OENO IVAS 2019 banner
IVES 9 IVES Conference Series 9 OENO IVAS 9 OENO IVAS 2019 9 Chemical and Biochemical reactions, including grape and wines microorganisms impact 9 When organic chemistry contributes to the understanding of metabolism mechanisms

When organic chemistry contributes to the understanding of metabolism mechanisms

Abstract

Many compounds of interest in wine are difficult to analyze since they are present in very small quantities or they are unstable. The need for reliable data led scientists to develop complex method in order to overcome the analytical difficulties and provide accurate quantitative data for grape or wine characterization.

For 10 years, we developed several chemical strategies to obtain analytical standards either as labelled analogues or as diastereomers to develop SIDA and DIDA analytical methods, respectively. These quantification methods afforded accurate and reliable results by suppressing analytical bias due to sample preparation. Several examples will be presented from deuterated analogues: varietal thiols [1], thiol precursors [2], Ochratoxin A [3], and diastereoisomers: Ochratoxin A [4] and hydroxycinnamic acids [5].

Another interesting application based on synthetic compounds lies in their possible exploitation as tracers. Indeed, the scale-up and optimization of chemical syntheses from μg to mg levels provided us with substantial amounts of molecules that could be used in metabolism studies. For example, we recently used labelled thiol precursors as tracers in Sauvignon Blanc musts for metabolism studies. Degradation of such tracers was monitored to highlight several key interconversion mechanisms and bring new elements in varietal thiol biogenesis knowledge [6]. In these applications, the choice of the labelling position (for Ochratoxin A for instance) or multilabelling possibilies (for thiol precursors) offer future opportunity to investigate detoxification process or to obtain insight in the metabolism of aroma precursors, respectively.

References

1. a) A. Roland, R. Schneider, A. Razungles and F. Cavelier, Varietal thiols in wine: Discovery, Synthesis and Applications, Chem. Rev. 2011, 111, 7355. b) R. Schneider, Y. Kotseridis, J.-L. Ray, C. Augier and R.Baumes, Quantitative determination of sulfur-containing wine odorants at sub parts per billion levels.
2. Development and application of a stable isotope dilution assay, J. Agri. Food Chem., 2003, 51, 3243. 2. H.Bonnaffoux, A.Roland, E.Rémond, S.Delpech, R.Schneider, F.Cavelier, First identification and quantification of S-3- (hexan-1-ol)-γ-glutamyl-cysteine in grape must as a potential thiol precursor, using UPLC-MS/MS analysis and stable iso-tope dilution assay, Food Chem., 2017, 237, 877.
3. A.Bouisseau, A.Roland, R.Schneider and F.Cavelier, First Synthesis of a Stable Isotope of Ochratoxin A Metabolite for a Reliable Detoxification Monitoring, Org. Lett., 2013, 15, 3888.
4. A.Roland, P.Bros, A.Bouisseau, F.Cavelier and R.Schneider, Analysis of Ochratoxin A in musts and wines by LCMS/MS: Comparison of Stable Isotope Dilution Assay and Diastereomeric Dilution Assay Methods, Anal. Chim. Acta, 2014, 818, 39.
5. F. Cavelier, A. Roland, A. Bouisseau, J. Martinez, R. Schneider. Method for the esterification of polar molecules, WO 2015 011230
6. H. Bonnaffoux, S. Delpech, E. Rémond, R. Schneider, A. Roland, F. Cavelier, Revisiting the evaluation strategy of varietal thiol biogenesis, Food Chem., 2018, 268, 126.

DOI:

Publication date: June 19, 2020

Issue: OENO IVAS 2019

Type: Article

Authors

Florine Cavelier Hugo Bonnaffoux, Anaïs Bouisseau, Stéphane Delpech, Aurélie Roland, Rémi Schneider

Université de Montpellier (France)

Contact the author

Keywords

organic chemistry, analytical chemistry, internal standards, aroma

Tags

IVES Conference Series | OENO IVAS 2019

Citation

Related articles…

Rapid damage assessment and grapevine recovery after fire

There is increasing scientific consensus that climate changeis the underlying cause of the prolonged dry and hot conditions that have increased the risk of extreme fire weather in many countries around the world. In December 2019, a bushfire event occurred in the Adelaide Hills, South Australia where 25,000 hectares were burnt and in vineyards and surrounding areas various degrees of scorching and infrastructure damage occurred. The ability to coordinate and plan recovery after a fire event relies on robust and timely data. The current practice for measuring the scale and distribution of fire damage is to walk or drive the vineyard and score individual vines based on visual observation. The process is time consuming, subjective, or semi-quantitative at best. After the December 2019 fires, it took many months to access properties and estimate the area of vineyard damaged. This study compares the rapid assessment and mapping of fire damage using high-resolution satellite imagery with more traditional ground based measures. Satellite imagery tracking vineyard recovery in the season following the bushfire is being correlated to field assessments of vineyard productivity such as canopy health and development, fertility and carbohydrate storage. Canopy health in the seasons following the fires correlated to the severity of the initial fire damage. Severely damaged vines had reduced canopy growth, were infertile or had very low fertility as well as lower carbohydrate levels in buds and canes during dormancy, which reduced productivity in the seasons following the bushfire event. In contrast, vines that received minor damage were able to recover within 1-2 years. Tools that rapidly and affordably capture the extent and severity of damage over large vineyard area will allow producers, government and industry bodies to manage decisions in relation to fire recovery planning, coordination and delivery, improving the efficiency and effectiveness of their response.

Measurement of redox potential as a new analytical winegrowing tool

Excell laboratory has initiated the development of an analytical method based on electrochemistry to evaluate the ability of wines to undergo or resist to oxidative phenomena. Electrochemistry is a powerful tool to probe reactions involving electron transfers and offers possibility of real-time measurements. In that context, the laboratory has implemented electrochemical analysis to assess oxidation state of different wine matrices but also in order to evaluate oxidative or reduced character of leaf and soil. Initially, our laboratory focused on dosage of compounds involved in responses of plant stresses and we were also interested in microbiological activity of soils. These analyses were compared with the measurement of redox potential (Eh) and pH which are two fundamental variables involved in the modulation of plant metabolism. Indeed, the variation of redox states of the plant reflects its biological activity but also its capacity to absorb nutriments. The Eh-pH conditions mainly determine metabolic processes involved in soil and leaf and our goal is to determine if this combined analytical approach will be sufficiently precise to detect biological evolutions (plant health, parasitic attack…).

Water deficit differentially impacts the performances and the accumulation of grape metabolites of new varieties tolerant to fungi

The use of resistant varieties is a long-term but promising solution to reduce chemical input in viticulture. Several important breeding programs in Europe and abroad are now releasing a range of new hybrids performing well regarding fungi susceptibility and producing good quality wines. Unfortunately, insufficient attention is paid by the breeders to the adaptation of these varieties to climatic changes, notably to the increased climatic demand and water deficit (WD). Thus, prior to the adoption of such varieties by the wine industry in Mediterranean regions, there is a need to consider their suitability to WD. This study aimed to characterize the different drought-strategies adopted by 6 new resistant varieties selected by INRAE in comparison to Syrah. To allow the assessment of long-term impacts of WD, field-grown vines were exposed to contrasted WD from 2018 to 2021 under a semi-arid Mediterranean climate. A gradient of WD was applied in the field and controlled through plant measurements at the single plant level. Grape development was non-destructively monitored to determine the arrest of berry phloem unloading. The impacts of WD on berry composition, including water, primary metabolites (sugars, organic acids), secondary metabolites (anthocyanins, thiols precursors) and main cations contents, were assessed at this specific stage. Results showed different varietal responses during the year and inter-annual acclimation in terms of plant water use efficiency, biomass accumulation, as well as yield components and berry composition. WD differentially reduced the accumulation of primary metabolites at plant and berry levels, but it little changed their concentrations in the fruits at the ripe stage. Moreover, WD differentially impacted the accumulation of secondary metabolites and major cations between the varieties. In the talk, we’ll present the main results regarding the WD impacts on fruit metabolites and enlarge the reflection about the practical assessment of the grapevine acclimation to WD.

Late season canopy management practices to reduce sugar loading and improve color profile of Cabernet-Sauvignon grapes and wines in the high irradiance and hot conditions of California Central Valley

Global warming is accelerating grape ripening, leading to unbalanced wines from fruit with high sugar content but poor aroma and colour development. Reducing the size of the photosynthetic apparatus after veraison has been shown to delay technological ripeness in cool climates, but methods have not been tested in areas with high irradiance and temperature where fruit exposure could have disastrous effects on berry composition. In this Cabernet-Sauvignon trial, we compared the application of an antitranspirant (pinolene), to severe canopy topping and above bunch zone leaf removal, all performed at mid-ripening, with an untouched control. We monitored the vines weekly by measuring stem water potential, gas exchange, fruit zone light exposure. We sampled berries to measure berry weight, total soluble solids, pH, titratable acidity, and the anthocyanin profile. At harvest, we assessed yield components, measured carbon isotope discrimination, rated sunburn on clusters, and produced experimental wines. We submitted harvest samples to metabolomic profiling through PFP-Q Exactive MS/MS and wines to sensory analysis. Application of the antitranspirant significantly reduced stomatal conductance and assimilation rate but did not affect the stem water potential. Inversely, leaf removal and topping increased water potential but did not affect leaf gas exchange. The late topping was the only treatment able to decrease sugar content (up to 2Bx), increase titratable acidity and pH, and improve anthocyanin content because of lower degradation of di-hydroxylated forms. Late leaf removal above the bunch zone increased lightning conditions in the canopy and produced the most significant damage on fruits. Yield components were not affected. This work suggests that late-season canopy management can effectively control ripening speeds and improve grapes and wines. Still, the effect on grape exposure in a critical time must be well balanced to avoid problems with the appropriate technique.

Better understand the soil wet bulb formation with subsurface or aerial drip irrigation in viticulture

The gradual change in rainfall patterns experienced in the south of France vineyards, especially around the Mediterranean sea, means that the vines are increasingly subject to summer drought. The winegrowers developped the use of irrigation techniques to ensure the maintenance of competitive yields in the production of wines under Protected Geographical Indication label. In practice, drip irrigation pipes can be installed above the ground or buried into the soil as well as at different distances from the vine row. The objective of this study was to examine the profiles of the wet bulbs of the soil obtained from two drip irrigation systems : aerial drip located under the vine row and subsurface drip placed in the middle of the inter-row. This experiment took place over two consecutive seasons (2020-2021) on a 3.4 ha Viognier plot in the Mediterranean region (PGI Oc, France) on sandy clay soil. The annual rainfalls were less than 400 mm. Soil water content probes were installed at different depths (20 – 40 – 60 – 80 cm) and at different lateralities from the vine row (30 – 60 – 90 – 120 cm) to control the formation of the soil wet bulb during irrigation. The mapping and the analysis of the data allowed a better understanding and differentiation of the water percolation when irrigating with subsurface or aerial drip. For the same amount of water and without differences of vine water status, it is shown that in a subsurface drip irrigation situation, the size of the wet bulb formed is larger than in aerial drip irrigation system.