A mechanistic investigation of H/D scrambling processes in flavonoids

Abstract

Several classes of flavonoids, such as anthocyanins, flavonols, flavanols and flavones, undergo a slow H/D exchange on aromatic ring A, leading to full deuteration at positions C(6) and C(8). Within the flavanol class, H-C(6) and H-C(8) of catechin and epicatechin are slowly exchanged in D2O to the corresponding deuterated analogues; even quercetin, a relevant flavonol representative, shows the same behaviour in a D2O/DMSOd6 1:1 solution. Detailed kinetic measurements of these H/D scrambling processes are here reported by exploiting the time-dependent changes of their peak areas in the 1H-NMR spectra taken at different temperatures. A unifying reaction mechanism is also proposed based on our detailed kinetic observations, even taking into account pH and solvent effects. Molecular modelling and QM calculations were also carried out to shed more light on several molecular details of the proposed mechanism.

DOI:

Publication date: September 16, 2021

Issue: Macrowine 2021

Type: Article

Authors

Graziano Guella

Biorganic Chemistry Lab/Dept. of Physics/University of Trento,Federico Bonaldo1, Fulvio Mattivi2, Daniele Catorci*, &, Panagiotis Arapitsas3, Graziano Guella1, * 1  Bioorganic Chemistry Laboratory, Department of Physics, University of Trento, Trento, Italy; 2 Department of Cellular, Computational and Integrative Biology – CIBIO and C3A, University of Trento, Trento, Italy; 3 Department of Food Quality and Nutrition, Research and Innovation Centre, Fondazione Edmund Mach (FEM), San Michele all’Adige, Italy; * D. Catorci passed away on June 27th, 2020

Contact the author

Keywords

flavonoids; chemistry of polyphenols; h/d isotopic scrambling; reaction mechanism

Citation

Related articles…

Analysis of some environmental factors and cultural practices that affect the production and quality of the Manto Negro, Callet and Prensal Blanc varieties

45 non irrigated vineyards distributed in the DO (Denomination) Pla i Llevant de Mallorca and the DO Binissalem Mallorca were used to investigate the characteristics of production and quality and their relationships certain environmental factors and cultural practices. The grape varieties investigated are autochthonous to the island of Mallorca, Manto Negro and Callet as red and Prensal Blanc as white. All plants were measured for four consecutive years in the main production and quality parameters. Among the environmental factors, the type of soil has been studied, more specifically its water retention capacity, the planting density, the age of the vineyard and the level of viral infection. The presence or absence of virus seems to have no effect on any component studied in the varieties studied. For the white variety Prensal Blanc age is negatively correlated with production and the number of bunches, nevertheless it does not cause any effect on the required quality parameters. However, for the red varieties Callet and Manto Negro, the age of the plantation is the variable that best correlates with the quality parameters, therefore the old vines should be the object of preservation by the viticulturists and winemakers in order to guarantee its contribution to the quality of the wines made with these varieties.

How can historical cultivars mitigate the effects of climate change?

IFV, INRAe and the national network “Partenaires de la Sélection Vigne” representing 37 organizations from the different wine regions, have been working increasingly closely over the last 2 decades towards the preservation of the French varietal patrimony. There are approximately 600 patrimonial varieties according to INRAe and SupAgro Montpellier experts, including ancient cultivars (400) and intravarietal crossbreeds obtained since the 19th century. In the context of a drastic reduction in such varieties from the mid 1980’s in favor of mainstream varieties, it was essential to carry out an inventory of old vines and vineyards. INRAe Vassal collection plays a key role here as it holds the largest diversity available, along with a rich bibliography and herbariums, offering us the opportunity to document and double check the identity of a cultivar, consolidating the expertise of ampelographers. The work is carried out in several stages, from verifying the existence of a variety in a small region, through to rehabilitation. During this session, the authors present the process that leads to the official registration of a variety. After this, IFV selection center takes over to initiate the process of selection and propagation. A specific focus within regions such as the Alps, Champagne and the South-West will provide details of the full procedure. Bia, Bouysselet, Chardonnay rose, Mecle and the aptly named Tardif, are some of the cultivars that have followed this procedure. Furthermore, a recent regulation established by INAO on “varieties of interest for adaptation purposes” might boost uptake by growers. Since 2006, 36 historical cultivars have been registered. Most of these have been neglected in the past due to late maturity, lack of sugar and high titratable acidity at harvest time. Such characteristics are today considered as positive qualities, not only in mitigation of the effects of climate change, but also as an opportunity for restoring diversity…

A blueprint for managing vine physiological balance at different spatial and temporal scales in Champagne

In Champagne, the vine adaptation to different climatic and technical changes during these last 20 years can be seen through physiological balance disruptions. These disruptions emphasize the general grapevine decline. Since the 2000s, among other nitrogen stress indicators, the must nitrogen has been decreasing. The combination of restricted mineral fertilizers and herbicide use, the growing variability of spring rainfall, the increasing thermal stress as well as the soil type heterogeneity are only a few underlying factors that trigger loss of physiological balance in the vineyards. It is important to weigh and quantify the impact of these factors on the vine. In order to do so, the Comité Champagne uses two key-tools: networking and modelization. The use of quantitative and harmonized ecophysiological indicators is necessary, especially in large spatial scales such as the Champagne appellation. A working group with different professional structures of Champagne has been launched by the Comité Champagne in order to create a common ecophysiology protocol and thus monitor the vine physiology, yearly, around 100 plots, with various cultural practices and types of soil. The use of crop modelling to follow the vine physiological balance within different pedoclimatic conditions enables to understand the present balance but also predict the possible disruptions to come in future climatic scenarios. The physiological references created each year through the working group, benefit the calibration of the STICS model used in Champagne. In return, the model delivers ecophysiology indicators, on a daily scale and can be used on very different types of soils. This study will present the bottom-up method used to give accurate information on the impacts of soil, climate and cultural practices on vine physiology.

Characterization of variety-specific changes in bulk stomatal conductance in response to changes in atmospheric demand and drought stress

In wine growing regions around the world, climate change has the potential to affect vine transpiration and overall vineyard water use due to related changes in atmospheric demand and soil water deficits. Grapevines control their transpiration in response to a changing environment by regulating conductance of water through the soil-plant-atmosphere continuum. Most vineyard water use models currently estimate vine transpiration by applying generic crop coefficients to estimates of reference evapotranspiration, but this does not account for changes in vine conductance associated with water stress, nor differences thought to exist between varieties. The response of bulk stomatal conductance to daily weather variability and seasonal drought stress was studied on Cabernet-Sauvignon, Merlot, Tempranillo, Ugni blanc, and Semillon vines in a non-irrigated vineyard in Bordeaux France. Whole vine sap flow, temperature and humidity in the vine canopy, and net radiation absorbed by the vine canopy were measured on 15-minute intervals from early July through mid-September 2020, together with periodic measurement of leaf area, canopy porosity, and predawn leaf water potential. From this data, bulk stomatal conductance was calculated on 15-minute intervals, and multiple regression analysis was performed to identify key variables and their relative effect on conductance. Attention was focused on addressing multicollinearity and time-dependency in the explanatory variables and developing regression models that were readily interpretable. Variability of vapor pressure deficit over the day, and predawn water potential over the season explained much of the variability in conductance, with relative differences in response coefficients observed across the five varieties. By characterizing this conductance response, the dynamics of vine transpiration can be better parameterized in vineyard water use modeling of current and future climate scenarios.

From a local to an international scale: sensory benchmarking of PDO wines. Quincy and Reuilly PDO wines (Sauvignon blanc) as a case study (France)

In a collective marketing strategy, the Protected Designation of Origin (PDO) can be used as a quality indicator. To highlight terroir specificities, it is useful to know how the wines are positioned on the local, national or international market from a sensory point of view. This is especially true for a comparison of varietal wines (e.g. Sauvignon blanc). We focus on the case of two closed Loire Valley PDO (France): Quincy and Reuilly. Three distinct tastings were organized. Firstly, at the local level comparing the 2 PDO (11 and 9 wines, 17 professional assessors); secondly at a regional level adding 3 closed PDO: Menetou-Salon, Sancerre and Pouilly-Fumé (3 wines per PDO, 16 assessors) and thirdly at an international level comparing these 5 PDO with Sauvignon Blanc wines coming from South Africa, New Zealand and Chile (1 to 3 wines per PDO, 19 assessors). All the wines were from the 2019 vintage and were considered to have a traditional elaboration process without contact with oak. A sensory descriptive analysis was performed using an aroma wheel allowing to combine a Check-All-That-Apply methodology, often used in sensory benchmarking, with a hierarchical structuration of the attributes. The aim is to facilitate data acquisition in a professional context without common training, to consider the hierarchical relationships among the attributes during the data analysis and to be able to characterize wines with a large range of sensorial variability. We use univariate, multivariate and clustering analyses. Similarities and differences between Quincy and Reuilly PDO wines and other Sauvignon blanc wines were identified. Specific attributes can distinguish the two PDO and different proximities exist with other local PDO, while clear differences were observed compared to international wines. Our study contributes to propose and discuss a method to do a wine sensory benchmarking highlighting sensory specificities linked to origin.