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…

Under-vine management effects on grapevine production, soil properties and plant communities in South Australia

Under-vine (UV) management has traditionally consisted of synthetic herbicide use to limit competition between weeds and grapevines. With growing global interest towards non-synthetic chemical use, this study aimed to capture the effects of alternative UV management at two commercial Shiraz vineyards in South Australia, where the sole management variables were UV management since 2016. In adjacent treatment blocks, cultivation (CU) was compared to spontaneous vegetation (SV) in McLaren Vale (MV), and herbicide was compared to SV in Eden Valley (EV). Soil water infiltration rates were slower and grapevine stem water potential was lower in CU compared to SV in MV, with the latter having a plant community dominated by soursob (Oxalis pes-caprae) during winter; while in EV, there was little separation between the treatments. Yields were affected at both sites, with SV being higher in MV and HE being higher in EV. In MV, the only effect on grape must was a lower 13C:12C isotope ratio in CU, indicating greater grapevine water stress. In the grape must at EV, SV had higher total soluble solids, total phenolics, anthocyanins, and yeast available nitrogen; and lower pH and titratable acidity. Pruning weights were not affected by the treatments in MV, while they were higher in HE at EV. Assessments revealed that the differing soil types at the two sites were likely the main determinants of the opposing production outcomes associated with UV management. In the silty loam soil of MV, the higher yields in SV were likely due to more plant-available water, as a potential result of the continuous soil bio-pores formed by winter UV vegetation. Conversely, in the loamy sand soils of EV with a lower cation exchange capacity, the lower yields and pruning weights in SV suggest the UV vegetation competed significantly with the grapevines for available water and nutrients.

Rootstock regulation of scion phenotypes: the relationship between rootstock parentage and petiole mineral concentration

Grapevine is grown as a graft since the end of the 19th century. Rootstocks not only provide tolerance to Phylloxera but also ensure the supply of water and mineral nutrients to the scion. Rootstocks are an important mean of adaptation to environmental conditions, because the scion controls the typical features of the grapes and wine. However, among the large diversity of rootstocks worldwide, few of them are commercially used in the vineyard. The aim of this study was to investigate the extent to which rootstocks modify the mineral composition of the petioles of the scion. Vitis vinifera cvs. Cabernet-Sauvignon, Pinot noir, Syrah and Ugni blanc were grafted onto 55 different rootstock genotypes and planted in a vineyard as three replicates of 5 vines. Petioles were collected in the cluster zone with 6 replicates per combination. Petiolar concentrations of 13 mineral elements (N, P, K, S, Mg, Ca, Na, B, Zn, Mn, Fe, Cu, Al) at veraison were determined. Scion, rootstock and the interaction explained the same proportion of the phenotypic variance for most mineral elements. Rootstock genotype showed a significant influence on the petiole mineral element composition. Rootstock effect explained from 7 % for Cu to 25 % for S of the variance. The difference of rootstock conferred mineral status is discussed in relation to vigor and fertility. Rootstocks were also genotyped with 23 microsatellite markers. Data were analysed according to genetic groups in order to determine whether the petiole mineral composition could be related to the genetic parentage of the rootstock. Thanks to a highly powerful design, it is the first time that such a large panel of rootstocks grafted with 4 scions has been studied. These results give the opportunity to better characterize the rootstocks and to enlarge the diversity used in the vineyard.

Influence of weather and climatic conditions on the viticultural production in Croatia

The research includes an analysis of the impact of weather conditions on phenological development of the vine and grape quality, through monitoring of four experimental cultivars (Chardonnay, Graševina, Merlot and Plavac mali) over two production years. In each experimental vineyard, which were evenly distributed throughout the regions of Slavonia and The Croatian Danube, Croatian Uplands,

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.

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.