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: 22/06/2022

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…

Amino nitrogen content in grapes: the impact of crop limitation

As an essential element for grapevine development and yield, nitrogen is also involved in the winemaking process and largely affects wine composition. Grape must amino nitrogen deficiency affects the alcoholic fermentation kinetics and alters the development of wine aroma precursors. It is therefore essential to control and optimize nitrogen use efficiency by the plant to guarantee suitable grape nitrogen composition at harvest. Understanding the impact of environmental conditions and cultural practices on the plant nitrogen metabolism would allow us to better orientate our technical choices with the objective of quality and sustainability (less inputs, higher efficiency). This trial focuses on the impact of crop limitation – that is a common practice in European viticulture – on nitrogen distribution in the plant and particularly on grape nitrogen composition. A wide gradient of crop load was set up in a homogeneous plot of Chasselas (Vitis vinifera) in the experimental vineyard of Agroscope, Switzerland. Dry weight and nitrogen dynamics were monitored in the roots, trunk, canopy and grapes, during two consecutive years, using a 15N-labeling method. Grape amino nitrogen content was assessed in both years, at veraison and at harvest. The close relationship between fruits and roots in the maintenance of plant nitrogen balance was highlighted. Interestingly, grape nitrogen concentration remained unchanged regardless of crop load to the detriment of the growth and nitrogen content of the roots. Meanwhile, the size and the nitrogen concentration of the canopy were not affected. Leaf gas exchange rates were reduced in response to lower yield conditions, reducing carbon and nitrogen assimilation and increasing intrinsic water use efficiency. The must amino nitrogen profiles could be discriminated as a function of crop load. These findings demonstrate the impact of plant balance on grape nitrogen composition and contribute to the improvement of predictive models and sustainable cultural practices in perennial crops.

Anthocyanin profile is differentially affected by high temperature, elevated CO2 and water deficit in Tempranillo (Vitis vinifera L.) clones

Anthocyanin potential of grape berries is an important quality factor in wine production. Anthocyanin concentration and profile differ among varieties but it also depends on the environmental conditions, which are expected to be greatly modified by climate change in the future. These modifications may significantly modify the biochemical composition of berries at harvest, and thus wine typicity. Among the diverse approaches proposed to reduce the potential negative effects that climate change may have on grape quality, genetic diversity among clones can represent a source of potential candidates to select better adapted plant material for future climatic conditions. The effects of individual and combined factors associated to climate change (increase of temperature, rise of air CO2 concentration and water deficit) on the anthocyanin profile of different clones of Tempranillo that differ in the length of their reproductive cycle were studied. The aim was to highlight those clones more adapted to maintain specific Tempranillo typicity in the future. Fruit-bearing cuttings were grown in controlled conditions under two temperatures (ambient temperature versus ambient temperature + 4ºC), two CO2 levels (400 ppm versus 700 ppm) and two water regimes (well-watered versus water deficit), both in combination or independently, in order to simulate future climate change scenarios. Elevated temperature increased anthocyanin acylation, whereas elevated CO2 and water deficit favoured the accumulation of malvidin derivatives, as well as the acylation and tri-hydroxylation level of anthocyanins. Although the changes in anthocyanin profile observed followed a common pattern among clones, such impact of environmental conditions was especially noticeable in one of the most widely distributed Tempranillo clones, the accession RJ43.

Using δ13C and hydroscapes as a tool for discriminating cultivar specific drought response

Measurement of carbon isotope discrimination in berry juice sugars at maturity (δ13C) provides an integrated assessment of water use efficiency (WUE) during the period of berry ripening, and when collected over multiple seasons can be used as an indication of drought stress response. Berry juice δ13C measurements were carried out on 48 different varieties planted in a common garden experiment in Bordeaux, France from 2014 through 2021 and were paired with midday and predawn leaf water potential measurements on the same vines in a subset of six varieties. The aim was to discriminate a large panel of varieties based on their stomatal behaviour and potentially identify hydraulic traits characterizing drought tolerance by comparing δ13C and hydroscapes (the visualisation of plant stomatal behaviour as a response to predawn water potential). Cluster analysis found that δ13C values are likely affected by the differing phenology of each variety, resulting in berry ripening of different varieties taking place under different stress conditions within the same year. We accounted for these phenological differences and found that cluster analysis based on specific δ13C metrics created a classification of varieties that corresponds well to our current empirical understanding of their relative drought tolerances. In addition, we analysed the water potential regulation of the subset of six varieties (using the hydroscape approach) and found that it was well correlated with some δ13C metrics. Surprisingly, a variety’s water potential regulation (specifically its minimum critical leaf water potential under water deficit) was strongly correlated to δ13C values under well-watered conditions, suggesting that base WUE may have a stronger impact on drought tolerance than WUE under water deficit. These results give strong insights on the innate WUE of a very large panel of varieties and suggest that studies of drought tolerance should include traits expressed under non-limiting conditions.

Vineyards and clay minerals: multi-technique analytical approach and correlations with soil properties

Purpose of this research is to quantitatively assess the mineral component of vineyard soils, with particular attention to the mineralogical analysis of clays, which represent an element of high importance in the vineyard culture as well as in general agriculture. An X-ray diffraction (XRD) / thermogravimetric (TG) multi-technique analytical approach was developed, tested on soil samples taken from vineyards around the world. This codified analytical procedure was necessary to obtain precise qualitative and quantitative mineralogical data, globally comparable to distinguish the geopedological identity of the vineyards. Soil samples from vineyards of various locations were analysed, in very different geological conditions. The bulk-rock quantitative phase analysis (QPA) was obtained by the Rietveld method while the detailed composition of the clay-sized fraction was determined by modelling of the oriented X-ray diffraction patterns. The research provided a precise classification of the mineral component of soils, distinguishing the mineral phases of the clays and the so-called mixed-layer clay minerals. We found that the content in mixed layers can be directly correlated with the water retention and the cation exchange capacity ​​of the soil, while the presence of other clayey minerals and phyllosilicates in this research did not affect this CEC parameter, which codes the fertility level of the soils. The study demonstrates that terroir, in particular soils formed in complex or very different geological conditions, can only be effectively interpreted by properly analysing its mineral phases, in particular the mixed-layer clay component. These are characteristic abiotic ecological indicators, which may have specific eco-physiological influences on the plant.

Elucidating vineyard site contributions to key sensory molecules: Identification of correlations between elemental composition and volatile aroma profile of site-specific Pinot noir wines

The reproducibility of elemental profile in wines produced across multiple vintages has been previously reported using grapes from a single scion clone of Vitis vinifera L. cv. Pinot noir. The grapevines were grown on fourteen different vineyard sites, from Oregon to southern California in the U.S.A., which span distances from approximately hundreds of meters to 1450 km, while elevations range from near sea level to nearly 500 m. In addition, sensorial (i.e. aroma, taste, and mouthfeel) and chemical (i.e. polyphenolic and volatile) differences across the different vineyard sites have also been observed among these wines at two aging time points. While strong evidence exists to support that grapes grown in different regions can produce wines with unique chemical and sensorial profiles, even when a single clone is used, the understanding of growing site characteristics that result in this reproducible differentiation continues to emerge. One hypothesis is that the elemental profile that a vineyard site imparts to the grape berries and the resulting wine is an important contributor to this differentiation in chemistry and sensory of wines. For example, various classes of enzymes that catalyze the formation of key aroma compounds or their precursors require specific metals. In this work, we begin to report correlations between elemental and volatile aroma profiles of site-specific Pinot noir wines, made under standardized winemaking conditions, that have been previously shown to be distinguished separately by these chemical analyses.