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…

Heat waves and drought stress impact grapevine growth and physiology

Recurring heat and drought episodes during the growing season can produce adverse impacts on grape production in many wine regions around the world.

100 ans d’évolution des règles relatives à l’encépagement des AOC viticoles françaises : quelles perspectives face aux enjeux contemporains

To characterize a wine, the most frequently used criteria describe its color, its origin, the grape varieties from which they come, or even for white wines its residual sugar content (dry, semi-dry, sweet). In france, the system of appellations of origin set up in 1919 was initially based solely on the notoriety and origin of the wines. But given the unfavorable consequences that this lack of details generated, the public authorities quickly integrated in 1927 into the “capus” law criteria for access to designations of origin, relating to the specific characteristics of the soils of the vineyards and the grape varieties used, in particular exclusion of interspecific hybrid varieties. In 1935 the creation of the aoc system confirmed the interest in precisely defining all the production conditions that must be implemented to be able to claim the benefit of an aoc, and grape varieties were an essential condition for acquisition.

Mechanisms involved in the heating of the environment by the aerodynamic action of a wind machine to protect a vineyard against spring frost

One of the main consequences of global warming is the rise of the mean temperature. Thus, the heat summation by the plants begins sooner in the early spring, and by cumulating growing degree-days, phenological development tends to happen earlier. However, spring frost is still a recurrent phenomenon causing serious damages to buds and therefore, threatening the harvests of the winegrowers. The wind machine is a solution to protect fruit crops against spring frost that is increasingly used. It is composed of a 10-m mast with a blowing fan at its peak. By tapping into the strength of the nocturnal thermal inversion, it sweeps the crop by propelling warm air above to the ground. Thus, stratification is momentarily suppressed. Furthermore, the continuous action of the machine, alone or in synergy, or the addition of a heater allow the bud to be bathed in a warmer environment. Also, the punctual action of the tower’s warm gust reaches the bud directly at each rotation period. All these actions allow the bud to continuously warm up, but with different intensities and over a different period. Although there is evidence of the effectiveness of the wind machines, the thermal transfers involved in those mechanisms raise questions about their true nature. Field measurements based on ultrasonic anemometers and fast responding thermocouples complemented by laboratory measurements on a reduced scale model allow to characterize both the airflow produced by the wind machine and the local temperature in its vicinity. Those experiments were realized in the vineyard of Quincy, in the framework of the SICTAG project. In the future paper, we will detail the aeraulic characterization of the wind machine and the thermal effects resulting from it and we will focus on how the wind machine warms up the local atmosphere and enables to reduce the freezing risk.

FUNGAL DIVERSITY AND DYNAMICS IN CHAMPAGNE VINEYARDS: FROM VINE TO WINE

Champagne is a well-known wine region in Northern France with distinct terroirs and three main grape varieties. As for any vineyard, wine quality is highly linked to the microbiological characteristics of the raw materials. However, Champagne grape microbiota, especially its fungal component, has yet to be fully characterized. Our study focused on describing this mycobiota, from vine to small scale model wine, for the two main Champagne grape varieties, Pinot Noir and Meunier, using complementary cultural and omics approaches.

Terroir effects on the response of Tempranillo grapevines to irrigation in four locations of Spain: agronomic performance and water relations

We report the effects of different drip irrigation treatments on the agronomic performance and water relations of Tempranillo grapevines, pruned to a bilateral cordon