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…

Polysaccharides and glycerol production by non-Saccharomyces wine yeasts in mixed fermentation

A great variability in the amount of polysaccharides recovered at the end of fermentations carried out by pure cultures of 89 non-Saccharomyces yeasts was observed. The utilization of the best polysaccharides producers in mixed cultures with S. cerevisiae resulted in considerable increases in the final concentration of polysaccharides and showed a strain dependent effect on glycerol production as compared to pure culture of S. cerevisiae.

Launching the GiESCO guide

Considering that the transfer of research results to the professional level is one of the keys to progress, GiESCO proposes to publish a technical guide supported by scientific references and in the form of standard sheets.

Grapevine downy mildew development as affected by chitosan spray treatments and metabolomics implications

Chitosan has been shown to enhance grapevine tolerance toward downy mildew while reducing the environmental impact of traditional protection products.

Tutela legale delle denominazioni di origine nel mondo (con aspetti applicativi)

Uno degli aspetti più importanti nel commercio internazionale dei vini a denominazione è quello del riconoscimento dei diritti di esclusiva garantiti sui e dal territorio geografico d’o­rigine. Al fine di cautelarsi nei confronti della sempre più agguerrita concorrenza mondiale, è opportuno adottare adeguate protezioni ufficiali e legali delle denominazioni che possono derivare sia dalla “naturalità” del prodotto stesso che dalla “originalità” più particolare.

Study of the vine performance and the wine composition of Tannat on the terroir of Colonia del Sacramento – Uruguay

Grape-growing terroirs were defined according to the method proposed by Falcetti and Asselin (1996) near of Colonia de Sacramento, a city of Uruguay situated on the left of the “Rio de la Plata”.