title: Pulse radiolysis and ultra-high-performance liquid chromatography/high-resolution mass spectrometry studies on the reactions of the carbonate radical with vitamin B12 derivatives.
abstract: The reactions of the carbonate radical anion (CO3 (.) (-) ) with vitamin B12 derivatives were studied by pulse radiolysis. The carbonate radical anion directly oxidizes the metal center of cob(II)alamin quantitively to give hydroxycobalamin, with a bimolecular rate constant of 2.0×10(9) M(-1) s(-1) . The reaction of CO3 (.) (-) with hydroxycobalamin proceeds in two steps. The second-order rate constant for the first reaction is 4.3×10(8) M(-1) s(-1) . The rate of the second reaction is independent of the hydroxycobalamin concentration and is approximately 3.0×10(3) s(-1) . Evidence for formation of corrinoid complexes differing from cobalamin by the abstraction of two or four hydrogen atoms from the corrin macrocycle and lactone ring formation has been obtained by ultra-high-performance liquid chromatography/high-resolution mass spectrometry (UHPLC/HRMS). A mechanism is proposed in which abstraction of a hydrogen atom by CO3 (.) (-) from a carbon atom not involved in the π conjugation system of the corrin occurs in the first step, resulting in formation of a Co(III) C-centered radical that undergoes rapid intramolecular electron transfer to form the corresponding Co(II) carbocation complex for about 50 % of these complexes. Subsequent competing pathways lead to formation of corrinoid complexes with two fewer hydrogen atoms and lactone derivatives of B12 . Our results demonstrate the potential of UHPLC combined with HRMS in the separation and identification of tetrapyrrole macrocycles with minor modifications from their parent molecule.
authors.affiliation: Department of Chemistry & Biochemistry, Kent State University, Kent, OH 44240 (USA).
authors.forename: Rohan S
authors.initials: RS
authors.lastname: Dassanayake
authors.forename: Jacob T
authors.initials: JT
authors.lastname: Shelley
authors.forename: Diane E
authors.initials: DE
authors.lastname: Cabelli
authors.forename: Nicola E
authors.initials: NE
authors.lastname: Brasch
mesh_terms: D002254:Carbonates / Q000737:chemistry; D002853:Chromatography, Liquid; D047028:Macrocyclic Compounds / Q000737:chemistry; D013058:Mass Spectrometry; D015394:Molecular Structure; D011675:Pulse Radiolysis; D014805:Vitamin B 12 / Q000031:analogs & derivatives* / Q000737:chemistry*
chemical_list: D002254:Carbonates; D047028:Macrocyclic Compounds; D014805:Vitamin B 12
keywords: carbonate radical; cobalamins; kinetics; pulse radiolysis; vitamin B12