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…

Towards multi-purpose valorisation of polyphenols from grape pomace: Pressurized liquid extraction coupled to purification by membrane processes

Grape by-products (including skins, seeds, stems and vine shoots) are rich in health promoting polyphenols. Their extraction from winery waste and their following purification are of special interest to produce extracts with high added value compounds. Meanwhile, the growing concern over environmental problems associated with economic constraints, require the development of environmentally sustainable extraction technologies. The extraction using semi-continuous subcritical water, as a natural solvent at high temperature and high pressure a technology is promising “green” technology that is environmentally friendly, energy efficient and improve the extraction process in plant tissues.

Metabolomics of grape polyphenols as a consequence of post-harvest drying: on-plant dehydration vs warehouse withering

A method of suspect screening analysis to study grape metabolomics, was developed [1]. By performing ultra-high performance liquid chromatography (UHPLC) – high-resolution mass spectrometry (HRMS) analysis of the grape extract, averaging 320-450 putative grape compounds are identified which include mainly polyphenols. Identification of metabolites is performed by a new HRMS-database of putative grape and wine compounds expressly constructed (GrapeMetabolomics) which currently includes around 1,100 entries.

Moscatel vine-shoot extracts as grapevine biostimulant to increase the varietal aroma of Airén wines

There is a growing interest in the exploitation of vine-shoots waste, since they are often left or burned. Sánchez-Gómez et al. [1] have shown that vines-shoots aqueous extracts have significant contents of bioactive compounds, among which several polyphenols and volatiles are highlighted. Recent studied had demonstrated that the chemical composition of vine-shoots is enhanced when vine-shoots are toasted
[2,3]. The application of vegetable products in the vineyards has led to significant changes towards a more “Sustainable Viticulture”. An innovative foliar application for Airén vine-shoot extracts have been carried out to the vineyard. It has been shown that they act as grape biostimulants, improving certain wine quality characteristics [4].

Effect of malolactic fermentation in barrels or stainless steel tanks on wine composition. Influence of the barrel toasting

Ellagitannin, anthocyanin and woody volatile composition of Cabernet Sauvignon wines aged in oak barrels for 12 months was evaluated. Depending on the container where malolactic fermentation (MLF) was carried out, two wine modalities were investigated: wines with MLF carried out in stainless steel tanks and barrel-fermented wines. Three toasting methods (medium toast, MT; medium toast with watering, MTAA; noisette) were considered for ageing of each wine modality. Sensory analyses (triangle and rating tests) were also performed. Two-way ANOVA of the raw experimental data revealed that the toasting method and the container where MLF took place, as well as the interaction between both factors, have a significant influence (p < 0.05) on ellagitannin, anthocyanin and woody volatile profiles of Cabernet Sauvignon wines.

Comprehensive exploration of wine aroma-related compounds as promoted by alternative vinification procedures in case of Zelen (Vitis vinifera L.) grapes processing

Not only vintner’s decisions in the vineyard, but also winemaker’s choices of technology approaches in the cellar play a significant role in the final wine style and quality. Whereas traditional technologies within chosen terroir are quite well explored and thus somehow predictable, there is no proper knowledge available on possible outcomes in case of implementing novel, alternative winemaking strategies. To reveal their effects on wine aroma compounds and sensory characteristics, two alternative strategies
(cryoextraction or addition of whole grape berries during last stages of fermentation) were compared to classical Vipava valley winemaking approach as normally used for an autochthonous variety Zelen. After separate vinification and bottling, all the experimental wines were subjected to semiquantitative metabolic profiling of volatile compounds (VOCs) by means of GC/MS and were then also sensorialy evaluated by pre-trained panel.