Macrowine 2021

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 influence of different fertiliser applications and canopy management practices on the potassium content and pH of juice and wine of Vitis vinifera L. cvs. Cabernet-Sauvignon and Cabernet franc

In an attempt to reduce the pH of juice and wine, different fertiliser applications and canopy management practices were evaluated in South Africa in a field trial. Fertiliser treatments entailed no, CaSO4, Ca(OH)2, and MgSO4 fertilisation.

Read More

Rapporti tra diverse tipologie di terreno e risposte produttive e qualitative delle uve Merlot e Carmenère nell’area DOC Piave

Da anni la ricerca viticola sta orientando le sue attenzioni verso lo studio della vocazionalità degli ecosistemi viticoli, perché fulcro della produttività della vite e qualità dei suoi frutti.

Read More

Sensory profile of wines obtained from disease-resistant varieties in La Rioja

The European wine industry is facing multiple challenges derived from climate change and the pressure of different fungal diseases that are compromising the production of traditional varieties. A sustainable alternative maybe the adoption of resistant varieties.
In this study, we have evaluated the enological potential of 9 resistant varieties (5 white and 4 red varieties) in La Rioja. Microvinifications were carried out with three biological replications. Oenological parameters were very diverse with acid content varying from 2.6 g/L to 6.6 g/L.

Read More

Développer des outils simples pour accompagner les viticulteurs dans leurs changements de pratiques et répondre aux enjeux du siècle à venir

French viticulture is currently facing major challenges as it enters the new century: climate change, the need to reduce inputs, societal issues, changing consumer habits, labor shortages …. Vinopôle bordeaux-aquitaine, to which the teams from the chambre d’agriculture de la gironde belong, supports winegrowers of the gironde and bergerac-duras regions in the gradual evolution of their practices.

Read More

Seed phenolics oxidation: development of a new ripening index 

During ripening seed tannins evolve, as demonstrated by the taste and color changes. In this work we tried to develop an objective, easy and fast index, useful for winemakers. In this direction we propose two different spectrophotometric indexes, one related to the molecular structure and tannin subunits linkages, and the other related to the antioxidant properties. Especially the second one gave very interesting and unexpected results.

Read More