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…

Monitoring of Sangiovese red wine chemical and sensory parameters along one-year aging in different tank materials and glass bottle

The aim of this study was to test how different tank materials could affect the chemical composition and the sensory profile of a red wine during an entire year of aging. For this scope, a single varietal Sangiovese wine was aged, after completing its malolactic fermentation, by using tanks made by different materials. Six thesis were involved in the aging experiment, in particular: stainless

Read More

Viticultural zoning in D.O.C. Ribeiro (Galicia, NW Spain)

L’AOC Ribeiro est la plus ancienne de Galice (NO de l’Espagne), avec une aire de production potentielle de 3.200 ha. Situé dans la région centrale de la vallée du Miño, le Ribeiro a un climat de tipe maritime tempéré qui se correspond avec la zone climatique II de Winkler.

Read More

Polyphenolic profile and dietary fiber content of skins and seeds from unfermented and fermented grape pomace

The valorization of winemaking byproducts is subordinated to the knowledge of their chemical characteristics. This work concerned the determination of the polyphenolic profile and the dietary fiber content of skins and seeds from unfermented and fermented pomace of different cultivars (Moscato bianco, Cortese, Arneis, Pinot Noir, Barbera, Grignolino, Nebbiolo), sampled from some wineries in the Piedmont area (Italy) during the 2020 harvest.

Read More

Optimization of aroma production in grape cell suspensions induced by chemical elicitor

Methyl-jasmonate (MeJA) induces the production of at least 25 compounds with sesquiterpene- like mass spectra in ‘Cabernet sauvignon’. Tost effective concentration of MeJA in stimulating the production of sesquiterpenes was found to be 500 µM if added when the cell suspensions had a PCV of 35 %, and 1000 if added when the cell suspensions had a PCV of 70 %.

Read More

Interest and impact of PVP/PVI (Polyvinylpyrrolidone/ Polyvinylimidazole) on winemaking and final quality of wines

Céline Sparrow a, Christophe Morge a, a SOFRALAB SAS, 79, av. A.A. Thévenet – CS 11031 – 51530 Magenta, France Consumers’ health and security force authorities to limit, in wine as in others food industry products, the concentration in « dangerous » molecules. Therefore the legal limit in heavy metals keeps on decreasing. As per proof EU regulation just decrease the stain concentration in wine from 0,2 to 0,15 mg/l. Certain changes , such as sodium arsenite treatment in vines, disappearance of brass in wineries to the benefit of stainless steel, limit even more the concentration of heavy metals in wines. But the use of copper derivates in vines treatments is difficult to replace. In the case of wine and its elaboration, the problem is even more complex. Indeed, regulation forces the wine producers to control the concentration of certain heavy metals in final wines.

Read More