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…

De novo Vitis champinii whole genome assembly allows rootstock-specific identification of potential candidate genes for drought and salt tolerance

Vitis champinii cultivars Ramsey and Dog-ridge are main choices for rootstocks to adapt viticulture in semi-arid and arid regions thanks to their distinctive tolerance to drought and salinity. However, genetic studies on non-vinifera rootstocks have heavily relied on the grapevine (Vitis vinifera) reference genome, which difficulted the assessment of the genetic variation between rootstock species and grapevines. In the present study, this limitation is addressed by introducing a novo phased genome assembly and annotation of Vitis champinii. This new Vitis champinii genome was employed as reference for mapping RNA-seq reads from the same species under drought and salt stresses, and for comparison the same reads were also mapped to the Vitis vinifera PN40024.V4 reference genome. A significant increase in alignment rate was gained when mapping Vitis champinii RNA-seq reads to its own genome, compared to the Vitis vinifera PN40024.V4 reference genome, thus revealing the expression levels of genes specific to Vitis champinii. Moreover, differences in coding sequences were observed in ortholog genes between Vitis champinii and Vitis vinifera, which therefore challenges previous differential expression analyses performed between contrasting Vitis genotypes on the same gene from the Vitis vinifera genome. Genes with possible implications in drought and salt tolerance have been identified across the genome of Vitis champinii, and the same genomic data can potentially guide the discovery of candidate genes specific from Vitis champinii for other traits of interest, therefore becoming a valuable resource for rootstock breeding designs, specially towards increased drought and salinity due to climate change.

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.

Frost risk projections in a changing climate are highly sensitive in time and space to frost modelling approaches

Late spring frost is a major challenge for various winegrowing regions across the world, its occurrence often leading to important yield losses and/or plant failure. Despite a significant increase in minimum temperatures worldwide, the spatial and temporal evolution of spring frost risk under a warmer climate remains largely uncertain. Recent projections of spring frost risk for viticulture in Europe throughout the 21st century show that its evolution strongly depends on the model approach used to simulate budburst. Furthermore, the frost damage modelling methods used in these projections are usually not assessed through comparison to field observations and/or frost damage reports.
The present study aims at comparing frost risk projections simulated using six spring frost models based on two approaches: a) models considering a fixed damage threshold after the predicted budburst date (e.g BRIN, Smoothed-Utah, Growing Degree Days, Fenovitis) and b) models considering a dynamic frost sensitivity threshold based on the predicted grapevine winter/spring dehardening process (e.g. Ferguson model). The capability of each model to simulate an actual frost event for the Vitis vinifera cv. Chadonnay B was previously assessed by comparing simulated cold thermal stress to reports of events with frost damage in Chablis, the northernmost winegrowing region of Burgundy. Models exhibited scores of κ > 0.65 when reproducing the frost/non-frost damage years and an accuracy ranging from 0.82 to 0.90.
Spring frost risk projections throughout the 21st century were performed for all winegrowing subregions of Bourgogne-Franche-Comté under two CMIP5 concentration pathways (4.5 and 8.5) using statistically downscaled 8×8 km daily air temperature and humidity of 13 climate models. Contrasting results with region-specific spring frost risk trends were observed. Three out of five models show a decrease in the frequency of frost years across the whole study area while the other two show an increase that is more or less pronounced depending on winegrowing subregion. Our findings indicate that the lack of accuracy in grapevine budburst and dehardening models makes climate projections of spring frost risk highly uncertain for grapevine cultivation regions.

Modeling the suitability of Pinot Noir in Oregon’s Willamette Valley in a changing climate

Air temperature is the key driver of grapevine phenology and a significant environmental factor impacting yield and quality for a winegrape growing region. In this study the optimal downscaled CMIP5 ensemble for computing thegrowing season average temperature (GST) viticulture climate classification index was determined to spatially compute on a decadal basis predictions of the GST climate index and the grapevine sugar ripeness (GSR) model for Pinot Noir throughout the Willamette Valley (WV) American Viticultural Area (AVA). Forecasts for average temperature and a 220 g/L target sugar concentration level were computed using daily Localized Constructed Analogs (LOCA) downscaled CMIP5 historic and Representative Concentration Pathways (RCP) future climate projections of minimum and maximum daily temperature. We explore spatiotemporal trends of the GST climate classification index and Pinot Noir specific applications of the GSR phenology model for the WV AVA. Spatiotemporal computations of the GST climate index and Pinot Noir specific applications of the GSR model enable the opportunity to explore relationships between their computed values with one intent being to provide updated GST ranges that better align with current temperature-based modeling understanding of Pinot Noir grapevine phenology and the viticultural application of LOCA CMIP5 climate projections for the WV AVA. The Pinot Noir specific applications of the GSR model or the GST index with updated bounds indicate that the percent of the WV AVA area suitable for Pinot Noir production is currently at or near its peak value in the upper 80s to lower 90s of this century.

The plantation frame as a measure of adaptation to climate change

The mechanization of vineyard work originally led to a reduction in planting densities due to the lack of machinery adapted to the vineyard. The current availability of specific machinery makes it possible to establish higher planting densities. In this work, three planting densities (1.40×0.80 m, 1.80×1 m and 2.20×1.20 m, corresponding to 8928, 5555 and 3787 plants/ha respectively) were studied with four varieties autochthonous of Galicia (northwestern Spain): Albariño and Treixadura (white), Sousón and Mencía (red). The vines were trained in a vertical shoot positioning system using a single Royat cordon, and pruned to spurs with two buds each. Agronomic data (yield, pruning wood weight, Ravaz index) and oenological data in must were collected. The higher planting density (1.40×0.80 m) had no significant effect on grape yield per vine in white varieties, although production per hectare was much higher due to the greater number of plants. In red varieties, this planting density resulted in a significantly lower production per vine, compensated by the greater number of plants. In addition, it significantly reduced the Brix degree in the must of the Albariño, Treixadura and Sousón varieties, and increased the total acidity in the latter two and Mencía. It also caused an increase in extractable and total anthocyanins and IPT in red grapes. The effects of high planting density on grapes are of great interest for the adaptation of varieties in the context of climate change. In the future, it could be advisable to modify the limits imposed by the appellations of origin on the planting density of these varieties in order to obtain more balanced wines.