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…

Climatic influences on Mencía grapevine phenology and grape composition for Amandi (Ribeira Sacra, Spain)

During the year 2009 we have studied the phenology and grape composition of Mencía cultivar in seven different situations (orientation and altitude) for Amandi subzone

First characterization of thiol precursors in colombard and gros manseng: comparison of two cultivation practices

AIM: Organic production of wine in the past years has known an important augmentation. This type of cultivation practice switches synthetic phytosanitary product for copper-based protection as fungicide.

Bioprotective non-Saccharomyces yeast as an alternative to sulfites for the winemaking process

Sulfur dioxide (SO2) is used in winemaking due of its antioxidant, antioxydasic and antiseptic properties. Excessive amount of SO2 can negatively impact wine sensory perception and be detrimental for health. Agri-food industries are more transparent towards consumers concerning addition of sulfites, and oenology is no exception in this clairvoyance. As a consequence, the increase of consumers preference for wine with low or absent of sulfites addition is notorious. In this context, the impact of low/zero sulfites winemaking process on the microbial community should be evaluated. Moreover, microbial agents corresponding to bioprotective cultures represent a growing interest as an alternative to sulfites preservation in the early stages of vinification. However, scientific studies conducted to demonstrate their real effect are almost rare.

Nutrients and heavy metals in a vineyard soil under organic, biodynamic and conventional management

Promoting sustainable agricultural practices is one of the challenges of the last decades. Organic and biodynamic viticulture can be an alternative to intensive viticulture, furthermore contributing to reduction of impact on environment and human health and guaranteeing soil preservation and quality products1. The aim of this experimentation was to evaluate the medium and long-term effects of different agronomic practices in viticulture on nutrient availability and heavy metal accumulation in soil.

Biodiversity and biocontrol ability of Trichoderma natural populations in soil vineyards from Castilla y León region (Spain)

Trichoderma is a microorganism present in many agricultural soils and some of its species could be used as natural biological control agents. In this work, the presence of natural populations of Trichoderma was estimated in soil vineyard and its biocontrol capacity against Phaeoacremonium minimum, one of the main agent causals of grapevine trunk diseases instead of using pesticides. Moreover, physicochemical variables in soil such as pH, organic matter and nutrients were evaluated to determine a possible correlation to natural populations of Trichoderma.