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…

Intravarietal diversity: an opportunity for climate change adaptation

Merlot grapevine is the second wine cultivar most planted in the world and especially in the Bordeaux wine region. This cultivar has many advantages in producing high quality wine; however, in the last decade, climate change has increased the sugar concentration in berries at harvest and shortened the maturation cycle. If this has been up to now a great opportunity to improve wine quality profile, we are touching the tipping point. High sugar concentration at harvest induces high alcool content in wine which can negatively impact wine quality. There are many viticultural and oenological practices possible to limit this effect. In this study we focus on plant material through intra-varietal diversity of Merlot cultivar.

Chemical and biochemical formation of polysulfides in synthetic and real wines using UHPLC-HRMS

ulfur compounds in wine have been studied for several years due to their impact on wine flavour, but the role of polysulfides is a recent topic. Polysulfides in wine are formed when two sulfhydryl groups oxidize, especially in presence of elemental sulfur or metal catalysts from field treatment residues (Ugliano et al. 2011). These compounds are odourless, but can degrade during storage and affect the wine quality. The mechanism of their formation is still largely unknown but different chemical and biochemical pathways have been suggested. Disulfides from cysteine (Cys) and glutathione (GSH) have been revealed in model wines (Kreitman et al. 2016) and more recently also higher polymerized forms in real wines (Van Leeuwen et al. 2020). Volatile varietal thiols like 3-mercaptohexanol (3MH) and 4-mercaptopentanone (4MMP) – flavour compounds with tropical or fruity notes – could undergo similar reactions, also with Cys and GSH, subsequently losing their flavour property (fate). Even more concerning is the possible release of H2S from polysulfides during storage, leading to undesired off-flavours (Sarrazin et al. 2010).

Switch genes as a key to understand the grapevine ripening disorder berry Shrivel?

The ripening of grapevine berries encompasses complex morphological and physiological processes, especially at veraison. Berry shrivel (BS) is a ripening physiological disorder affecting grape berries with visible symptoms appearing short after veraison. The main symptoms of BS are a strong reduction in sugar accumulation, inhibited anthocyanin biosynthesis and high pH values. The most popular red grape cultivar in Austria “Blauer Zweigelt” (Vitis vinifera L.) is specifically prone to develop the BS ripening disorder and up to date a no specific cause or causes could be identified. Recently omics approaches have identified and characterized key processes during grapevine ripening. Among them a small subset of genes, called SWITCH, have been described as markers for the onset of the ripening process in fruits.

A browser application for comprehensive 3-dimensional LC × LC × IM – MS data analysis to study grape and wine polyphenols

The analysis of structurally diverse proanthocyanidins in grapes and wine is challenging. Comprehensive two-dimensional liquid chromatography (LC×LC) and ion mobility spectrometry-mass spectrometry (IMS-MS) are increasingly used to address the challenges associated with the analysis of highly complex samples such as wine and grapes

Biotype diversity within the autochthonous ‘Bobal’ grapevine variety

Bobal is the second most widely grown Spanish red grape variety (54,165 has), mainly cultivated in the Valencian Community and especially, in Utiel-Requena region (about 67% of 34,000 has). In this study, agronomic and enological parameters were determined in 98 biotypes selected during 2018 and 2019 in more than 50 vineyards over 50 years-old in the Utiel-Requena region. Moreover, a multi-criteria approach considering temperature and rainfall (Fig. 1A), among other parameters, was made to establish three different zones within the region (Fig. 1B), where in the future the selected biotypes will evaluated. In fact, in 2020, 4 replicates and 12 vines per biotype were planted in an experimental vineyard to preserve this important intra-cultivar diversity.