Macrowine 2021

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…

The selection of Vitis vinifera L. cultivars based on berry texture, iPBS genetic markers, and noble rot susceptibility analysis

The selection of a suitable grape variety (Vitis vinifera L.) for specific viticulture and oenology objectives is a considerable challenge in the context of climate change.

Read More

Viticultural parameters and enological performance of six Merlot clones in two contrasting vintages

Vitis vinifera L. and other Vitis have high genetic variations for cultivars or varieties. Many countries carried out strong efforts creating new clones of varieties, mainly focusing on plants free of viruses and other grapevine diseases, but also on different agronomical and enological characteristics of the plants. The aim of this study was to evaluate six clones of Merlot in the traditional viticulture of southeastern Brazil, focusing on distinct characteristics of yield, enological potential of grapes and wine typicality, in order to improve wine quality.

Read More

Enhancing plant defense: carbon dots for efficient spray-induced gene silencing 

Ectopic RNA application for plant defense faces challenges in tree crops, including size, diffusion, and stability of active compounds such as ribonucleoproteins and nucleic acids. While existing strategies involve expressing dsRNA in transgenic plants targeting pathogens, our research strives to develop a transient RNAi system based on Spray-Induced Gene Silencing (SIGS). This approach aims to circumvent legal barriers and public concerns associated with genetically modified organisms (GMOs). Our strategy integrates SIGS with branched polyethyleneimine-functionalized Carbon Dots (bPEI-CDs) as nanocarriers, effectively addressing unique delivery challenges in plant defense as RNA stability and uptake enhancement

Read More

Influence du terroir et de la conduite du verger sur la vigueur, le développement et la productivité des pommiers. Conséquences sur la teneur en sucres des pommes

Dans le cadre d’une étude globale de l’influence du type de sol et de la conduite du verger sur la composition des pommes à cidre, une attention particulière est portée sur les facteurs amonts de la qualité comme

Read More

Evaluation of aroma characteristics in Vitis amurensis grapes across different regions by using HS-SPME-GC/MS

Background: Aroma compounds are important secondary metabolite in grapes and play important roles in the flavor and quality of grape berries and their wines. Vitis amurensis grape belongs to the East Asian Vitis spp., with excellent cold and disease resistance, and exhibits strong brewing potential. However, it has not been effectively utilized and there is no systematic research on the aroma compounds of V. amurensis grapes.
Methods: To provide sufficient experimental evidence for the characteristic aroma of V. amurensis grape, HS-SPME-GC/MS was used to identify the aroma compounds of five V. amurensis (‘Beiguohong’, ‘Beiguolan’, ‘Shuangfeng’, ‘Shuanghong’, ‘Shuangyou’) and three interspecific hybrids (‘Beibinghong’, ‘Xuelanhong’, ‘Zuoyouhong’) grapes in Zuojia and Ji’an. The grape berries were collected at harvest in 2020, 2021 and 2022.

Read More