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…

Heatwaves and grapevine yield in the Douro region, crop model simulations

Heatwaves or extreme heat events can be particularly harmful to agriculture. Grapevines grown in the Douro winemaking region are particularly exposed to this threat, due to the specificities of the already warm and dry climatic conditions. Furthermore, climate change simulations point to an increase in the frequency of occurrence of these extreme heat events, therefore posing a major challenge to winegrowers in the Mediterranean type climates. The current study focuses on the application of the STICS crop model to assess the potential impacts of heatwaves in grapevine yields over the Douro valley winemaking region. For this purpose, STICS was applied to grapevines using high-resolution weather, soil and terrain datasets over the Douro. To assess the impact of heatwaves, the weather dataset (1989-2005) was artificially modified, generating periods with anomalously high temperatures (+5 ºC), at certain onset dates and with specific durations (from 5 to 9 days). The model was run with this modified weather dataset and results were compared to the original unmodified runs. The results show that heatwaves can have a very strong impact on grapevine yields, strongly depending on the onset dates and duration of the heatwaves. The highest negative impacts may result in a decrease in the yield by up to -35% in some regions. Despite some uncertainties inherent to the current modelling assessment, the present study highlights the negative impacts of heatwaves on viticultural yields in the Douro region, which is critical information for stakeholders within the winemaking sector for planning suitable adaptation measures.

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.

Genotypic variability in root architectural traits and putative implications for water uptake in grafted grapevine

Root system architecture (RSA) is important for soil exploration and edaphic resources acquisition by the plant, and thus contributes largely to its productivity and adaptation to environmental stresses, particularly soil water deficit. In grafted grapevine, while the degree of drought tolerance induced by the rootstock has been well documented in the vineyard, information about the underlying physiological processes, particularly at the root level, is scarce, due to the inherent difficulties in observing large root systems in situ. The objectives of this study were to determine genetic differences in the root architectural traits and their relationships to water uptake in two Vitis rootstocks genotypes (RGM, 140Ru) differing in their adaptation to drought. Young rootstocks grafted upon the Riesling variety were transplanted into cylindrical tubes and in 2D rhizotrons under two conditions, well watered and moderate water stress. Root traits were analyzed by digital imaging and the amount of transpired water was measured gravimetrically twice a week. Root phenotyping after 30 days reveal substantial variation in RSA traits between genotypes despite similar total root mass; the drought-tolerant 140Ru showed higher root length density in the deep layer, while the drought-sensitive RGM was characterised by shallow-angled root system development with more basal roots and a larger proportion of fine roots in the upper half of the tube. Water deficit affected canopy size and shoot mass to a greater extent than root development and architectural-related traits for both 140Ru and RGM, suggesting vertical distribution of roots was controlled by genotype rather than plasticity to soil water regime. The deeper root system of 140Ru as compared to RGM correlated with greater daily water uptake and sustained stomata opening under water-limited conditions but had little effect on above-ground growth. Our results highlight that grapevine rootstocks have constitutively distinct RSA phenotypes and that, in the context of climate change, those that develop an extensive root network at depth may provide a desirable advantage to the plant in coping with reduced water resources.

Use of multispectral satellite for monitoring vine water status in mediterranean areas

The development of new generations of multispectral satellites such as Sentinel-2 opens possibilities as to vine water status assessment (Cohen et al., 2019). Based on a three years field campaign, a model of Stem Water Potential (SWP) estimation on vine using four satellite bands in Red, Red-Edge, NIR and SWIR domains was developed (Laroche-Pinel et al., 2021). The model relies on SWP field measures done using a pressure chamber (Scholander et al., 1965), which is a common, robust and precise method to assess vine water status (Acevedo-Opazo et al., 2008). The model was mainly developed from from SWP measures on Syrah N (Laroche Pinel E., 2021).

A large scale monitoring was organized in different vineyards in the Mediterranean region in 2021. 10 varieties amongst the most represented in this area were monitored (Cabernet sauvignon N, Chardonnay B, Cinsault N, Grenache N, Merlot N, Mourvèdre N, Sauvignon B, Syrah N, Vermentino B, Viognier B). The model was used to produce water status maps from Sentinel-2 images, starting from the beginning of June (fruit set) up to September (harvest). The average estimated SWP for each vine was compared to actual field SWP measures done by wine growers or technicians during usual monitoring of irrigation programs. The correlations between mean estimated SWP and mean measured SWP were at the same level than expected by the model. (Laroche Pinel, 2021) The general SWP kinetics were comparable. The estimated SWP would have led to same irrigation decisions concerning the date of first irrigation in comparison with measured SWP.

Acevedo-Opazo, C., Tisseyre, B., Ojeda, H., Ortega-Farias, S., Guillaume, S. (2008). Is it possible to assess the spatial variability of vine water status? OENO One, 42(4), 203.
Cohen, Y., Gogumalla, P., Bahat, I., Netzer, Y., Ben-Gal, A., Lenski, I., … Helman, D. (2019). Can time series of multispectral satellite images be used to estimate stem water potential in vineyards? In Precision agriculture ’19, The Netherlands: Wageningen Academic Publishers, pp. 445–451.
Laroche-Pinel, E., Duthoit, S., Albughdadi, M., Costard, A. D., Rousseau, J., Chéret, V., & Clenet, H. (2021). Towards vine water status monitoring on a large scale using sentinel-2 images. remote sensing, 13(9), 1837.
Laroche-Pinel,E. (2021). Suivi du statut hydrique de la vigne par télédétection hyper et multispectrale. Thèse INP Toulouse, France.
Scholander, P.F., Bradstreet, E.D., Hemmingsen, E.A., & Hammel, H.T. (1965). Sap pressure in vascular plants: Negative hydrostatic pressure can be measured in plants. Science, 148(3668), 339–346.

Adapting the vineyard to climate change in warm climate regions with cultural practices

Since the 1980s global regime shift, grape growers have been steadily adapting to a changing climate. These adaptations have preserved the region-climate-cultivar rapports that have established the global trade of wine with lucrative economic benefits since the middle of 17th century. The advent of using fractions of crop and actual evapotranspiration replacement in vineyards with the use of supplemental irrigation has furthered the adaptation of wine grape cultivation. The shift in trellis systems, as well as pruning methods from positioned shoot systems to sprawling canopies, as well as adapting the bearing surface from head-trained, cane-pruned to cordon-trained, spur-pruned systems have also aided in the adaptation of grapevine to warmer temperatures. In warm climates, the use of shade cloth or over-head shade films not only have aided in arresting the damage of heat waves, but also identified opportunities to reduce the evapotranspiration from vineyards, reducing environmental footprint of vineyard. Our increase in knowledge on how best to understand the response of grapevine to climate change was aided with the identification of solar radiation exposure biomarker that is now used for phenotyping cultivars in their adaptability to harsh environments. Using fruit-based metrics such as sugar-flavonoid relationships were shown to be better indicators of losses in berry integrity associated with a warming climate, rather than solely focusing on region-climate-cultivar rapports. The resilience of wine grape was further enhanced by exploitation of rootstock × scion combinations that can resist untoward droughts and warm temperatures by making more resilient grapevine combinations. Our understanding of soil-plant-atmosphere continuum in the vineyard has increased within the last 50 years in such a manner that growers are able to use no-till systems with the aid of arbuscular mycorrhiza fungi inoculation with permanent cover cropping making the vineyard more resilient to droughts and heat waves. In premium wine grape regions viticulture has successfully adapted to a rapidly changing climate thus far, but berry based metrics are raising a concern that we may be approaching a tipping point.