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 effects of alternative herbicide free cover cropping systems on soil health, vine performance, berry quality and vineyard biodiversity in a climate change scenario in Switzerland

There is an urgent need in viticulture to adopt alternative herbicide-free soil management strategies to mitigate climate change, increase biodiversity, reduce plant protection products and improve soil quality while minimizing detrimental effects on grapevine’s stress tolerance and fruit quality. To propose sustainable solutions, adapted to different pedoclimatic conditions in Switzerland, we developed a multidisciplinary 4-year project, started in 2020. Objectives of the project are to a) evaluate the impact of green covers (spontaneous flora, winter cover crop and permanent ground cover) on environmental and agronomic parameters and b) develop subsequently innovative strategies for different viticultural contexts of Switzerland. The project is divided into 3 phases: 1) diagnosis, 2) on-farm and 3) on-station experiments. Phase 1) consisted in an assessment of 30 commercial vineyards all over Switzerland, where growers already use different herbicide-free soil management strategies. The most promising practices identified in this exploratory phase will be replicated in commercial vineyards across Switzerland (“on-farm”) as well as in a classical randomized block design in an experimental plot (“on-station”). For phase 1), measurements consisted in evaluation of soil status (compaction, structure, roots development), soil microbial diversity (metagenomics), plant diversity and biomass, vine physiology (water stress, vigor, leaf nitrogen) and berry quality (acidity, sugar, available nitrogen). Interestingly, the permanent ground cover resulted in a higher Shannon index thus a higher biodiversity as compared to the other itineraries. The winter cover crop increased vine nitrogen and vigor while deteriorating soil quality, leaving the soil more exposed and compacted likely due to more frequent tillage. The spontaneous flora led to higher berry sugar accumulation, less nitrogen and higher malic acid concentration putatively due to a higher water retention of the flora in a particularly wet vintage. Phases 2) and 3) are required to confirm those tendencies, over the 3 next vintages and different climatic conditions.

Spatial determination of areas in the Western Balkans region favorable for organic production

In problematic conditions for production of grapes and wine caused by the COVID-19 pandemic and the resulting occurrence of wine surpluses, producers are increasingly turning to the innovative viticulture and winemaking of products that are more appealing to the market and the consumers. On the other hand, consumption of the food safety or organic products, and therefore of organic grapes and wine, is increasingly common in the world, in particular in Europe. The Regional Rural Development Standing Working Group (SWG RRD), as a regional intergovernmental organization gathers actors in the viticulture and winemaking sector from states and territories of the Western Balkans (South-East Europe) in the Expert Working Group for Wine, with the aim of improving viticulture and winemaking in this region through joint activities. In accordance with the aforementioned, the SWG RRD is working on advancing organic production of grapes and wine, and on recognition of specificities of the terroir of wine-growing areas in Western Balkans. In addition, as part of the project “Facilitation of Exchange and Advice on Wine Regulations in Western Balkan Countries” helmed by the German Federal Ministry of Food and Agriculture, in addition to harmonization of relevant legislation with EU regulations, efforts are being invested towards recognition of organic wines. Within activities and project implemented by this organization, expert analyses and scientific research of the terroir of Western Balkans were carried out, and some of the results are presented in this paper.

Towards a regional mapping of vine water status based on crowdsourcing observations

Monitoring vine water status is a major challenge for vineyard management because it influences both yield and harvest quality. It is also a challenge at the territorial scale for identifying periods of high water restriction or zones regularly impacted by water stress. This information is of major importance for defining collective strategies, anticipating harvest logistic or applying for irrigation authorisation. At this spatial scale, existing tools and methods for monitoring vine water status are few and often require strong assumptions (e.g. water balance model). This paper proposes to consider a collaborative collection of observations by winegrowers and wine industry stakeholders (crowdsourcing) as an interesting alternative. Indeed, it allows the collection of a large number of field observations while pooling the collection effort. However, the feasibility of such a project and its interest in monitoring vine water status at regional scale has never been tested.

The objective of this article is to explore the possibility of making a regional map of vine water status based on crowdsourcing observations. It is based on the study of the free mobile application ApeX-Vigne, which allows the collection of observations about vine shoot growth. This information is easy to collect and can be considered, under certain conditions, as a proxy for vine water status. This article presents the first results obtained from the nearly 18,000 observations collected by winegrowers and wine industry stakeholders during 2019, 2020 and 2021 seasons. It presents the vine shoot growth maps obtained at regional scale and their evolution over the three vintages studied. It also proposes an analysis of the factors that favoured the number of observations collected and those that favoured their quality. These results open up new perspectives for monitoring vine water status at a regional scale but above they provide references for other crowdsourcing projects in viticulture.

The impact of sustainable management regimes on amino acid profiles in grape juice, grape skin flavonoids, and hydroxycinnamic acids

One of the biggest challenges of agriculture today is maintaining food safety and food quality while providing ecosystem services such as biodiversity conservation, pest and disease control, ensuring water quality and supply, and climate regulation. Organic farming was shown to promote biodiversity and carbon sequestration, and is therefore seen as one possibility of environmentally friendly production. Consumers expect organically grown crops to be free from chemical pesticides and mineral fertilizers and often presume that the quality of organically grown crops is different or higher compared to conventionally grown crops. Integrated, organic, and biodynamic viticulture were compared in a replicated field trial in Geisenheim, Germany (Vitis vinifera L. cv. Riesling). Amino acid profiles in juice, grape skin flavonoids, and hydroxycinnamic acids were monitored over three consecutive seasons beginning 7 years after conversion to organic and biodynamic viticulture, respectively. In addition, parameters such as soil nutrient status, yield, vigor, canopy temperature, and water stress were monitored to draw conclusions on reasons for the observed changes. Results revealed that the different sustainable management regimes highly differed in their amino acid profiles in juice and also in their skin flavonol content, whereas differences in the flavanol and hydroxycinnamic acid content were less pronounced. It is very likely that differences in nutrient status and yield determined amino acid profiles in juice, although all three systems showed similar amounts of mineralized nitrogen in the soil. Canopy structure and temperature in the bunch zone did not differ among treatments and therefore cannot account for the observed differences in favonols. A different light exposure of the bunches in the respective systems due to differences in vigor together with differences in berry size and a different water status of the vines might rather be responsible for the increase in flavonol content under organic and biodynamic viticulture.

Exploring resilience and competitiveness of wine estates in Languedoc-Roussillon in the recent past: a multi-level perspective

The Languedoc-Roussillon wineries are facing a decline in wine yields particularly PGI yields due to many factors. Climate change is just ones, but is expected to increase in the future. There is also structurally a large heterogeneity of yield profiles among terroirs, varieties and strategies. This work investigates the link between yield, competitiveness and resilience to explore how resilient winegrowers have been in the recent past. To this end two approaches have been combined; (i) an accountancy database analysis at estate scale and (ii) municipality level competitiveness analysis. A new resilience indicator that characterizes the capacity of an estate to absorb yield variation is also defined. The FADN database between 2000 and 2018 of ex-Languedoc-Roussillon (France) and other data are used to analyse the current situation and the past evolution of competitiveness and resilience by type of estate (type of farm: PGI and/or PDO & type of commercialization: bulk and/or bottles). The net margin, which defines competitiveness, is not correlated to yield for all types but depends on the type of commercialization and the level of specialisation. The resilience indicator shows that the net margin of estates specialized in PGI is particularly sensitive to yield declines. We also show that price evolutions seem to compensate the effect of yield losses for the majority of types. Municipality scale analysis shows the links between local pedoclimate, yield, commercialization strategies and price. Overlapping a PDO with a PGI does not always increase a municipality’s PGI competitiveness. It is difficult to make links between causes and effects due to the complexity of the wine production system. Production diversification may be a solution. Resorting to the two level of analysis helps resolving the data gap that is necessary to explore the links between yield and economic performance of the wine estates in the long term.