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…

Climate and the evolving mix of grape varieties in Australia’s wine regions

The purpose of this study is to examine the changing mix of winegrape varieties in Australia so as to address the question: In the light of key climate indicators and predictions of further climate change, how appropriate are the grape varieties currently planted in Australia’s wine regions? To achieve this, regions are classified into zones according to each region’s climate variables, particularly average growing season temperature (GST), leaving aside within-region variations in climates. Five different climatic classifications are reported. Using projections of GSTs for the mid- and late 21st century, the extent to which each region is projected to move from its current zone classification to a warmer one is reported. Also shown is the changing proportion of each of 21 key varieties grown in a GST zone considered to be optimal for premium winegrape production. Together these indicators strengthen earlier suggestions that the mix of varieties may be currently less than ideal in many Australian wine regions, and would become even less so in coming decades if that mix was not altered in the anticipation of climate change. That is, grape varieties in many (especially the warmest) regions will have to keep changing, or wineries will have to seek fruit from higher latitudes or elevations if they wish to retain their current mix of varieties and wine styles.

Effect of one-year cover crop and arbuscular mycorrhiza inocululation in the microbial soil community of a vineyard

The microbial composition of the soil is an important factor to consider in viticulture, since its influence on the “terroir” and on the organoleptic properties of the wine have been demonstrated. Different agronomic techniques have the potential to modify the composition and functionality of the soil microbial community. Maintaining green covers is known to increase soil microbial diversity. The direct application of inoculum of beneficial microorganisms to the soil has also been used to increase their abundance. However, the environmental conditions of each site seem to have a determining weight in the result of these practices. In this study, we compared the effect on the microbial community of a cover crop with legumes in autumn and the inoculation of grapevines with commercial inoculum bases on Rhizophagus irregularis and Funeliformis mosseae in the previous spring. The study has been carried out in a vineyard in Binissalem, Mallorca, Spain. After applying the treatments, we will analyze the soil microbial communities using the data obtained from Illumina amplification of soil DNA from the 16S and ITS regions to analyze bacteria and fungi community, respectively. In addition, we will record the physicochemical characteristics of the soil at each sampling point. The result showed that agronomic management, in the short term, has less influence than soil characteristics on the composition of the soil microbiome. With these results, we can conclude that in a vineyard, agricultural techniques should focus on improving the characteristics of the soil to improve the biodiversity of the soil microbiota.

Mobile device to induce heat-stress on grapevine berries

Studying heat stress response of grapevine berries in the field often relies on weather conditions during the growing season. We constructed a mobile heating device, able to induce controlled heat stress on grapes in vineyards. The heater consisted of six 150 W infrared lamps mounted in a profile frame. Heating power of the lamps could be controlled individually by a control unit consisting of a single board computer and six temperature sensors to reach a pre-set temperature. The heat energy applied to individual berries within a cluster decreases by the squared distance to the heat source, enabling the establishment of temperature profiles within individual clusters. These profiles can be measured by infrared thermography once a steady state has been reached. Radiant flux density received by a berry depending on the distance was calculated based on a view factor and measured lamp surface temperature and resulted to 665 Wm-2 at 7cm. Infrared thermography of the fruit surface was in good agreement with measurements conducted with a thermocouple inserted at epidermis level. In combination with infrared thermography, the presented device offers possibilities for a wide range of applications like phenotyping for heat tolerance in the field to proceed in the understanding of the complex response of plants to heat stress. Sunburn necrosis symptoms were artificially induced with the aid of the device for cv. Bacchus and cv. Sylvaner in the 2020 and 2021 growing season. Threshold temperatures for sunburn induction (LT5030min) were derived from temperature data of single berries and visual sunburn assessment, applying logistic regression. A comparison of threshold temperatures for the occurrence of sunburn necrosis confirmed the higher susceptibility of cv. Bacchus. The lower susceptibility of cv. Sylvaner did not seem to be related to its phenolic composition, rendering a thermoprotective role of berry phenolic compounds unlikely.

The modification of cultural practices in grapevine cv. Syrah, does it modify the characteristics of the musts?

The work shows the results of a year of experimentation (2020) in a Syrah variety vineyard in La Roda (Castilla-La Mancha, Spain). The trial approach was on a randomized block design with two factors: Irrigation (I) and Pruning (P).
Irrigation schedules were adjusted to apply amounts close to 1,500 m3/ha. With this provision, 2 different irrigation treatments were proposed: I1) Start of irrigation from pea-sized grape to post-harvest (providing at least 20 % of the total amount of irrigation water to be provided post-harvest); I2) Start of irrigation from pea-sized grape to harvest (usual irrigation practice in the study area). Pruning was proposed with two treatments, one at the end of January (P1), which is pruning on a conventional date; and P2) pruning carried out at the beginning of budding. In total, 4 repetitions were designed with 4 elementary plots, each one of them representing one of the proposed treatments (I1P1; I1P2; I2P1; I2P2). In total, 16 plots were worked on and each elementary plot consisted of 30 strains, distributed in 3 lines.
The productive response was evaluated with the yield results of the harvest harvested at 23 ºBrix. The qualitative response was measured in the musts through the indices of technological (acidity, pH and potassium) and phenolic maturity and aromatic compounds in free and glycosylated fractions. The treatments tested had, in general, an effect on the different variables analyzed.

Influence of a spontaneous cover crop on the vineyard and soil erosion under Mediterranean climate

Sixty five % of the agricultural area of the Basque Country located in the DO Ca Rioja corresponds to vineyards. More than 40% of it has an average slope greater than 10%, which makes it sensitive to erosive processes. Furthermore, it is foreseeable that extreme weather events (storms, hail, extreme heat and cold, etc.) will be favored due to climate change. Cover cropping can mitigate this risk, and therefore the objective of this work is to evaluate the impact that a vegetable cover has on the agronomic behavior of the vineyard, the quality of the grape and soil erosion. For this, a trial has been carried out with a Graciano variety vineyard with a slope between 10% -20% during the years 2020 and 2021. Conventional tillage management in the area has been compared (4-6 passes per year of tillage machinery) versus spontaneous vegetation cover management in the vineyard. This implies not tilling and allowing the grass of the land to colonize the range between the lines of vines, controlling their height through 1-3 mowing passes per year, always trying to affect the surface of the land as little as possible. The vegetative growth, yield and quality of the grape and wine was measured. Furthermore, erosion has been measured using Gerlasch boxes. The yield was lower in the second year of the trial in the cover crop treatment, but erosion was significantly reduced.