Grape-Derived Polysaccharide Extracts Rich in Rhamnogalacturonans-II as Potential Modulators of White Wine Flavor Compounds.

Many authors have investigated the role of mannoproteins on wine quality, but very few have analyzed the use of grape-derived polysaccharides as they are not commercially available. In this study, purified grape-derived polysaccharides from red wine (WPP) and winemaking by-products (DWRP: Distilled Washing Residues Polysaccharides) were used as potential fining agents to modulate white wine flavor. Phenolics and volatile compounds were analyzed in the control and wines treated with WPP, DWRP, and commercial mannoproteins (CMs) after one and twelve months of bottling, and a sensory analysis was conducted. WPP and DWRP, rich in rhamnogalacturonans-II, showed themselves to be good modulators of wine aroma and astringency. Improvement in wine aroma was related to an increase in all volatile families expect higher alcohols and volatile acids. The modulation of astringency and bitterness was related to a reduction in the proanthocyanidin content and its mean degree of polymerization. Extracts with polysaccharides with higher protein contents presented a higher retention of volatile compounds, and DWRP extract had more positive effects on the overall aroma. Our novel results present the possibility of obtaining valuable polysaccharides from distilled washing residues of wine pomaces, which could promote its valorization as a by-product. This is the first time the potential use of this by-product has been described.

Impact of grape variety, berry maturity and size on the extractability of skin polyphenols during model wine-like maceration experiments.

BACKGROUND: Skin cell walls modulate anthocyanin and tannin extraction from grape skins. However, relationships between the composition of alcohol-insoluble cell wall solids (AIS) and extraction are still unclear. Our objectives were to characterize the impact of variety, berry size and ripeness on skin AIS composition (polysaccharides, proteins) and polyphenol extraction during maceration. RESULTS: Grape skin composition and its impact on polyphenol extraction was compared for two varieties - Carignan and Grenache - with skins of berries sorted according to their size and density. Extractions were performed under model wine-like maceration conditions. Fresh skins had similar content of polymeric tannins, but strongly differed in their anthocyanin content (higher in Carignan and in the ripest berries) and composition (higher proportions in coumaroylated anthocyanins in Carignan). Anthocyanin extraction was proportionally much higher in Grenache, which was not just related to the Carignan's higher levels in coumaroylated anthocyanins. Chemical reactions decreased anthocyanin concentrations in solution for both varieties. Tannin extraction for Grenache was slightly higher and faster than for Carignan. Skin AISs differed slightly between the two varieties in their carbohydrate composition and protein content, but not between modalities. Polyphenol analyses in the precipitates evidenced at the end of the maceration and in residual skins highlighted differences between the two varieties and between berries with different ripeness. CONCLUSION: Structural information on the cell wall network and on its changes during maceration, along with a better understanding of the chemical reactions of anthocyanins and tannins, is needed to better relate grape and wine polyphenol composition. © 2020 Society of Chemical Industry.

Inhibition Mechanisms of Wine Polysaccharides on Salivary Protein Precipitation.

In this work, high-performance liquid chromatography, fluorescence quenching, nephelometry, and sodium dodecyl sulfate polyacrylamide gel electrophoresis were used to study the effect of polysaccharides naturally present in wine [rhamnogalacturonan II (RG II) and arabinogalactan proteins (AGPs)] on the interaction between salivary proteins (SP) together present in saliva and tannins (punicalagin (PNG) and procyanidin B2). In general, the RG II fraction was more efficient to inhibit SP precipitation by tannins, especially for acidic proline-rich proteins (aPRPs) and statherin/P-B peptide, than AGPs. The RG II fraction can act mainly by a competition mechanism in which polysaccharides compete by tannin binding. However, in the presence of Na+ ions in solution, no RG II effect was observed on SP-tannin interactions. On the other hand, dependent upon the saliva sample as well as the tannin studied, AGPs can act by both mechanisms, competition and ternary (formation of a ternary complex with SP-tannin aggregates enhancing their solubility).

The impact of distillation process on the chemical composition and potential prebiotic activity of different oligosaccharidic fractions extracted from grape seeds.

The study was designed to evaluate how the distillation process is able to affect the composition and bioactivity of oligosaccharides contained in the grape seeds. Different oligosaccharidic fractions have been extracted both before and after grape pomace distillation in order to valorize this by-product. A multistep solid-phase extraction approach (C-18 and carbograph cartridges) has been applied to purify and fractionate the oligosaccharidic compounds. Chemical characterization of the fractions was performed using a UPLC-ESI-MSn method. Complex oligosaccharides consist principally of neutral oligosaccharides rich in arabinose and glucose. Then, the oligosaccharides contained in the different fractions as potential functional ingredients with prebiotic activity toward well-known probiotic bacteria, such as Lactobacillus acidophilus and Lactobacillus plantarum, were evaluated. Data showed how, in some combination, oligosaccharidic fractions obtained may be considered a novel "functional ingredient" with potential prebiotic activity mainly towards L. acidophilus.

The three-dimensional structure of the mega-oligosaccharide rhamnogalacturonan II monomer: a combined molecular modeling and NMR investigation.

In this study, we describe the first optimized molecular models of the mega-oligosaccharide rhamnogalaturonan II, that is found in the primary cell walls of all higher plants. The 750 MHz 1H NMR data previously reported and new heteronuclear correlation spectra (sensitivity-enhanced HSQC and HSQC-TOCSY) were first reassigned in light of the modifications in the primary structure. In turn, the experimental NMR data revealed the presence of an additional sugar, alpha-Araf (E-chain), and also the disaccharidic repeating unit of RG-I, another component of the pectic matrix. Due to a fuller picture of the primary structure of RG-II, a much more complete assignment of the NOE data has been achieved. A systematic computational study based on these NOEs lead us to a realistic three-dimensional description of the RG-II, in excellent agreement with the molecular dimensions obtained from various experimental methods.

Chronic oral administration of rhamnogalacturonan-II dimer, a pectic polysaccharide, failed to accelerate body lead detoxification after chronic lead exposure in rats.

Lead is a ubiquitous heavy metal and its toxicity remains an important public health issue. In previous work, we reported that ingestion of rhamnogalacturonan-II dimer (dRGII), a pectic polysaccharide, may decrease intestinal absorption and status of Pb in rats. Here, we evaluated the potential detoxifying effect of different doses of dRGII after chronic oral Pb exposure in rats. For this purpose, six groups of ten male Wistar rats weighing 150g were treated as follows: group A received a semi-purified control diet for 6 weeks; groups B, C, D, E and F received the same diet plus 3 mg Pb (as acetate) for 3 weeks. Group B was then killed. Groups C, D, E, and F continued to receive the semi-purified control diet containing 0, 2, 6 or 18g dRGII/kg diet for 3 additional weeks. During the last 5 d, a Pb conventional balance study was performed. Rats were then anaesthetized and tissues were sampled for Pb and essential minerals assay. The results showed that residual Pb in the added dRGII was not available for absorption. However, the added dRGII failed to induce any significant increase in faecal or urinary Pb excretion. Consequently, at the end of the study the intestinal Pb absorption and balance remained unchanged in the animals receiving the different doses of dRGII. In line with this, we showed that dRGII administration was not effective in decreasing tibia or kidney Pb levels in rats. In conclusion, Pb complexed by dRGII in fruits and vegetables and fruit juice is thus mostly unavailable for intestinal absorption. However, the addition of dRGII after chronic Pb exposure does not help Pb detoxification.