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…

Understanding the physiological responses of Sauvignon blanc vines to sequential extreme weather events: implications for vineyard management in a changing climate

Climate plays a predominant role in vines’ growth and productivity and several environmental variables are already known to pose challenges to grapevine production and the horticultural industry as a whole. In this context, a number of extreme weather events already occurring and expected to occur in the next decades even more frequently and with higher magnitude results from current climate change scenario. The aim of this study was to examine the physiological responses of roots, leaves, and berries of Vitis vinifera cv. Sauvignon blanc to consecutive and combined stressors simulated in a semi-controlled environment.

DNA-free editing to improve stress resilience of wine grape genotypes recalcitrant-to-regeneration

Wine viticulture, being firmly linked to the vine-terroir relationship, has always encountered significant bottlenecks to genetic innovation. Nonetheless, the development of new breeding strategies leading to the selection of stress resilient genotypes is urgent, especially in viticulture, where it would allow reducing the use of chemical treatments adopted to control fungal diseases. Genome editing represents an extremely promising breeding technique. Unfortunately, the well-known recalcitrance of several wine grape cultivars to in vitro regeneration strongly limits the exploitation of this approach, which to our knowledge has so far been developed on table grape genotypes with high regeneration potential.

Impact of reduction alcohol techiniques in the aromatic chemical profile of rosé Tempranillo wines

Studying the impact of reducing alcohol techniques in the chemical composition of the aromatic profile of rosé Tempranillo wines from the spanish region of Castilla-La Mancha INTRODUCTION: In the last decades there has been an increseasing demand of wines with low or non-existing alcohol concentration due to the negative effects that alcohol has in health. In spite of that, there are not laws that protect these products, and there is also a great difficulty in the elaboration of these type of wines due to the increasing temperatures because of climate change. This is why the oenological industry has made great advances in the development of different techniques that could satisfy consumers’ demands without modifying wine quality. The most used techniques have been post-fermentative ones.

Relation between phenolic content, antioxidant capacity, oxygen consumption rate of diverse tannins

The work was aimed at comparing some analytical methods used to characterize oenological tannins and the measure of oxygen consumption rate (OCR), in order to provide oenologists with a rapid method to test the antioxidant capacity of tannin based products and a tool to choose the best suited product for each purpose.

Drought affects vineyard soil microbiome: approach to select micro-organisms adapted to drought

Climate transition with frequent heat waves and long drought periods threatens grapevine productivity and wine quality in the Mediterranean regions. Microorganisms are known to contribute to plant fitness and to stimulate plant resilience against biotic and abiotic factors.
In this work, it was assessed the impact of long-term drought on soil microbiome associated to grapevine in open field in Alentejo, renowned Portuguese wine region.
Soil and plant tissues of drought tolerant Syrah cultivar exposed to three irrigation levels (100%- FI, 50%-DI ETc; rain-fed–NI) for 5 years were sampled for two years (2022-2023). Metabarcoding analysis of soil bacteria (16S V4 rRNA) and fungi (ITS sub-region) were integrated with soil physiochemical properties and leaves´ physiological data. Pre-dawn leaf water potential and stomatal conductance confirmed the imposed drought scenarios. Even though, α- and β-diversity of prokaryotic and eukaryotic microbial communities differed more by season than water availability, samples clustered according to soil water content and pH (p<0.05). Fungal communities show higher differences in the structure across treatments than bacteria. In 2023, 16 bacterial against 61 fungal ASVs were significatively different in abundance between NI and FI. Beijerinckiaceae, Bradyrhizobiaceae (Alphaproteobacteria) and Nocardioidaceae, Streptomycetaceae (Actinobacteria) families resulted to be significatively more abundant in NI, while Ascomycota, Basidyomicota and Mortierellomycota are the most important fungal phyla in NI. With culturomics data, this study aims to gather insights into how soil microbiome is remodelled under drought and contribute to select bacterial and fungal taxa with potential to mitigate drought stress in vineyards.