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…

Chemistry and analysis of key volatile compounds of wine and their precursors in grape

A relatively small number of the many volatile substances of wine, often present at trace
concentrations, are considered as key volatile compounds. These compounds often exist in grapes
under poorly odoriferous or non volatile forms as aroma precursors.

Impact of fining agents on Swiss Pinot noir red wines

In the context of climate change, excessive bitterness and astringency in wines have become increasingly prevalent. While variety selection and viticultural practices offer long-term solutions, they require considerable time before yielding practical results. In contrast, fining remains an accessible and immediate tool for winemakers.

The effects of antioxidants and gas sparging on New Zealand white wines

This study aims to investigate the effects of different conditions of grape processing or fermentation on the aroma profile of New Zealand white wines.

Mapping grape composition in the field using VIS/SWIR hyperspectral cameras mounted on a UTV

Assessing grape composition is critical in vineyard management. It is required to decide the harvest date and to optimize cultural practices toward the achievement of production goals. The grape composition is variable in time and space, as it is affected by the ripening process and depends on soil and climate conditions.

Determination of metallic elements in Chilean wines by atomic absorption spectroscopy and inductively coupled plasma–mass spectrometry

The chemical composition of wines depends on series of variables such as the type of grape, edaphoclimatic conditions, and viticulture and winemaking practices employed during production. Metallic elements play a significant role during winemaking (e.g. as catalysts of oxidation reactions) and have been previously employed for the classification of wines according to provenance. In this work, we focused on the analysis of metallic elements (K, Na, Ca, Zn, Cu, Fe, Mg, Mn, Ni, Cr, Al, Pb, Cd, Hg, Se, Co, Sn and As) in 145 Chilean wine samples (102 reds and 43 white wines), of seven grape varieties, and five of the major wine producing regions in Chile.