Macrowine 2021
IVES 9 IVES Conference Series 9 Alternative fate of varietal thiols in wine: identification, formation, and enantiomeric distribution of novel 1,3-oxathianes

Alternative fate of varietal thiols in wine: identification, formation, and enantiomeric distribution of novel 1,3-oxathianes

Abstract

AIM: This study aimed to explore an alternative fate of varietal thiols by identifying and characterising cis-2-methyl-4-propyl-1,3-oxathiane (cis-2-MPO) and cis-2,4,4,6-tetramethyl-1,3-oxathiane (cis-TTMO) in wine. Elucidating these new pathways could aid in explaining the loss of varietal thiols and would further our understanding of the stereochemical relationships between oxathianes and varietal thiols.

METHODS: GC-MS was used to identify cis-2-MPO,1 and a stable isotope dilution assay (SIDA) was developed to quantify its enantiomers after separation with a chiral β-cyclodextrin GC column.2 Varietal thiols and their enantiomers were analysed by SIDA with HPLC-MS/MS to determine their relationship with cis-2-MPO. Production of cis-2-MPO and its correlation with 3-SH, 3-SHA, and acetaldehyde was studied by profiling the evolution of these volatiles during alcoholic fermentation (AF) of Sauvignon blanc (SB) juice fermented with J7, VIN13, and their co-inoculum.3

RESULTS: cis-2-MPO, derived from 3-SH and acetaldehyde, was identified and then measured at up to 460 ng/L (equivalent to 385 ng/L of 3-SH) in a set of wines. Analysis of (2R,4S)-2-MPO and (2S,4R)-2-MPO, arising from thiol enantiomers (3S)-3-SH and (3R)-3-SH, showed respective concentrations of up to 250 and 303 ng/L. The enantiomeric ratio of (2R,4S)-/(2S,4R)-2-MPO was 43:57 whereas that of (3S)-/(3R)-3-SH in the same wines was 51:49.2 Strong correlations were revealed for both 3-SH and cis-2-MPO and their related enantiomeric pairs.The AF study showed cis-2-MPO was produced from an early stage of AF and reached a peak of 847 ng/L (VIN13 ferment) before gradually declining to 50-65 ng/L. Its evolution profile was identical to that of acetaldehyde and 3-SHA, with moderate to strong correlations found for the analytes.Additionally, cis-TTMO, derived from 4-MSPOH and acetaldehyde, was identified in wine as a single enantiomer at concentrations of up to 28 ng/L (equivalent to 23 ng/L of 4-MSPOH). An aroma detection threshold of 14.9 µg/L was determined for cis-TTMO, and this new volatile was described as ‘citrus’, ‘green’, ‘sweet/caramel’, and ‘mango’, shifting toward ‘onion/sweaty’ and ‘sulfurous’ at higher concentrations.2

CONCLUSIONS

The knowledge gained helps rationalise the fate of varietal thiols via the production of oxathianes in wine, and reveals the stereochemical links between these related compounds. A chemical formation pathway to oxathianes was verified and may also apply to other thiols bearing the 1,3-sulfanylalkanol substitution through the reaction with acetaldehyde.

DOI:

Publication date: September 13, 2021

Issue: Macrowine 2021

Type: Article

Authors

Xingchen Wang

Department of Wine Science and Waite Research Institute, The University of Adelaide (UA), PMB 1, Glen Osmond, SA 5064, Australia,Liang, CHEN, Université de Bordeaux, Unité de Recherche Œnologie, EA 4577, USC 1366 INRAE, Institut des Sciences de la Vigne et du Vin, 33882, Villenave d’Ornon cedex, France Dimitra L., CAPONE, Department of Wine Science and Waite Research Institute, Australian Research Council Training Centre for Innovative Wine Production, UA, PMB 1, Glen Osmond, SA 5064, Australia Aurélie, ROLAND, SPO, Univ Montpellier, INRAE, Institut Agro, Montpellier, France David W., JEFFERY, Department of Wine Science and Waite Research Institute, Australian Research Council Training Centre for Innovative Wine Production, UA, PMB 1, Glen Osmond, SA 5064, Australia

Contact the author

Keywords

3-sulfanylhexan-1-ol, 4-methyl-4-sulfanylpentan-2-ol, acetaldehyde, chiral stationary phase, odour detection threshold, sauvignon blanc, stable isotope dilution assay, gas chromatography–mass spectrometry

Citation

Related articles…

Leaf vine content in nutrients and trace elements in La Mancha (Spain) soils: influence of the rootstock

The use of rootstock of American origin has been the classic method of fighting against Phylloxera for more than 100 years. For this reason, it is interesting to establish if different rootstock modifies nutrient composition as well as trace elements content that could be important for determining the traceability of the vine products. A survey of four classic rootstocks (110-Richter, SO4, FERCAL and 1103-Paulsen) and four new ones (M1, M2, M3 and M4) provided by Agromillora Iberia. S.L.U., all of them grafted with the Tempranillo variety, has been carried out during 2019. The eight rootstocks were planted in pots of 500 cc, on three soils with very different characteristics from Castilla-La Mancha (Spain). In the month of July, the leaves were collected and dried in a forced air oven for seven days at 40ºC. Then, the samples were prepared for the analysis determination, carried out by X-Ray fluorescence spectrometry. The results obtained showed that in the case of content in mineral elements in leaf, separated by soil type, we can report the importance of few elements such as Si, Fe, Pb and, especially, Sr. The rootstock does not influence the composition of the vine leaf for the studied elements that are the most important in determining the geochemical footprint of the soil. The influence of the soil can be discriminated according to some elements such as Fe, Pb, Si and, especially, Sr.

Impact on leaf morphology of Vitis vinifera L. cvs Riesling and Cabernet Sauvignon under Free Air Carbon dioxide Enrichment (FACE)

Atmospheric carbon dioxide (CO2) concentration has continuously increased since pre-industrial times from 280 ppm in 1750, and is predicted to exceed 700 ppm by the end of 21st century. For most of C3 plant species elevated CO2 (eCO2) improve photosynthetic apparatus results in an increased plant biomass production. To investigate the effects of eCO2 on morphological leaf characteristics the two Vitis vinifera L. cultivars, Riesling and Cabernet Sauvignon, grown in the Geisenheim VineyardFACE (Free Air Carbon dioxide Enrichment) system were used. The FACE site is located at Geisenheim University (49° 59′ N, 7° 57′ E, 94 m above sea level), Germany and was implemented in 2014 comparing future atmospheric CO2-concentrations (eCO2, predicted for the mid-21st century) with current ambient CO2-conditions (aCO2). Experiments were conducted under rain-fed conditions for two consecutive years (2015 and 2016). Six leaves per repetition of the CO2 treatment were sampled in the field and immediately fixed in a FAA solution (ethanol, H2O, formaldehyde and glacial acetic acid). After 24 h leaf samples were transferred and stored in an ethanol solution. Subsequently, leaf tissue was dehydrated using ethanol series and embedded in paraffin. By using a rotary microtomesections of 5 µm were prepared and fixed on microscopic slides. Subsequent the samples were stained using consecutive staining and washing solutions. Afterwards pictures of the leaf cross-sections were taken using a light microscope and consecutive measurements were conducted with an open source image software. Differences found in leaf cross-sections of the two CO2 treatments were detected for the palisade parenchyma. Leaf thickness, upper and lower epidermis and spongy parenchyma remained less affected under eCO2 conditions. The observed results within grapevine leaf tissues can provide first insights to seasonal adaptation strategies of grapevines under future elevated CO2 concentrations.

A better understanding of the climate effect on anthocyanin accumulation in grapes using a machine learning approach

The current climate changes are directly threatening the balance of the vineyard at harvest time. The maturation period of the grapes is shifted to the middle of the summer, at a time when radiation and air temperature are at their maximum. In this context, the implementation of corrective practices becomes problematic. Unfortunately, our knowledge of the climate effect on the quality of different grape varieties remains very incomplete to guide these choices. During the Innovine project, original experiments were carried out on Syrah to study the combined effects of normal or high air temperature and varying degrees of exposure of the berries to the sun. Berries subjected to these different conditions were sampled and analyzed throughout the maturation period. Several quality characteristics were determined, including anthocyanin content. The objective of the experiments was to investigate which climatic determinants were most important for anthocyanin accumulation in the berries. Temperature and irradiance data, observed over time with a very thin discretization step, are called functional data in statistics. We developed the procedure SpiceFP (Sparse and Structured Procedure to Identify Combined Effects of Functional Predictors) to explain the variations of a scalar response variable (a grape berry quality variable for example) by two or three functional predictors (as temperature and irradiance) in a context of joint influence of these predictors. Particular attention was paid to the interpretability of the results. Analysis of the data using SpiceFP identified a negative impact of morning combinations of low irradiance (lower than about 100 μmol m−2 s−1 or 45 μmol m−2 s−1 depending on the advanced-delayed state of the berries) and high temperature (higher than 25oC). A slight difference associated with overnight temperature occurred between these effects identified in the morning.

Effect of vigour and number of clusters on eonological parameters and metabolic profile of Cabernet Sauvignon red wines

Vegetative growth and yield are reported to affect grape and wine quality. They can be controlled through different techniques linked to vine management. The objective of this research was to determine the effect of vine vigour and number of clusters per vine on physicochemical composition and phenolic profile of red wines. The experiment was carried out during two vegetative cycles, with cv. Cabernet Sauvignon grafted onto Paulsen 1103. Three vine vigour were defined, according to shoot weight at previous harvests, being low, medium and high. Five treatments of number of clusters were used for each vigour, with 15, 22, 29, 36, and 45 clusters per vine. Grapes from all treatments were harvested in the same day from Brix and total acidity criteria. Thirty days after bottling, classical analyzes and phenolic compounds were performed. As results, different responses were obtained from each vintage. In 2020, a dry season from veraison to harvest, grapes and wines obtained from low vigour treatment and 45 clusters per vine was the highest in sugar and alcohol content respectively, while grapes and wines from high vigour and 15 clusters presented the lowest sugar and alcohol content. Total anthocyanins were higher in treatment with low vigour and 15 clusters, while the lowest amounts were found in low vigour with 45 clusters, as well as medium and high vigour with 36 clusters per vine. Total tannins were higher in high vigour with 22 clusters and medium vigour with 29 clusters, while were lower in low vigour with 36 clusters. In 2021, a wet season at harvest, responses were different, and great variations were observed between treatments. As conclusions, yield and vine vigour had strong influence on grape and wine quality, promoting different enological potentials on which can be indicated/used for aging strategies of red and even rosé wines.

Effect of partial net shading on the temperature and radiation in the grapevine canopy, consequences on the grape quality of cv. Gros Manseng in PDO Pacherenc-du-vic-Bilh

As elsewhere, southwestern France vineyards face more recurrent summer heat waves these last years. Among the possibilities of adaptation to this climate changing parameter, the use of net shading is a technique that allow for limiting canopy exposure to radiations. In this trial, we tested net shading installed on one face of the canopy, on a north-south row-oriented plot of cv. Gros Manseng trained on VSP system in the PDO Pacherenc-du-Vic-Bilh. The purpose was to characterize the effects on the ambient canopy temperatures and radiations during the season and to observe the consequences on the composition of grapes and wines. Two sorts of net were used with two levels of obstruction (50% and 75%) of the photosynthesis active radiation (PAR). They have been installed on the west side of the canopy and compared to a netless control. Temperature and PAR sensors registered hourly data during the season. On specific summer day (hot and sunny) manual measurements took also place on bunches (temperature) and in different spots of the canopy (PAR). The results showed that, on clear days, the radiation is lowered by the shade nets respecting the supplier criteria. The effects on the ambient canopy temperature were inconstant on this plot when we observed the data from the global period of shading between fruit set and harvest. However, during hot days (>30°C), the temperature in the canopy was reduced during afternoon and the temperature of the bunch surface was reduced as well comparing to the control. A decrease of the maturity parameters of the berries, sugar and acidity, was also observed. Concerning the wine aromatic potential, no differences clearly appeared.