cultivar, region, grape ripeness, viticultural practices and winemaking techniques. However, the concentration and composition of these macromolecules is dependent not only on grape tannin and polysaccharide concentration and composition, but also their extractability and, in the case of polysaccharides, their formation by yeast. Through studies into the influence of grape maturity, winemaking and sensory impacts of red grape polysaccharides, seed and skin tannins, recent research in our laboratory has shown that the processes involved in the extraction of these macromolecules from grapes and their retention in wine are very complex.