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…

The use of rootstock as a lever in the face of climate change and dieback of vineyard

As viticulture faces challenges such as climate change or vineyard dieback, the choice of the variety and rootstock becomes more and more crucial. To study rootstock levers in the Bordeaux region, a parcel of Cabernet Sauvignon (CS) was planted with four rootstocks in 2014. Twenty repetitions of each of the following four rootstocks were set up: 101-14 MGt, Nemadex AB, 420A MGt and Gravesac. The number of bunches, yields and pruning weights of the vine shoots were measured individually on 240 vines from 2017 to 2021. Since 2020, nitrogen status assessed by assimilable nitrogen level, hydric status assessed by δ13C and berry maturity were measured on 80 samples taken from 20 repetitions of the four rootstocks. A lower yield was measured for CS grafted onto Nemadex AB due to the lower number of bunches and the lower weight of berries. The differences between the other three rootstocks are small, but CS grafted onto 420A MGt was the most productive. The CS grafted onto Nemadex AB had the lowest pruning weight while 101-14 MGt had the highest. In 2020, δ13C showed a more moderate water stress with 101-14 MGt and 420A MGt than with Nemadex AB. Surprisingly, the Gravesac was under more stress than the 101-14 MGt. The nitrogen status in the berries was better for Nemadex AB but this was perhaps due to the significantly lower weight of the berries.Rootstock 101-14 MGt attained the highest accumulation of sugars in the berries while 420A MGt allows to preserve higher acidity. The parcel is still young which may explain some of the results. These measures must therefore be continued over the next several years to fully assess the effects of these rootstocks on the development of the vines and the quality of the production under new climatic conditions.

The impact of leaf canopy management on eco-physiology, wood chemical properties and microbial communities in root, trunk and cordon of Riesling grapevines (Vitis vinifera L.)

In the last decades, climate change required already adaptation of vineyard management. Increase in temperature and unexpected weather events cause changes in all phenological stages requiring new management tools. For example, defoliation can be a useful tool to reduce the sugar content in the berries creating differences in the wine profiles. In a ten-year field experiment using Riesling (Vitis vinifera L, planted 1986, Geisenheim, Germany), various mechanical defoliation strategies and different intensities were trialed until 2016 before the vineyard was uprooted. Wood was sampled from the plant compartments root, trunk, cordon and shoot for analyses of physicochemical properties (e.g. lignin and element content, pH, diameter), nonstructural carbohydrates and the microbial communities. The aim of the study was to investigate the influence of reduced canopy leaf area on the sink-source allocation into different compartments and potential changes of the fungal and prokaryotic wood-inhabiting community using a metabarcoding approach. Severe summer pruning (SSP) of the canopy and mechanical defoliation (MDC) above the bunch zone decreased the leaf area by 50% compared to control (C). SSP reduced the photosynthetic capacity, which resulted in an altered source-sink allocation and carbohydrate storage. With lower leaf area, less carbohydrates are allocated. This for example resulted in a decreased trunk diameter. Further, it affected the composition of the grapevine wood microbiota. SSP and MDC management changed significantly the prokaryotic community composition in wood of the root samples, but had no effect in other compartments. In general, this study found strong compartment and less management effects of the microbial community composition and associated physicochemical properties. The highest microbial diversities were identified in the wood of the trunk, and several species were recorded the first time in grapevine.

Different soil types and relief influence the quality of Merlot grapes in a relatively small area in the Vipava Valley (Slovenia) in relation to the vine water status

Besides location and microclimatic conditions, soil plays an important role in the quality of grapes and wine. Soil properties influence…

Inhibition of Oenococcus oeni during alcoholic fermentation by a selected Lactiplantibacillus plantarum strain

The use of selected cultures of the species Lactiplantibacillus plantarum in Oenology has grown in prominence in recent years. While initial applications of this species centred very much around malolactic fermentation (MLF), there is strong evidence to show that certain strains can be harnessed for their bio-protective effects. Unwanted spontaneous MLF during alcoholic fermentation (AF), driven by rogue Oenococcus oeni, is a winemaking deviation that is very difficult to manage when it occurs. This work set out to determine the efficacy of one particular strain of Lactiplantibacillus plantarum(Viniflora® NoVA™ Protect), against this problem in Cabernet Sauvignon must. The work was carried out at commercial scale and in a winery environment and compared the bio-protective culture with the more traditional approach of reducing must pH by the addition of tartaric acid. The combination of both was also investigated. The concentration of both Oenococcus oeni and Lactiplantibacillus plantarum was determined using qPCR. The adventitious Oenococcus oeni showed the most growth during AF in the control wine, whereas in the wines treated with Lactiplantibacillus plantarum a bacteriostatic effect against this species was observed. This effect was comparable to the wines treated with tartaric acid. This has particular commercial relevance for controlling the flora in musts with high pH, or when the addition of tartaric acid is either not permitted or is prohibitive for other reasons.

Upscaling the integrated terroir zoning through digital soil mapping: a case study in the Designation of Origin Campo de Borja

homogeneous zones by intersecting several partial zonings of major factors that influence vineyard growth. Each of them follows specific process from their corresponding disciplines. Soil zoning specifically refers to a Soil Resource Inventory map that has traditionally been generated by conventional soil mapping methods. These methods have shortcomings in reaching fine cartographic and categorical details and involve significant expenses, which undermines their applicability. A new framework named Digital Soil Mapping has introduced quantitative models by statistical techniques to establish soil-landscape relationships and is able to provide intensive scale cartography.

In the present study, a microzoning at 1:10.000 scale is generated from an initial zoning, where the conventional soil map with polytaxic map units is replaced by a new one from digital techniques that disaggregates them. The comparison between the zonings considers a quantitative evaluation of capability for each Homogeneous Terroir Unit by means of the Viticultural Quality Index and its categorization based on its distribution by map. The spatial intersection of both maps gives rise to a confusion matrix in which the flows of class variations after the substitution are assessed.

The results show a five-fold increase in the number of Homogeneous Terroir Units identified and a larger differentiation among them, evidenced by a wider range in the capability index distribution. Both elements are accompanied by an increase in the detection of areas of higher potential within previously undervalued uniform zones.These features are a direct effect of the improvements brought by Digital Soil Mapping techniques and would verify the advantages of their implementation in the Integrated Terroir zoning. Eventually, such new highly detailed terroir units would benefit precision viticulture and sustainable management practices.