Alternative Mechanisms of Betacyanin Oxidation by Complexation and Radical Generation
Abstract
The use of natural pigments such as betalains in food and health-related products is often limited by said pigments’ relative oxidative stabilities in the products or physiological matrices. Determination of the mechanism of oxidation may inform future development and delivery of better stabilized molecules for improved outcomes. In order to best determine the oxidation mechanism of betanin, a natural food colorant, our efforts were directed toward structural elucidation (LCMS-IT-TOF and NMR) of previously tentatively identified key dehydrogenation products that had been generated as a result of betanin, decarboxylated betanin, and neobetanin oxidation by 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) cation radicals. The resultant oxidation products, the neo-derivatives, were the most stable and survived the preparative isolation and purification process. Structural analyses subsequently confirmed that these compounds, as well as neobetanin, were also the key products of alternative pathways of betanin and 2-decarboxy-betanin oxidation when catalyzed by Cu 2+ cations in aqueous solutions at pH close to neutral. Therefore, the structures of the following five neo- or xanneo-derivatives (14,15- or 2,3,14,15-dehydrogenated derivatives, respectively) were confirmed: neobetanin, 2-decarboxy-neobetanin, 2-decarboxy-xanneobetanin, 2,17-bidecarboxy-xanneobetanin, and 2,15,17-tridecarboxy-xanneobetanin. This research confirmed that Cu 2+ -catalyzed oxidation of betanin and 2-decarboxy-betanin results in generation of neo-derivatives of betanin. In contrast, Cu 2+ -catalyzed oxidation of 17-decarboxy-betanin and 2,17-bidecarboxy-betanin resulted mostly in formation of betanin xan-derivatives. A relevant mechanism of Cu 2+ -catalyzed oxidation of the pigments is proposed herein that suggests that the oxidation of betanin can possibly occur in the region of the dihydropyridinic ring and can omit the stage of methide quinone formation in the dihydroindolic system.
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The bioactivity of betalains depends on stability within food matrices, as pH, temperature and light exposure can influence degradation and bioavailability.
“However, their bioactivity depends on stability within food matrices, as pH, temperature and light exposure can influence degradation and bioavailability [73,74].”
From Dietary Nitrate-Rich Vegetables as Natural Modulators of Health: Mechanisms and Benefits in Ageing Populations (2026) · cites this paper as [73]
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- Authors
- Kumorkiewicz, A., Szmyr, N., Popenda, Ł., Pietrzkowski, Z., & Wybraniec, S.
- Affiliations
- Department of Analytical Chemistry, Institute C-1, Faculty of Chemical Engineering and Technology, Cracow University of Technology, ul. Warszawska 24, Cracow 31-155, Poland
- Cracow University of Technology (PL)
- Adam Mickiewicz University in Poznań (PL)
- VDF FutureCeuticals, Inc. (United States) (US)
- Corresponding author
- Wybraniec, Sławomir
- Venue
- Journal of Agricultural and Food Chemistry
- Publisher
- American Chemical Society (ACS)
- Published
- 2019-06-03
- Volume
- 67
- Issue
- 26
- Pages
- 7455-7465
- ISSN
- 0021-8561 (ISSN-L)
- 1520-5118
- OpenAlex
- W2948959932
- Cited by
- 26
- References
- 30
- Citations by year
- 2026: 2 · 2025: 3 · 2024: 5 · 2023: 6 · 2022: 3 · 2021: 5 · 2020: 2
- FWCI
- 1.93
- Type
- journal article
- Language
- en
- Open access
- closed
- Licence
- Locations
- Journal of Agricultural and Food Chemistry (publishedVersion)
- PubMed (publishedVersion)
- Funders
- Narodowe Centrum Nauki (UMO-2014/13/B/ST4/04854)
- Topics
- Life Sciences › Agricultural and Biological Sciences › Food Science › Botanical Research and Applications
- Health Sciences › Medicine › Biochemistry › Phytochemicals and Antioxidant Activities
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Biotechnology › Microbial Metabolism and Applications
- Keywords
- betanin, betalains, oxidation mechanism, natural food colorants, oxidative stability
- MeSH terms
- Chromatography, High Pressure Liquid, Decarboxylation, Food Coloring Agents, Free Radicals, Oxidation-Reduction, Plant Extracts, Spectrometry, Mass, Electrospray Ionization, Beta vulgaris, Betacyanins
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