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…

Podcasts – Terroir Congress 2020

All about “Australian grapevine stories”

Optimised extraction and preliminary characterisation of mannoproteins from non-Saccharomyces wine yeasts

The use of non-Saccharomyces yeast species for the improvement of wine technological and oenological properties is a topic that has gained much interest in recent years [1]. Their application as co-starter cultures sequential to the inoculation of Saccharomyces cerevisiae and in aging on the lees has been shown to improve aspects such as protein stability and mouthfeel [2].

Effect of ozone application for low-input postharvest dehydration of wine grapes 

The postharvest dehydration of grapes is a traditional practice to obtain wines with unique traits (e.g. sweet, dry/reinforced). The modern facilities (dehydrating rooms) used for this purpose are equipped with systems for artificially controlling the inside environment parameters, to obtain the desired dehydration kinetic and preserve the grapes from grey mold (Botrytis cinerea) infection, However, the conditioning systems are extremely energy-demanding and the identification and practical applications of solutions effective in controlling/reducing the postharvest decay would reduce the costs of the operation of the dehydration facilities. To this end, we explored the potential of ozone-based treatments on harvested grapes and preliminarily tested if the treatment could impact the normal behavior and metabolism of grapes during the traditionally slow dehydration practice.

Trends and challenges in International Wine Trade. The need for new strategies for companies and regions.

Trends already extended for more than 12 years show a decline in both consumption and international trade, particularly in volume. However, there are also positive signs in several categories of wine, segments and markets, as well as a better trend in terms of value. How are these trends affecting wine producers and distributors? Are they short or long term? do they mean radical and permanent changes to which a way of adaptation has to be found or are they just temporary changes that may only require some calm? How are companies adapting to these new trends? Which are their effects on wine regions?

Function, barriers, and the environmental benefits of reuse bottle system for wine

With 0.3 to 0.7 kg CO2eq per 0.75 L wine, the glass bottle is the main contributor to the carbon footprint of a bottle of wine.