The adducts of cyano- and aquacobalamin with hypochlorite

Hypochlorite is known to oxidatively degrade the corrin ring of cobalamin. Here, transient reaction intermediates are described in the reaction of aqua as well as of cyano-cobalamin with hypochlorite, using stopped-flow UV–vis kinetics. For aqua-cobalamin, the intermediate is assigned as arising fro...

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Published inJournal of biological inorganic chemistry Vol. 28; no. 6; pp. 583 - 589
Main Authors Lehene, Maria, Brânzanic, Adrian M. V., Silaghi-Dumitrescu, Radu
Format Journal Article
LanguageEnglish
Published Cham Springer International Publishing 01.09.2023
Springer Nature B.V
Subjects
Benzimidazoles
Biochemistry
Biomedical and Life Sciences
Inorganic chemistry
Intermediates
Life Sciences
Microbiology
Original Paper
Vitamin B12
UV–vis
DFT
Hypochlorous acid
Cobalt
Vitamin B
Stopped-flow
Vitamin B12
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Summary:Hypochlorite is known to oxidatively degrade the corrin ring of cobalamin. Here, transient reaction intermediates are described in the reaction of aqua as well as of cyano-cobalamin with hypochlorite, using stopped-flow UV–vis kinetics. For aqua-cobalamin, the intermediate is assigned as arising from substitution of the aqua ligand with hypochlorite. For cyano-cobalamin, the intermediate is proposed to arise from substitution of the benzimidazole ligand trans to the cyanide. In both cases, the intermediates would feature a new Co(III)-OCl − bond—which is also supported by density functional theory (DFT) calculations. Graphical abstract
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ISSN:1432-1327
0949-8257
1432-1327
DOI:10.1007/s00775-023-02015-z