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 one-year cover crop and arbuscular mycorrhiza inocululation in the microbial soil community of a vineyard

The microbial composition of the soil is an important factor to consider in viticulture, since its influence on the “terroir” and on the organoleptic properties of the wine have been demonstrated. Different agronomic techniques have the potential to modify the composition and functionality of the soil microbial community. Maintaining green covers is known to increase soil microbial diversity. The direct application of inoculum of beneficial microorganisms to the soil has also been used to increase their abundance. However, the environmental conditions of each site seem to have a determining weight in the result of these practices. In this study, we compared the effect on the microbial community of a cover crop with legumes in autumn and the inoculation of grapevines with commercial inoculum bases on Rhizophagus irregularis and Funeliformis mosseae in the previous spring. The study has been carried out in a vineyard in Binissalem, Mallorca, Spain. After applying the treatments, we will analyze the soil microbial communities using the data obtained from Illumina amplification of soil DNA from the 16S and ITS regions to analyze bacteria and fungi community, respectively. In addition, we will record the physicochemical characteristics of the soil at each sampling point. The result showed that agronomic management, in the short term, has less influence than soil characteristics on the composition of the soil microbiome. With these results, we can conclude that in a vineyard, agricultural techniques should focus on improving the characteristics of the soil to improve the biodiversity of the soil microbiota.

Early fermentation aroma profiles of grape must produced by various non-Saccharomyces starters

Saccharomyces cerevisiae is the most commonly used yeast species in winemaking. The recent research showed that non-Saccharomyces yeasts as fermentation starters show numerous beneficial features and can be utilized to reduce wine alcoholic strength, regulate acidity, serve as bioprotectants, and finally improve wine aromatic complexity. The majority of published studies on this topic investigated the influence of sequential or co-inoculations of non-Saccharomyces and S. cerevisiae yeasts on the aroma of final wine.

Investigating three proximal remote sensing techniques for vineyard yield monitoring

Yield monitoring can provide the winegrowers with information for precise production inputs during the season, thereby, ensuring the best possible harvest. Yield estimation is currently achieved through an intensive process that is destructive and time-consuming. However, remote sensing provides a group of proximal technologies and techniques for a non-destructive and less time-consuming method for yield monitoring.The objective of this study was to analyse three different approaches, for measuring grapevine yield close to harvest.

Influence of Potential Alcohol and pH Adjustment on Polyphenols and Sensory Characteristics of Red Wines Produced at Different Harvest Time Points

Wine quality is influenced by grape maturity, typically monitored by measuring sugar content and acidity.

EFFECTIVENESS OF APPLIED MATERIALS IN REDUCING THE ABSORPTION OF SMOKE MARKER COMPOUNDS IN A SIMULATED WILDFIRE SCENARIO

Smoke taint (ST) is a grape-wine off-flavour that may occur when grapes absorb volatile phenols (VPs) originating from wildfire smoke (1). ST is associated with the negative sensory attributes such as smoky and ashy notes. VPs are glycosylated in the plant and thus present in both free and bound forms (2; 3). Wildfire smoke has resulted in a decline in grape and wine quality and financial losses which has become a prominent issue for the global wine industry.