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…

Study of the content of amino acids and biogenic amines in sparkling red wines

The production of red sparkling wines is lower in Spain in comparison with the winemaking of white or rosé sparkling wines. In red sparkling wine processing it is essential to obtain suitable base wines that should have moderate alcohol content, high acidity, good color values, an adequate mouth-feel and a sweet tannin. Grapes for sparkling wine production have to be harvested at low maturity stages, with lower alcohol contents and higher acidities, which will that the phenolic maturity of the grapes is also low, showing green tannins. This paper analyses different treatments in order to minimize these inconveniences: cold maceration-prefermentation and delestage to elaborate the grapes with lower maturity, must nanofiltration, and the partial osmosis of the wines made from grapes with an adequate maturity degree.

Mousy off-flavor detection: a rapid LCMS/MS method

These days, consumers are interested in food products linked to the environment and the concept of naturalness. They prefer “free” products, such as those with no pesticide residues or no added sulfur dioxide (so2) in wines. In fact, so2 is the most widely used preservative in winemaking, as it has multiple properties at low cost: it is antioxidant, antioxidasic and antimicrobial.

Influence of early leaf removal on the yield and composition of the grape of three white varieties in the D.O.Ca.Rioja (Spain)

Defoliation is one of the green operations more used in viticulture, whose results can be very different depending on the variety and the moment of realization. Early leaf removal consists of the elimination

Enological characterization of mold resistant varieties grown in the Trentino Alpine Region

Among the different strategies used in vine growing to fight against mold diseases, it can be pointed out the hybridation of traditional grape varieties with others, presenting a genetic resistance to pathogen attack. The research in this field has been encouraged in recent years due to the increased concern about human safety and environmental pollution linked to the use of agrochemicals. This approach allows to limit the number of treatments and the type of active compounds used in vine management. The environment determines the pressure degree of the diseases on vines and the biologic response of the plant to their attack.

Dispersive liquid-liquid microextraction for the quantification of terpens in wines

In a highly competitive worldwide market, a current challenge for the beverage sector is to diversify the range of products and to offer wines and spirits with typicity and character.

During alcoholic fermentation, wine yeasts generate a large variety of volatile metabolites, including acetate esters, ethyl fatty acid esters, higher alcohols, volatile fatty acids and volatile sulfur compounds that contribute to the aroma profile of wine. These molecules, refered as fermentative aromas, are the most abundant volatile compounds synthetized by yeasts and the metabolic pathways involved in their formation have been well characterized. Furthermore, other molecules with a major organoleptic impact may be produced during wine fermentation including terpene derivatives. However, little information is available on the contribution of yeasts to the formation of these molecules, in particular on their ability to synthethise de novo the terpens derivatives or to produce hydrolytic enzymes involved in the release of varietal precursors.