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…

1H-NMR-based Metabolomics to assess the impact of soil type on the chemical composition of Mediterranean red wines

The aim of this study was to evaluate the effects of different soil types on the chemical composition of Mediterranean red wines, through untargeted and targeted 1H-NMR metabolomics. One milliliter of raw wine was analyzed by means of a Bruker Avance II 400 spectrometer operating at 400.15 MHz. The spectra were recorded by applying the NOESYGPPS1D pulse sequency, to achieve water and ethanol signals suppression. No modification of the pH was performed to avoid any chemical alteration of the matrix. The generation of input variables for untargeted analysis was done via bucketing the spectra. The resulting dataset was preprocessed prior to perform unsupervised PCA, by means of MetaboAnalyst web-based tool suite. The identification of compounds for the targeted analysis was performed by comparison to pure compounds spectra by means of SMA plug-in of MNova 14.2.3 software. The dataset containing the concentrations (%) of identified compounds was subjected to one-way analysis of variance (ANOVA) to highlight significant differences among the wines. The untargeted analysis, carried out through the PCA, revealed a clear differentiation among the wines. The fragments of the spectra contributing mostly to the separation were attributed to flavonoids, aroma compounds and amino acids. The targeted analysis leaded to the identification of 68 compounds, whose concentrations were significant different among the wines. The results were related to soils physical-chemical analysis and showed that: 1) high concentrations of flavan-3-ols and flavonols are correlated with high clay content in soils; 2) high concentrations of anthocyanins, amino acids, and aroma compounds are correlated with neutral and moderately alkaline soil pH; 3) low concentrations of flavonoids and aroma compounds are correlated with high soil organic matter content and acidic pH. The 1H-NMR metabolomic analysis proved to be an excellent tool to discriminate between wines originating from grapes grown on different soil types and revealed that soils in the Mediterranean area exert a strong impact on the chemical composition of the wines.

Grape must quality and mesoclimatic variability in Fruška Gora wine-growing region, Serbia

The Fruška Gora mountain is a traditional wine-growing region in Serbia situated in the Pannonian Basin. Due to such a position, the vicinity of the Danube River and the presence of concave configuration, it is suitable for grape production. This paper provides analyses of spatial variations in meteorological parameters and grape juice quality within Fruška Gora wine region over three consecutive vintages (2018-2020). The examined period can be defined as warm with cool nights during September (AVG 18,9°C; GDD 1918°C; CI 12°CF) and with the presence of mesoclimatic variability. The East part of the study area was somewhat drier and hotter compared to other parts of the region. The analyses of grape must samples (190 in total) of five cultivars (Cabernet-Sauvignon, Merlot, Chardonnay, Sauvignon blanc and Grašac (Welschriesling)) commonly grown across the region (19 sites), were performed using Fourier Transform Infrared Technology (FTIR). Among all cultivars, Sauvignon blanc was harvested first in the East area (DOY=246±5, GDD at harvest=1552±74, 22.2±0.7 °Brix), while the latest harvest was recorded for Cabernet-Sauvignon in the West (DOY=283±5, GDD at harvest=1936±187, 23.4±1.0 °Brix ). Both the red and white cultivars had higher acidity and YAN in the grape must if the vines were grown in the North and East compared to South and West areas. According to PCA analysis, Grašac showed the lowest variation in grape must chemical composition. Thus, the results confirm that Grašac is the most stable cultivar in Fruška Gora. All monitored cultivars reached technological fruit ripeness by the end of the growing season. However, it was difficult to reach full ripeness of red cultivars, mostly beacuse of uncoupling of technolocical and phenolic ripeness. Thus, Cabernet-Sauvignon had higher variations in GDD sums at harvest compared to other cultivars, which probably increased variations in grape must quality.

Second pruning as a strategy to delay maturation in cv. ‘Touriga nacional’ in the Portuguese Douro region

The advance in maturation of wine grapes is an important climate change risk related effect that could affect warm regions like Portuguese Douro Wine Region. Indeed, the climate analysis over the past years registered a decrease in the precipitation, significant higher average temperatures, and a more frequent occurrence of extreme weather events, including heat waves. In these conditions the length from anthesis until maturation is shortened and the uncoupling of technical and phenolic maturity results in berries with higher sugar concentration (and lower acidity), but lower anthocyanins, tannins, and total phenolic concentration, which produce unbalanced wines.
In this work, an innovative strategy of crop forcing, based on forcing vine regrowth after a second pruning of green shoots, was tested, aimed at delaying ripening until the temperature becomes lower and, therefore, preventing acidity loss and increasing anthocyanin-to-sugar ratio. The experiments were conducted in 2019 and 2020 in a commercial vineyard of ‘Touriga Nacional’ located in the Douro Region. Crop forcing was conducted 15 (CF1) to 30 (CF2) days after fruit set. Vines pruned with conventional methods were used as control (CF0). Results confirmed that fruit ripening was shifted from the hot season (August/September), until a cooler period (October through early-November). At harvest, grapevine berries from CF1 and CF2 presented lower pH and higher acidity, than control, with no significant differences in colour intensity and phenolic levels composition. Sugar content was lower in CF2-treated vines in both seasons. However, in CF-treated vines the number and size of clusters were significantly lower (up to 88% reduction) than in control plants. A metabolomics analysis of mature berries from CF-treated vines and control is underway. Crop forcing was indeed effective in producing a more balance berry composition but severely reduced grapevine yield,

Mesoclimate impact on Tannat in the Atlantic terroir of Uruguay

The study of climate is relevant as an element conditioning the typicity of a product, its quality and sustainability over the years. The grapevine development and growth and the final grape and wine composition are closely related to temperature, while climate components vary at mesoscale according to topography and/or proximity to large bodies of water. The objective of this work is to assess the mesoclimate of the Atlantic region of Uruguay and to determine the effect of topography and the ocean on temperature and consequently on Tannat grapevine behavior.

Soil quality in Beaujolais vineyard. Importance of pedology and cultural practices

A pedological study was carried out from 2009 to 2017 in Beaujolais vineyard, to improve physical and chemical knowledge of soils. It was completed in 2016 and 2017 by the current study, dealing with microbial aspects, in order to build a reference frame for improved advice in soil management. Microbial biomass was measured on representative plots of the six most common soil types identified in Beaujolais and, for each soil type, on plots with different levels of the main impacting parameters: total organic carbon, pH, cation exchange capacity, extractable copper. A total of 59 soil samples were collected. Confirming the results of various trials carried out in Beaujolais over the past 20 years, the results of the present study showed that the soils were still alive, but exhibited a large variability of biological parameters, which appeared dependant on both pedological and anthropic factors. Therefore, a good interpretation of biological parameters and advice for vine growers must rely on a pedologically-based referential with differentiated main driving factors. For example, the control of pH is of primary importance in granitic soils and in no way organic matter addition can improve soil quality if pH is too low. Conversely, in calcareous soils, biological parameters are more directly affected by direct or indirect (cover crops for example) inputs of organic matter. The use of biological parameters, such as microbial biomass, is of great potential value to improve advice on agro-viticultural practices (soil management, fertilization, liming, etc.), basis of a sustainable wine production on fragile soils.