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Mechanistic information on the nitrite-controlled reduction of aquacob(III)alamin by ascorbate at physiological pH.

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Mechanistic information on the nitrite-controlled reduction of aquacob(III)alamin by ascorbate at physiological pH.

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Polaczek, Justyna Orzel, Lukasz Stochel, Grazyna Van Eldik, Rudi
Description	Country affiliation: Poland Author Affiliation: Polaczek J ( Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060, Kraków, Poland.)
Abstract	The interaction with nitric oxide (NO) is an important aspect of the biological activity of vitamin B12 (Cbl). Whereas the formation of nitroxylcobalamin (CblNO) via the binding of NO to reduced CblCo(II) has been studied in detail before, the possible intracellular formation of CblNO via reduction of nitrocobalamin (CblNO2) is still questionable. To study this further, spectroscopic and kinetic studies on the reaction of CblNO2 with the intracellular antioxidant ascorbic acid (Asc) were performed in aqueous solution at the physiological pH of 7.2. It was found that the redox pathway of this reaction requires anaerobic conditions as a result of the rapid re-oxidation of reduced CblCo(II). In the studied system, both CblOH2 and CblNO2 are reduced to CblCo(II) by ascorbate at pH 7.2, the CblOH2 complex being two orders of magnitude more reactive than CblNO2. Clear evidence for redox cycling between CblOH2/CblNO2 and CblCo(II) under aerobic conditions was observed as an induction period during which all oxygen was used prior to the formation of CblCo(II) in the presence of an excess of ascorbate. No evidence for the intermediate formation of CblNO or NO radicals during the reduction of CblNO2 could be found. Nitrocob(III)alamin can be reduced by ascorbic acid under physiological conditions. The products of the reaction are cob(II)alamin and nitrite ion. This reaction is ca. 200 times slower than the one involving aquacob(III)alamin.
File Format	HTM / HTML
ISSN	09498257
Issue Number	6
Volume Number	20
e-ISSN	14321327
Journal	JBIC Journal of Biological Inorganic Chemistry
Language	English
Publisher	Springer
Publisher Date	2015-09-01
Publisher Place	Germany
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Discipline Biochemistry Ascorbic Acid Chemistry Metabolism Vitamin B 12 Analogs & Derivatives Hydrogen-ion Concentration Kinetics Models, Molecular Oxidation-reduction Oxygen Journal Article Research Support, Non-u.s. Gov't
Content Type	Text
Resource Type	Article
Subject	Biochemistry Inorganic Chemistry

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Mechanistic information on the nitrite-controlled reduction of aquacob(III)alamin by ascorbate at physiological pH

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