Macrowine 2021
IVES 9 IVES Conference Series 9 First quantification of glut-3SH-SO3 and glut-3SH-al in juice and wine

First quantification of glut-3SH-SO3 and glut-3SH-al in juice and wine

Abstract

3-Sulfanylhexan-1-ol (3SH) is a key impact odorant of white wines such as Sauvignon Blanc.[1] In particular, the varietal characters of Sauvignon Blanc, especially from Marlborough New Zealand, are strongly influenced by the concentrations of 3SH.[2,3] 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 fully understood.[1,4] The polyfunctional varietal thiols can be 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.[4]

One precursor of particular interest is the glutathione conjugate to the aldehyde form of 3SH, 3S-glutathionylhexanal (glut-3SH-al). The presence 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. Additionally, the bisulfite adduct of glut-3SH-al (glut-3SH-SO3) has been identified in wine samples.[5,6] The interconversion of glut-3SH-al and glut-3SH-SO3 is of great interest as this equilibrium 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.[6]

A method for the extraction and quantification of glut-3SH-al and glut-3SH-SO3 has been developed, using previously synthesised deuterated analogues of these compounds to ensure reliable quantification.[7] The compounds are separated using solid phase extraction (SPE), followed by oxime derivatisation and MRM analysis on an LC-QqQ. This method has been validated using standard addition of synthetic glut-3SH-al and was found to be linear up to 1000 ppb.

Using this method, we have analysed the glut-3SH-al and glut-3SH-SO3 content of laboratory scale synthetic grape media samples before, during, and after fermentation, as well as a selection of commercial wines and grape juices. With the SPE and LC-QqQ analysis described here, the glut-3SH-al and glut-3SH-SO3 content of a wide range of grape derived samples can be measured, a valuable piece of the puzzle in elucidating 3SH biogenesis.

DOI:

Publication date: September 7, 2021

Issue: Macrowine 2021

Type: Article

Authors

Jennifer Muhl

School of Chemical Sciences, The University of Auckland,Lisa PILKINGTON, School of Chemical Sciences, The University of Auckland  Bruno FEDRIZZI, School of Chemical Sciences, The University of Auckland  Rebecca DEED, School of Chemical Sciences, School of Biological Sciences, The University of Auckland

Contact the author

Keywords

3-sulfanylhexan-1-ol, Aroma Precursors, Analytical Method, Isotopic Labelling, LC-MS/MS

Citation

Related articles…

Comparison of imputation methods in long and varied phenological series. Application to the Conegliano dataset, including observations from 1964 over 400 grape varieties

A large varietal collection including over 1700 varieties was maintained in Conegliano, ITA, since the 1950s. Phenological data on a subset of 400 grape varieties including wine grapes, table grapes, and raisins were acquired at bud break, flowering, veraison, and ripening since 1964. Despite the efforts in maintaining and acquiring data over such an extensive collection, the data set has varying degrees of missing cases depending on the variety and the year. This is ubiquitous in phenology datasets with significant size and length. In this work, we evaluated four state-of-the-art methods to estimate missing values in this phenological series: k-Nearest Neighbour (kNN), Multivariate Imputation by Chained Equations (mice), MissForest, and Bidirectional Recurrent Imputation for Time Series (BRITS). For each phenological stage, we evaluated the performance of the methods in two ways. 1) On the full dataset, we randomly hold-out 10% of the true values for use as a test set and repeated the process 1000 times (Monte Carlo cross-validation). 2) On a reduced and almost complete subset of varieties, we varied the percentage of missing values from 10% to 70% by random deletion. In all cases, we evaluated the performance on the original values using normalized root mean squared error. For the full dataset we also obtained performance statistics by variety and by year. MissForest provided average errors of 17% (3 days) at budbreak, 14% (4 days) at flowering, 14.5% (7 days) at veraison, and 17% (3 days) at maturity. We completed the imputations of the Conegliano dataset, one of the world’s most extensive and varied phenological time series and a steppingstone for future climate change studies in grapes. The dataset is now ready for further analysis, and a rigorous evaluation of imputation errors is included.

Effect of the commercial inoculum of arbuscular mycorrhiza in the establishment of a commercial vineyard of the cultivar “Manto negro

The favorable effect of symbiosis with arbuscular mycorrhizal fungi (AMF) has been known and studied since the 60s. Nowadays, many companies took the chance to start promoting and selling commercial inoculants of AMF, in order to be used as biofertilizers and encourage sustainable biological agriculture. However, the positive effect of these commercial biofertilizers on plant growth is not always demonstrated, especially under field conditions. In this study, we used a commercial inoculum on newly planted grapevines of a local cultivar grafted on a common rootstock R110. We followed the physiological status of vines, growth and productivity and functional biodiversity of soil bacteria during the first and second years of 20 inoculated with commercial inoculum bases on Rhizophagus irregularis and Funeliformis mosseaeAMF at field planting time and 20 non-inoculated control plants. All the parameters measured showed a neutral to negative effect on plant growth and production. The inoculated plants always presented lower values of photosynthesis, growth and grape production, although in some cases the differences did not reach statistical significance. On the contrary, the inoculation supposed an increase of the bacterial functional diversity, although the differences were not statistically significant either. Several studies show that the effect of inoculation with AMF is context-dependent. The non-favorable effects are probably due to inoculation ineffectiveness under complex field conditions and/or that, under certain conditions, AMF presence may be a parasitic association. This puts into question the effectiveness of its application in the field. Therefore, it is recommended to only resort to this type of biofertilizer when the cultivation conditions require it (e.g., very low previous microbial diversity, foreseeable stress due to drought, salinity, or lack of nutrients) and not as a general fertilization practice.

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.

De novo Vitis champinii whole genome assembly allows rootstock-specific identification of potential candidate genes for drought and salt tolerance

Vitis champinii cultivars Ramsey and Dog-ridge are main choices for rootstocks to adapt viticulture in semi-arid and arid regions thanks to their distinctive tolerance to drought and salinity. However, genetic studies on non-vinifera rootstocks have heavily relied on the grapevine (Vitis vinifera) reference genome, which difficulted the assessment of the genetic variation between rootstock species and grapevines. In the present study, this limitation is addressed by introducing a novo phased genome assembly and annotation of Vitis champinii. This new Vitis champinii genome was employed as reference for mapping RNA-seq reads from the same species under drought and salt stresses, and for comparison the same reads were also mapped to the Vitis vinifera PN40024.V4 reference genome. A significant increase in alignment rate was gained when mapping Vitis champinii RNA-seq reads to its own genome, compared to the Vitis vinifera PN40024.V4 reference genome, thus revealing the expression levels of genes specific to Vitis champinii. Moreover, differences in coding sequences were observed in ortholog genes between Vitis champinii and Vitis vinifera, which therefore challenges previous differential expression analyses performed between contrasting Vitis genotypes on the same gene from the Vitis vinifera genome. Genes with possible implications in drought and salt tolerance have been identified across the genome of Vitis champinii, and the same genomic data can potentially guide the discovery of candidate genes specific from Vitis champinii for other traits of interest, therefore becoming a valuable resource for rootstock breeding designs, specially towards increased drought and salinity due to climate change.

Effects of graft quality on growth and grapevine-water relations

Climate change is challenging viticulture worldwide compromising its sustainability due to warmer temperatures and the increased frequency of extreme events. Grafting Vitis vinifera L.