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…

Ripening of cv. Cabernet Sauvignon grapes: polysaccharides fractions evolution and phenolic extractability

Polysaccharides and more specifically pectins, make up a significant portion of the cell wall material of the plant cells including the grapes. During the fruit ripening the associated softening is related to the breakdown of the cell wall polysaccharides. During this process, it is expected that polysaccharides that are soluble in red wine will be formed influencing its texture. Anthocyanins are responsible for the wine color and tannins for the astringency, body and bitterness of the wine. In the skins, these compounds are located in the cell vacuoles and the barrier that conditions their extractability is the skin cell wall that may determine the mechanical resistance, the texture and the ease of processing berries. The aim of this work was study the evolution of the polysaccharides and the anthocyanin and tannin extractability during the ripening period in Cabernet Sauvignon grapes, trying to correlate these variables.

Simulating the impact of climate change on viticultural systems in various European vineyards

Aim: Global climate change affects regional climates and hold implications for wine growing regions worldwide (Jones, 2007, 2015; van Leeuwen and Darriet, 2016). The prospect of 21st century climate change consequently is one of the major challenges facing the wine industry (Keller, 2010).

Influence des facteurs naturels du terroir sur la maturation du raisin en Alsace

A study of the influence of environmental factors on the ripening of grapes under the conditions of Alsace is carried out. Emphasis is placed on the analysis of the mesoclimate and pedoclimate. The experiment is conducted on a network of plots of gewurztraminer grafted on SO4. The production conditions are standardized throughout the device.

From vine to wine : a multi-trait experiment for increasing the varietal diversity in the bordeaux wine region. How to adapt to climate change without damaging terroir expression?

Context and purpose of the study climate change is impacting wine typicity across the globe, raising concerns in wine regions historically renowned for the quality of their terroir. Replacing some of the plant material can be an efficient lever for adapting to climate change. However, the change of cultivars also raises questions about the region’s wine typicity. This study, based on seven years of data, investigates the potential adaptability of over 50 different varieties in the bordeaux wine region.

Volatile composition of Cabernet Sauvignon wines from Argentina, Portugal and Spain

Cabernet Sauvignon is one of the most cultivated grape varieties worldwide being grown in different environmental conditions due to its excellent adaptability. Volatile compounds deeply contribute to the sensory properties of wines therefore to wine quality. The aim of this work was to compare the aroma profile of Cabernet Sauvignon wines from different geographical areas and climatic conditions, namely from Argentina, Portugal and Spain, from the vintage 2022. In addition, the volatile composition of the Cabernet Sauvignon Portuguese wines from three vintages was evaluated.