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…

Effect of two water deficit regimes on the agronomic response of 12 grapevine varieties cultivated in a semi-arid climate

The Mediterranean basin is one of the most vulnerable regions to Climate Change effects. According to unanimous forecasts, the vineyards of Castilla-La Mancha will be among the most adversely affected by rising temperatures and water scarcity during the vine’s vegetative period. One potential strategy to mitigate the negative impacts of these changes involves the identification of grapevine varieties with superior water use efficiency, while ensuring satisfactory yields and grape quality.

Delimitation of Saint-Bris AOC: example of reasonning delimitation criteria from production customs

La définition de l’Appellation d’Origine précise que les caractères du produit doivent être dus au milieu géographique, celui-ci intégrant des facteurs naturels et humains.

Direct NMR evidence for the dissociation of sulfur-dioxide-bound acetaldehyde under acidic conditions: Impact on wines oxidative stability

SO2 reaction with electrophilic species present in wine, including in particular carbonyl compounds, is responsible for the reduction of its protective effect during wine aging. In the present study, direct 1H NMR profiling was used to monitor the reactivity of SO2 with acetaldehyde under wine-like oxidation conditions.

Mobilizing endogenous transposable elements for grapevine improvement: a genomic and epigenomic approach in New Zealand Sauvignon Blanc

Efforts to improve the New Zealand wine industry’s climate resilience and sustainability through grapevine improvement are limited by germplasm availability and a reliance on Sauvignon Blanc exports. To address this, we are working to generate a population of 12,000 individuals with unique genetic traits, from which to select future clones for major export varieties.

Sauvignon Blanc plantlets are being regenerated from embryogenic callus, using an approach designed to mobilise endogenous transposable elements as mutagens.

Capture depletion of grapevine DNA: an approach to advance the study of microbial community in wine

The use of next-generation sequencing (NGS) has helped understand microbial genetics in oenology. Current studies mainly focus on barcoded amplicon NGS but not shotgun sequencing, which is useful for functional analyses. Since the high percentage of grapevine DNA conceals the microbial DNA in must, the majority of sequencing data is wasted in bioinformatic analyses. Here we present capture depletion of grapevine whole genome DNA.