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…

From grapes to sparking wines: Aromas evaluation in a vine-spacing

Aim: Wine aromatic profile is a combination of viticulture and oenological practices and it is related to character, quality, and consumer acceptance. Based on the competition between soil capacity and canopy development, and on the potential to produce sparkling wines at Caldas, in the south region of Minas Gerais (Brazil) (21°55´S and 46°23´W, altitude 1.100m), the aim of this work was the evaluation of the development of aromas (secondary metabolites) from grapes to sparkling wines in a vine-spacing experiment and whether the distance between the vines can influence the aromatic profile of the sparkling wines (final product). 

Fine-scale projections of future climate in the vineyards of southern Uruguay

In viticulture, climate change significantly impacts the plant’s development and the quality and characteristics of wines. These variations are often observed over short distances in a wine-growing region and are linked to local features (slope, soil, seasonal climate, etc.). The high spatial variability of climate caused by local factors is often of the same order or even higher than the temperature increase simulated by the different IPCC scenarios.

Antioxidant activity of yeast peptides released during fermentation and autolysis in model conditions

Aging wine on lees benefits different wine sensory and technological properties including an enhanced resistance to oxidation. Several molecules released by yeast, such as membrane sterols and glutathione, have been previously proposed as key factors for this activity [1].

Emerging pest pressures in viticulture: a brief review of Argyrotaenia Ljungiana in Eastern Europe

As viticulture faces increasing threats from emerging pests, understanding and dealing with new infestations is crucial.

Application of remote sensing by unmanned aerial vehicles to map variability in Ontario Riesling and Cabernet Franc vineyards

The objective of this investigation was to verify usefulness of proximal sensing technology and unmanned aerial vehicles (UAVs) for mapping variables e.g., vine size (potential vigor), soil and vine water status, yield, fruit composition, and virus incidence in vineyards.