IVAS 2022 banner
IVES 9 IVES Conference Series 9 IVAS 9 IVAS 2022 9 Unraveling the mystery of 3SH: Quantifying glut-3SH-al and its bisulfite adduct in a range of white grape juice and wine samples

Unraveling the mystery of 3SH: Quantifying glut-3SH-al and its bisulfite adduct in a range of white grape juice and wine samples

Abstract

3-Sulfanylhexan-1-ol (3SH) is a key impact odorant of white wines such as Sauvignon Blanc. In particular, the varietal characters of Sauvignon Blanc, especially from Marlborough NZ, are strongly influenced by the concentrations of 3SH. Although only trace levels of 3SH are needed to impart perceptible aroma characters of passionfruit and grapefruit, the biogenesis of this compound during fermentation is not yet well understood. The polyfunctional varietal thiols are produced during fermentation by metabolism of non-volatile precursors such as glutathione and cysteine conjugates of 3SH, however the routes by which these precursors are metabolised are complex, and not fully elucidated. 1One precursor of particular interest is the glutathione conjugate to the aldehyde form of 3SH, 3S-glutathionylhexanal (glut-3SH-al). Retention of the aldehyde functional group drastically changes the reactivity of the precursor in wine-like systems. Recent work by this group has shown that this compound can exist as tautomers in solution, suggesting possible new reaction pathways for the metabolism of glut 3SH-al. 2 Additionally, the bisulfite adduct of glut-3SH-al (glut-3SH-SO3) has been identified in wine samples, as SO2 is widely present in wine media. 3,4 The interconversion of glut-3SH-al and glut-3SH-SO3 is of great interest as it is an equilibrium and will be influenced by the concentrations of both glut-3SH-al and free SO2 in the sample. As such, it is thought that glut-3SH-SO3 may exist in finished wines as a potential reservoir for the release of 3SH which could extend the life of the fruity characters which are so desirable in young white wines. 4 We have developed a method for the extraction and quantification of glut-3SH-al and glut-3SH-SO3, using previously synthesised deuterated analogues of these compounds to ensure reliable quantification.5 The compounds are separated using solid-phase extraction (SPE), followed by oxime derivatisation and MRM analysis on an LC-QqQ. This method enables determination of the glut-3SH-al and glut-3SH-SO3 content of a wide range of grape-derived samples, a valuable piece of the puzzle in elucidating 3SH biogenesis.

Using this method, we have analysed the glut-3SH-al and glut-3SH-SO3 content of a wide range of white wines from around NZ, investigating the impact of location, age, and noble rot or late harvest on the precursor content of these wines. This insight into factors impacting glut-3SH-al and glut-3SH-SO3 content in commercial wines, and the possible influence on the finished wine aroma, adds another piece to the puzzle of 3SH and 3SHA biogenesis in wines. Indeed, despite the contribution of these volatile thiols to the aroma of botrytised white wines, these wines contain significantly lower, or negligible, concentrations of glut-3SH-al and glut-3SH-SO3, something which will be explored further in future work

DOI:

Publication date: June 22, 2022

Issue: IVAS 2022

Type: Article

 

Authors

Muhl Jennifer¹, Deed Rebecca¹,², Pilkington Lisa¹ and Fedrizzi Bruno¹

¹The University of Auckland, School of Chemical Sciences

²The University of Auckland, School of Biological Sciences

Contact the author

Keywords

LC-QQQ, 3-sulfanylhexan-1-ol, glut-3SH-al, aroma compound precursors, white wine

Tags

IVAS 2022 | IVES Conference Series

Citation

Related articles…

Mapping and tracking canopy size with VitiCanopy

Understanding vineyard variability to target management strategies, apply inputs efficiently and deliver consistent grape quality to the winery is essential. However, despite inherent vineyard variability, the majority are managed as if they are uniform. VitiCanopy is a simple, grower-friendly tool for precision/digital viticulture that allows users to collect and interpret objective spatial information about vineyard performance. After four years of field and market research, an upgraded VitiCanopy has been created to achieve a more streamlined, technology-assisted vine monitoring tool that provides users with a set of superior new features, which could significantly improve the way users monitor their grapevines. These new features include:
• New user interface
• User authentication
• Batch analysis of multiple images
• Ease the learning curve through enhanced help features
• Reporting via the creation of colour maps that will allow users to assess the spatial differences in canopies within a vineyard.
Use-case examples are presented to demonstrate the quantification and mapping of vineyard variability through objective canopy measurements, ground-truthing of remotely sensed measurements, monitoring of crop conditions, implementation of disease and water management decisions as well as creating a history of each site to forecast quality. This intelligent tool allows users to manage grapevines and make informed management choices to achieve the desired production targets and remain profitable.

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.

The modification of cultural practices in grapevine cv. Syrah, does it modify the characteristics of the musts?

The work shows the results of a year of experimentation (2020) in a Syrah variety vineyard in La Roda (Castilla-La Mancha, Spain). The trial approach was on a randomized block design with two factors: Irrigation (I) and Pruning (P).
Irrigation schedules were adjusted to apply amounts close to 1,500 m3/ha. With this provision, 2 different irrigation treatments were proposed: I1) Start of irrigation from pea-sized grape to post-harvest (providing at least 20 % of the total amount of irrigation water to be provided post-harvest); I2) Start of irrigation from pea-sized grape to harvest (usual irrigation practice in the study area). Pruning was proposed with two treatments, one at the end of January (P1), which is pruning on a conventional date; and P2) pruning carried out at the beginning of budding. In total, 4 repetitions were designed with 4 elementary plots, each one of them representing one of the proposed treatments (I1P1; I1P2; I2P1; I2P2). In total, 16 plots were worked on and each elementary plot consisted of 30 strains, distributed in 3 lines.
The productive response was evaluated with the yield results of the harvest harvested at 23 ºBrix. The qualitative response was measured in the musts through the indices of technological (acidity, pH and potassium) and phenolic maturity and aromatic compounds in free and glycosylated fractions. The treatments tested had, in general, an effect on the different variables analyzed.

Use of multispectral satellite for monitoring vine water status in mediterranean areas

The development of new generations of multispectral satellites such as Sentinel-2 opens possibilities as to vine water status assessment (Cohen et al., 2019). Based on a three years field campaign, a model of Stem Water Potential (SWP) estimation on vine using four satellite bands in Red, Red-Edge, NIR and SWIR domains was developed (Laroche-Pinel et al., 2021). The model relies on SWP field measures done using a pressure chamber (Scholander et al., 1965), which is a common, robust and precise method to assess vine water status (Acevedo-Opazo et al., 2008). The model was mainly developed from from SWP measures on Syrah N (Laroche Pinel E., 2021).

A large scale monitoring was organized in different vineyards in the Mediterranean region in 2021. 10 varieties amongst the most represented in this area were monitored (Cabernet sauvignon N, Chardonnay B, Cinsault N, Grenache N, Merlot N, Mourvèdre N, Sauvignon B, Syrah N, Vermentino B, Viognier B). The model was used to produce water status maps from Sentinel-2 images, starting from the beginning of June (fruit set) up to September (harvest). The average estimated SWP for each vine was compared to actual field SWP measures done by wine growers or technicians during usual monitoring of irrigation programs. The correlations between mean estimated SWP and mean measured SWP were at the same level than expected by the model. (Laroche Pinel, 2021) The general SWP kinetics were comparable. The estimated SWP would have led to same irrigation decisions concerning the date of first irrigation in comparison with measured SWP.

Acevedo-Opazo, C., Tisseyre, B., Ojeda, H., Ortega-Farias, S., Guillaume, S. (2008). Is it possible to assess the spatial variability of vine water status? OENO One, 42(4), 203.
Cohen, Y., Gogumalla, P., Bahat, I., Netzer, Y., Ben-Gal, A., Lenski, I., … Helman, D. (2019). Can time series of multispectral satellite images be used to estimate stem water potential in vineyards? In Precision agriculture ’19, The Netherlands: Wageningen Academic Publishers, pp. 445–451.
Laroche-Pinel, E., Duthoit, S., Albughdadi, M., Costard, A. D., Rousseau, J., Chéret, V., & Clenet, H. (2021). Towards vine water status monitoring on a large scale using sentinel-2 images. remote sensing, 13(9), 1837.
Laroche-Pinel,E. (2021). Suivi du statut hydrique de la vigne par télédétection hyper et multispectrale. Thèse INP Toulouse, France.
Scholander, P.F., Bradstreet, E.D., Hemmingsen, E.A., & Hammel, H.T. (1965). Sap pressure in vascular plants: Negative hydrostatic pressure can be measured in plants. Science, 148(3668), 339–346.

Effect of multi-level and multi-scale spectral data source on vineyard state assessment

Currently, the main goal of agriculture is to promote the resilience of agricultural systems in a sustainable way through the improvement of use efficiency of farm resources, increasing crop yield and quality under climate change conditions. This last is expected to drastically modify plant growth, with possible negative effects, especially in arid and semi-arid regions of Europe on the viticultural sector. In this context, the monitoring of spatial behavior of grapevine during the growing season represents an opportunity to improve the plant management, winegrowers’ incomes, and to preserve the environmental health, but it has additional costs for the farmer. Nowadays, UAS equipped with a VIS-NIR multispectral camera (blue, green, red, red-edge, and NIR) represents a good and relatively cheap solution to assess plant status spatial information (by means of a limited set of spectral vegetation indices), representing important support in precision agriculture management during the growing season. While differences between UAS-based multispectral imagery and point-based spectroscopy are well discussed in the literature, their impact on plant status estimation by vegetation indices is not completely investigated in depth. The aim of this study was to assess the performance level of UAS-based multispectral (5 bands across 450-800nm spectral region with a spatial resolution of 5cm) imagery, reconstructed high-resolution satellite (Sentinel-2A) multispectral imagery (13 bands across 400-2500 nm with spatial resolution of <2 m) through Convolutional Neural Network (CNN) approach, and point-based field spectroscopy (collecting 600 wavelengths across 400-1000 nm spectral region with a surface footprint of 1-2 cm) in a plant status estimation application, and then, using Bayesian regularization artificial neural network for leaf chlorophyll content (LCC) and plant water status (LWP) prediction. The test site is a Greco vineyard of southern Italy, where detailed and precise records on soil and atmosphere systems, in-vivo plant monitoring of eco-physiological parameters have been conducted.