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…

Chemical and sensory evaluation of Bordeaux wines (Cabernet sauvignon and Merlot) and correlation with wine age

This study was carried out on 24 vintages of Cabernet sauvignon and on 7 vintages of Merlot produced by two different Bordeaux growing areas. Proanthocyanidin monomers and oligomers, and several parameters of the proanthocyanidin fraction were analytically assessed.

Metabolomic fingerprint changes during the alcoholic fermentation at industrial level of Muscat of Alexandria grape must

Muscat of Alexandria is one of the oldest cultivars still existing, globally recognized for its distinctive aroma, and the primary grape variety cultivated in the Greek Island of Lemnos, yielding various white wines with designated origins.

Simulated climate change in a Mediterranean organic vineyard altered the plant physiology and decreased the vine production

This study focuses on investigating the effects of climate change on the plant physiology and berries of Vitis vinifera cv “Monastrell” in a commercial vineyard managed organically in Southeastern Spain (Jumilla, Murcia). For this purpose, open top chambers and rainout shelters were employed to simulate warming (~2-7 ºC, W) and rainfall reduction (~30%, RR) respectively. Additionally, a combination of both treatments (W+RR) was employed. Vines without either top chambers or rainout shelters were considered as control (C). The experiment was established in February of 2023. Predawn leaf water potential (measured using a pressure chamber), stomatal conductance (assessed with a porometer at mid-morning) and leaf chlorophyll and flavonoid content (measured using the Dualex® leaf clip sensor) were analyzed at veraison (5 months after the installation of structures).

Analysis of mousy off-flavour wines

Winemakers are increasingly experimenting with new techniques, such as spontaneous fermentation, prolonged yeast contact, higher pH, minimal sulphur dioxid, filtration and clarification or oxidative ageing. Along with this, the risk of microbial spoilage increases, and so the off-flavour mousiness, long time underestimated, is becoming more frequent. Characteristic of the mousy off-flavour is the delayed perception after swallowing the wine. After a few seconds the flavour appears, reminiscent of a dirty mouse cage. There are three known compounds that cause mousy off-flavor: 2-ethyltetrahydropyridine, 2-acetyltetrahydopyridine, and 2-acetylpyrroline. Yeasts such as Dekkera/Brettanomyces and heterofermentative lactic acid bacteria like Lactobacillus hilgardii can release these compounds.

Organic volatile compounds as suitable markers of grapevine response to defense elicitors in the vineyard

In greenhouse, emission of volatile organic compounds (VOC) by grapevine leaves has already been reported in response to the defence elicitor sulfated laminarin (PS3) [1]. In order to check that this response was not specific to PS3, experiments were conducted on Vitis cv Marselan plantlets with several other elicitors of different chemical structures: i.e. Bastid® (COS-OGA),