IVAS 2022 banner
IVES 9 IVES Conference Series 9 IVAS 9 IVAS 2022 9 A browser application for comprehensive 3-dimensional LC × LC × IM – MS data analysis to study grape and wine polyphenols

A browser application for comprehensive 3-dimensional LC × LC × IM – MS data analysis to study grape and wine polyphenols

Abstract

The analysis of structurally diverse proanthocyanidins in grapes and wine is challenging. Comprehensive two-dimensional liquid chromatography (LC×LC) and ion mobility spectrometry-mass spectrometry (IMS-MS) are increasingly used to address the challenges associated with the analysis of highly complex samples such as wine and grapes. Hyphenation of these techniques in form of a comprehensive three-dimensional LC×LC×IMS separation system coupled to high resolution – mass spectrometry significantly increases separation power. The gain of separation power results in very opulent and complex four-dimensional data structure. One of the main challenges of such a system is the lack of commercial software to accommodate the resulting four-dimensional data. We therefore developed a Python protocol using Jupyter notebooks for the extraction, visualization and interpretation of such data. Jupyter notebooks allow all methods of signal and data processing and even interactive visualizations. The user, however, needs programming skills to employ the notebooks. To make the data analysis approach available to analytical chemists without programming skills, we developed an interactive analytical browser application based on the Python package Plotly’s Dash.

The visualization of an extracted ion chromatogram (EIC) of the LC×LC×IMS-MS data is achieved by a 3-dimensional scatter plot representing the first and second dimension retention times and the IMS drift time on the x-, y- and z-axis of the scatter plot, respectively. Peaks appear as clouds of data points in this three-dimensional space. A mouse click on a data point shows the high-resolution mass spectrum in a separate bar plot. An example of the usage of the browser app includes separations of the procyanidin trimers (865 m/z) found in grape seed extract

DOI:

Publication date: June 23, 2022

Issue: IVAS 2022

Type: Article

Authors

Vestner Jochen¹, Venter Pieter², Fischer Ulrich1 and De Villiers André²

¹Institute for Viticulture and Oenology, DLR Rheinpfalz
²Department of Chemistry and Polymer Science, Stellenbosch University

Contact the author

Keywords

comprehensive multidimensional chromatography, liquid chromatography, ion mobility spectrometry, data analysis, polyphenols

Tags

IVAS 2022 | IVES Conference Series

Citation

Related articles…

Climate projections over France wine-growing region and its potential impact on phenology

Climate change represents a major challenge for the French wine industry. Climatic conditions in French vineyards have already changed and will continue to evolve. One of the notable effects on grapevine is the advancing growing season. The aim of this study is to characterise the evolution of agroclimatic indicators (Huglin index, number of hot days, mean temperature, cumulative rainfall and number of rainy days during the growing season) at French wine-growing regions scale between 1980 and 2019 using gridded data (8 km resolution, SAFRAN) and for the middle of the 21th century (2046-2065) with 21 GCMs statistically debiased and downscaled at 8 km. A set of three phenological models were used to simulate the budburst (BRIN, Smoothed-Utah), flowering, veraison and theoretical maturity (GFV and GSR) stages for two grape varieties (Chardonnay and Cabernet-Sauvignon) over the whole period studied. All the French wine-growing regions show an increase in both temperatures during the growing season and Huglin index. This increase is accompanied by an advance in the simulated flowering (+3 to +9 days), veraison (+6 to +13 days) and theoretical maturity (+6 to +16 days) stages, which are more noticeable in the north-eastern part of France. The climate projections unanimously show, for all the GCMs considered, a clear increase in the Huglin index (+662 to 771 °C.days compared to the 1980-1999 period) and in the number of hot days (+5.6 to 22.6 days) in all the wine regions studied. Regarding rainfall, the expected evolution remains very uncertain due to the heterogeneity of the climates simulated by the 21 models. Only 4 regions out of 21 have a significant decrease in the number of rainy days during the growing season. The two budburst models show a strong divergence in the evolution of this stage with an average difference of 18 days between the two models on all grapevine regions. The theoretical maturity is the most impacted stage with a potential advance between 40 and 23 days according to wine-growing regions.

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.

Measurement of redox potential as a new analytical winegrowing tool

Excell laboratory has initiated the development of an analytical method based on electrochemistry to evaluate the ability of wines to undergo or resist to oxidative phenomena. Electrochemistry is a powerful tool to probe reactions involving electron transfers and offers possibility of real-time measurements. In that context, the laboratory has implemented electrochemical analysis to assess oxidation state of different wine matrices but also in order to evaluate oxidative or reduced character of leaf and soil. Initially, our laboratory focused on dosage of compounds involved in responses of plant stresses and we were also interested in microbiological activity of soils. These analyses were compared with the measurement of redox potential (Eh) and pH which are two fundamental variables involved in the modulation of plant metabolism. Indeed, the variation of redox states of the plant reflects its biological activity but also its capacity to absorb nutriments. The Eh-pH conditions mainly determine metabolic processes involved in soil and leaf and our goal is to determine if this combined analytical approach will be sufficiently precise to detect biological evolutions (plant health, parasitic attack…).

Green berries on Gewürztraminer (Vitis vinifera L.) in South Tyrol (Italy)

The grape variety Gewürztraminer is known to be affected by two physiological disorders namely berry shrivel and bunch stem necrosis. During the season 2014 we noticed a new symptomatology type of ripening disorder on the variety. The new symptom showed not all berries fallowing the normal maturation stages, but single berries remaining at a soft but green stage till harvest. The broad distribution of these so called “green berries” symptoms in different production sites of our region, caused huge damage due to the difficulty of eliminating single berries per bunch before harvesting. Therefore, the Research Centre Laimburg began to investigate the reasons and origins of this new symptom. This work shows the results of first attempts to find causes for the symptom as well as the resulting approach to mitigate symptoms. Applications of magnesium leaf fertilizer showed first promising results against this putative disorder. To study the causal effect of the green berries 30 symptomatic vineyards in 2014 have been selected for a monitoring during the season 2016. To evaluate the foliar nutrient treatment two vineyards have been selected for application of magnesium sulfate and magnesium chloride. Leaf and berry nutrient analysis, as well as the main quality parameters during ripening have been performed. As soon as “green berries” symptoms appeared, incidence and severity have been evaluated. Most of the symptomatic vineyards of the 2016 monitoring showed light to clear magnesium deficit symptoms on their foliage. Only during the seasons 2020 and 2021 “green berries” symptoms could be found in the leaf fertilizer treatment vineyards. Both seasons showed a significant effect of the magnesium treatments to reduce the incidence and severity of the symptom. It seems that the appearance of the “green berries” symptom on Gewürztraminer is correlated to a disturbed uptake of magnesium of the vines.

Climate and the evolving mix of grape varieties in Australia’s wine regions

The purpose of this study is to examine the changing mix of winegrape varieties in Australia so as to address the question: In the light of key climate indicators and predictions of further climate change, how appropriate are the grape varieties currently planted in Australia’s wine regions? To achieve this, regions are classified into zones according to each region’s climate variables, particularly average growing season temperature (GST), leaving aside within-region variations in climates. Five different climatic classifications are reported. Using projections of GSTs for the mid- and late 21st century, the extent to which each region is projected to move from its current zone classification to a warmer one is reported. Also shown is the changing proportion of each of 21 key varieties grown in a GST zone considered to be optimal for premium winegrape production. Together these indicators strengthen earlier suggestions that the mix of varieties may be currently less than ideal in many Australian wine regions, and would become even less so in coming decades if that mix was not altered in the anticipation of climate change. That is, grape varieties in many (especially the warmest) regions will have to keep changing, or wineries will have to seek fruit from higher latitudes or elevations if they wish to retain their current mix of varieties and wine styles.