Kinetics and mechanism of the reversible binding of nitric oxide to reduced cobalamin $B_{12r}$ (Cob(II)alamin)

doi:10.1021/ja010530a

Kinetics and mechanism of the reversible binding of nitric oxide to reduced cobalamin $B_{12r}$ (Cob(II)alamin)

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Kinetics and mechanism of the reversible binding of nitric oxide to reduced cobalamin $B_{12r}$ (Cob(II)alamin)

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title:	Kinetics and mechanism of the reversible binding of nitric oxide to reduced cobalamin $B_{12r}$ (Cob(II)alamin)
author:	Wolak Maria, Zahl Achim, Schneppensieper Thorsten, Stochel Grażyna , van Eldik Rudi
journal title:	Journal of the American Chemical Society
volume:	123
issue:	40
date of publication :	2001
pages:	9780-9791
ISSN:	0002-7863
eISSN:	1520-5126
DOI:	10.1021/ja010530a
language:	English
journal language:	English
abstract in English:	The reduced form of aquacobalamin binds nitric oxide very effectively to yield a nitrosyl adduct, Cbl(II)-NO. UV-vis, $^{1}\textrm{H-}$, $^{31}\textrm{P}-$, and $^{15}\textrm{N}$ NMR data suggest that the reaction product under physiological conditions is a six-coordinate, "base-on" form of the vitamin with a weakly bound R-dimethylbenzimidazole base and a bent nitrosyl coordinated to cobalt at the $\beta$-site of the corrin ring. The nitrosyl adduct can formally be described as Cbl(III)- $NO^{-}$. The kinetics of the binding and dissociation reactions was investigated by laser flash photolysis and stopped-flow techniques, respectively. The activation parameters, $\Delta$H⧧, $\Delta$S⧧, and $\Delta$V⧧, for the forward and reverse reactions were estimated from the effect of temperature and pressure on the kinetics of these reactions. For the "on" reaction of Cbl(II) with NO, the small positive $ $\Delta$S⧧ and $ $\Delta$V⧧ values suggest the operation of a dissociative interchange ($I_{d}$) substitution mechanism at the Co(II) center. Detailed laser flash photolysis and $^{17}\textrm{O}$ NMR studies provide evidence for the formation of water-bound intermediates in the laser flash experiments and strongly support the proposed $I_{d}$ mechanism. The kinetics of the "off" reaction was studied using an NO-trapping technique. The respective activation parameters are also consistent with a dissociative interchange mechanism.
affiliation:	Wydział Chemii : Zakład Chemii Nieorganicznej
type:	journal article
subtype:	academic paper

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