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…

Territoires et zones viticoles. Aspects climatiques, pédologiques, agronomiques. Caractérisation des terroirs viticoles: une étude systémique

On assiste actuellement à l’émergence d’une demande sociale forte à l’égard de fonctions par ailleurs traditionnelles de l’agriculture, qui concernent la gestion des ressources du milieu, le maintien d’un tissu social rural, la valorisation des territoires ruraux et l’entretien des paysages.

Managing changes in taste: lessons from champagne in britain 1800-1914

This paper focuses on how taste in wine (and other foods) changes and the implications of this process
for producers and merchants.
It draws primarily on the changing taste of and taste for champagne in Britain in the 19th century. Between 1850 and 1880 champagne went from a dosage level of around 20% (20 grams sugar / litre) to 0%. Champagne became the ‘dinner wine of the elite – drunk with roast meat and savoury dishes.
Contemporaries accepted that while most people could distinguish the taste of good champagne from that of bad, very few could distinguish very good from good.

Aroma profile of ‘Pedro Ximenez’ sweet musts obtained from dried grapes by different methods

Aroma fraction of musts from grapes ‘Pedro Ximenez’ traditionally sun-dried and chamber-dried at 40 ºC and at 50 ºC during 8, 5 and 4 days respectively, destined for the production of sweet wines in Montilla-Moriles region (southern Spain) was studied.

From the “climats de Bourgogne” to the terroir in bottles

From a chemical composition point of view, wine is the result of complex interplays between environmental, genetic and human factors. The notion of terroir in viticulture involves the vine and its environment, including phenology, geography, geology, pedology and local climate of a vineyard, along with human inputs.

Changes in grape-associated microbiome as a consequence of post-harvest withering

AIM: Grape withering is an oenological post-harvest process used for production of reinforced and sweet wines. Drying can be carried out by keeping the ripe grape in traditional large, well-aired rooms (non-controlled environment) or, more and more often, in a warehouse under controlled conditions of airflow and relative humidity (controlled environment)[1].