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…

Effect of different plant fibers on the elimination of undesirable compounds in red wine. Correlation with its polysaccharide composition

The presence of undesirable compounds in wines, such as OTA, biogenic amines and pesticides residues, affects wine quality and can cause health problems for the consumer. The main tool that a winemaker has to reduce their content in the wine is fining. However, some of the fining agents commonly used in the winery can cause allergies or even increase the protein content in the wine, increasing the turbidity. To avoid these problems, the use of plant fibers may be an alternative, such as those from grape pomace[1] or other plant origins.

Read More

Climate change, regional adaptation necessities and impact on grape and wine composition – an integrated view on a moving target

Grapevines are cultivated on 6 out of 7 continents, roughly between latitudes 4° and 56° in the Northern Hemisphere and between 6° and 42° in the Southern Hemisphere across a large diversity of climates (oceanic, warm oceanic, transition temperate, continental, cold continental, Mediterranean, subtropical, attenuated tropical, and arid climates).

Read More

On the impact of preformed α-dicarbonyls in the production of Strecker aldehydes. Exploring the addition of sacrificial amino acids as a tool to reduce Strecker aldehydes production

The reaction between Strecker amino acids and α-dicarbonyls is a key pathway in the formation of Strecker aldehydes (SA), which are crucial oxidation-related odorants in wine [1].

Read More

Staying hydrated – not easy when it’s hot!

Heat and drought episodes during the growing season are becoming more frequent and more severe in many of the world’s grape‐growing regions

Read More

Climate, grapes, and wine: structure and suitability in a variable and changing climate

Climate is a pervasive factor in the success of all agricultural systems, influencing whether a crop is suitable to a given region, largely controlling crop production and quality

Read More