OENO IVAS 2019 banner
IVES 9 IVES Conference Series 9 OENO IVAS 9 OENO IVAS 2019 9 Analytical developments from grape to wine, spirits : omics, chemometrics approaches… 9 Molecular characterization of wines nucleophilic potential by ultra-performance liquid chromatography high resolution mass spectrometry

Molecular characterization of wines nucleophilic potential by ultra-performance liquid chromatography high resolution mass spectrometry

Abstract

The knowledge about the molecular fraction associated to white wines oxidative stability is still poorly understood. However, the role of S- N- congaing compounds, like glutathione (GSH) and other peptides, as a source of reductant in many oxidation reactions protecting against heavy metals toxicity, or lipids and polyphenols oxidation as ROS-scavenger is today very well established. GSH is also reported being an important antioxidant, reacting as nucleophile substance that conjugates straightforwardly with reactive electrophiles resulting in foods and beverages chemical oxidative stability. It has been shown that, GSH efficiency against wines sensory oxidative stability is related to wines antioxidant metabolome consisting of N- and S- containing compounds like amino acids, aromatic compounds and peptides. These compounds present a strong nucleophilic character and their reactivity with wines electrophiles such as oxidized polyphenols, suggests the formation of stable adducts presenting lower oxidative potential. We consider that the knowledge behind the chemical composition of wines antioxidant metabolome is a key factor to estimate wines aging potential. 

In that respect, the present study introduces an original determination of the pool of nucleophilic compounds that can react with quinones in wine acidic conditions. One step derivatization of nucleophiles has been realized in wines with no pH adjustment by using 4‑methyl‑1,2‑benzoquinone (Q) as a nucleophilic probe. LC‑MS‑QToF analysis of 92 white followed by Multivariate analysis (PLS‑DA) and Wilcoxon test allowed to isolate up to 141 putative nucleophilic compounds. Only 20 of these compounds were detected without derivatization, showing an increase in detection level by quinone trapping, especially for thiols. Moreover, annotation using online database (Oligonet, Metlin and KEGG) as well as elementary formula determined by isotopic profile and MS² analysis allowed to show an important proportion of amino acids and peptides and to identify 4 compounds (GSH, Cys, homocysteine and Pro). The majority of the putative peptides can contain amino acids that are known to have antioxidant properties (Val, Leu, Ile, Pro, Trp, Cys and Met). 

 

These results show that derivatization of wines using Q allows to enhance thiol detection levels and to determine a pool of untargeted nucleophilic compounds that can be part of wines antioxidant metabolome

DOI:

Publication date: June 19, 2020

Issue: OENO IVAS 2019

Type: Article

Authors

Remy Romanet, Florian Bahut, Maria Nikolantonaki, Regis Gougeon

Univ. Bourgogne Franche-Comté, AgroSup Dijon, PAM UMR A 02.102, Institut Universitaire de la Vigne et du Vin, Jules Guyot, 21000 Dijon, France

Contact the author

Keywords

LC-QToF-MS, Nucleophilic compounds, Untargeted analysis, White wines oxidative stability 

Tags

IVES Conference Series | OENO IVAS 2019

Citation

Related articles…

Inhibition of Oenococcus oeni during alcoholic fermentation by a selected Lactiplantibacillus plantarum strain

The use of selected cultures of the species Lactiplantibacillus plantarum in Oenology has grown in prominence in recent years. While initial applications of this species centred very much around malolactic fermentation (MLF), there is strong evidence to show that certain strains can be harnessed for their bio-protective effects. Unwanted spontaneous MLF during alcoholic fermentation (AF), driven by rogue Oenococcus oeni, is a winemaking deviation that is very difficult to manage when it occurs. This work set out to determine the efficacy of one particular strain of Lactiplantibacillus plantarum(Viniflora® NoVA™ Protect), against this problem in Cabernet Sauvignon must. The work was carried out at commercial scale and in a winery environment and compared the bio-protective culture with the more traditional approach of reducing must pH by the addition of tartaric acid. The combination of both was also investigated. The concentration of both Oenococcus oeni and Lactiplantibacillus plantarum was determined using qPCR. The adventitious Oenococcus oeni showed the most growth during AF in the control wine, whereas in the wines treated with Lactiplantibacillus plantarum a bacteriostatic effect against this species was observed. This effect was comparable to the wines treated with tartaric acid. This has particular commercial relevance for controlling the flora in musts with high pH, or when the addition of tartaric acid is either not permitted or is prohibitive for other reasons.

Optimizing stomatal traits for future climates

Stomatal traits determine grapevine water use, carbon supply, and water stress, which directly impact yield and berry chemistry. Breeding for stomatal traits has the strong potential to improve grapevine performance under future, drier conditions, but the trait values that breeders should target are unknown. We used a functional-structural plant model developed for grapevine (HydroShoot) to determine how stomatal traits impact canopy gas exchange, water potential, and temperature under historical and future conditions in high-quality and hot-climate California wine regions (Napa and the Central Valley). Historical climate (1990-2010) was collected from weather stations and future climate (2079-99) was projected from 4 representative climate models for California, assuming medium- and high-emissions (RCP 4.5 and 8.5). Five trait parameterizations, representing mean and extreme values for the maximum stomatal conductance (gmax) and leaf water potential threshold for stomatal closure (Ψsc), were defined from meta-analyses. Compared to mean trait values, the water-spending extremes (highest gmax or most negative Ysc) had negligible benefits for carbon gain and canopy cooling, but exacerbated vine water use and stress, for both sites and climate scenarios. These traits increased cumulative transpiration by 8 – 17%, changed cumulative carbon gain by -4 – 3%, and reduced minimum water potentials by 10 – 18%. Conversely, the water-saving extremes (lowest gmax or least negative Ψsc) strongly reduced water use and stress, but potentially compromised the carbon supply for ripening. Under RCP 8.5 conditions, these traits reduced transpiration by 22 – 35% and carbon gain by 9 – 16% and increased minimum water potentials by 20 – 28%, compared to mean values. Overall, selecting for more water-saving stomatal traits could improve water-use efficiency and avoid the detrimental effects of highly negative canopy water potentials on yield and quality, but more work is needed to evaluate whether these benefits outweigh the consequences of minor declines in carbon gain for fruit production.

Extreme canopy management for vineyard adaptation to climate change: is it a good idea?

Climate change constitutes an enormous challenge for humankind and for all human activities, viticulture not being an exception. Long-term strategic changes are probably needed the most, but growers also need to deal with short-term changes: summers that are getting progressively warmer, earlier harvest dates and higher pH in musts and wines. In the last 10-15 years, a relevant corpus of research is being developed worldwide in order to evaluate to which extent extreme canopy management operations, aimed at reducing leaf area and, thus, limiting the source to sink ratio, could be useful to delay ripening. Although extreme canopy management can result in relevant delays in harvest dates, longer term studies, as well as detailed analysis of their implications on carbohydrate reserves, bud fertility and future yield are desirable before these practices can be recommended.

Assessment of the impact of actions in the vineyard and its surrounding environment on biodiversity in Rioja Alavesa (Spain)

Traditional viticulture areas have experienced in the last decades an intensification of field practices, linked to an increased use of fertilisers and phytosanitary products, and to a more intensive mechanization and uniformization of the landscape. This change in management has sometimes led to higher rates of soil erosion andloss of soil structure, fertility decline, groundwater contamination, and to an increased pressure of pests and diseases. Additionally, intensification usually leads to a simplification of landscapes, of particular concern in prestigious wine grape regions where the economical revenue encourages the conversion of land use from natural habitats to high value wine grape production. To revert this trend, it is necessary that growers implement actions that promote biodiversity in their vineyards. The aim of this study is to assess the impact of the implementation of cover crops, vegetational corridors, dry stone walls and vineyard biodiversity hotspots estimated through the study of arthropods. The work has been carried out in four vineyards in Rioja Alavesa belonging to Ostatu winery, where these infrastructures were implemented in 2020. The presence and diversity of arthropods was studied by capturing them at different times in the season and at different distances from the infrastructure using pit-fall traps in the soil and yellow, white and blue chromatic traps at the canopy level. This is a preliminary study in which all adult insects were sorted to the taxonomic level of order and Coleoptera were classified to morphospecies. The results obtained show that there is a relationship between the basic characteristics of the vineyard and the arthropods captured, with a positive effect, although also dependent on the vineyard, of the presence of infrastructure.

Differential responses of red and white grape cultivars trained to a single trellis system – the VSP

Commercial grape production relies on training grapevine cultivars onto a variety of trellis systems. Training allows for well-lit leaves and clusters, maximizing fruit quality in addition to facilitating cultivation, harvesting, and diseases control. Although grapevines can be trained onto an infinite variety of trellis systems, most red and white cultivars are trained to the standard VSP (Vertical Shoot Positioning) system. However, red and white cultivars respond differently to VSP in fruit composition and growth characteristics, which are yet to be fully understood. Therefore, the objective of this study was to examine the influence of the VSP trellis system on fruit composition of three red, Cabernet Sauvignon, Merlot and Syrah, and three white, Chardonnay, Riesling, and Gewurztraminer cultivars grown under uniform growing conditions in the same vineyard. All cultivars were monitored for maturity and harvested at their physiologically maximum possible sugar concentration to compare various fruit quality attributes such as Brix, pH, TA, malic and tartaric acids, glucose and fructose, potassium, YAN, and phenolic compounds including total anthocyanins, anthocyanin profile, and tannins. A distinct pattern in fruit composition was observed in each cultivar. In regards to growth characteristics, Syrah grew vigorously with the highest cluster weight. Although all cultivars developed pyriform seeds, the seed size and weight varied among all cultivars. Also varied were mesocarp cell viability, brush morphology, and cane structure. This knowledge of the canopy architectural characteristics assessed by the widely employed fruit compositional attributes and growth characteristics will aid the growers in better management of the vines in varied situations.