Effect of Hb on Fe—S—NOꢀcomplex activity
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 12, December, 2010
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the participation of the coordinated hydroxyl ion. The
intramolecular proton transfer between the hydroxy groups
in this dimer facilitates the electron transfer between the
ions of Feꢀcontaining complexes, which is, in fact, the
disproportionation reaction. An increase in the oxidation
state of Fe by 2 in the complex [Fe(SR)(O)(NO)2] comꢀ
pared to the starting complex 1 leads to a decrease in its
donor ability and a weakening of the Fe—NO bond.
In addition, in the mixedꢀvalence dinuclear complex
[Fe(SR)(O)(NO)2]...[Fe(SR)(H2O)(NO)2], in which the
oxo and aqua ligands are linked by a hydrogen bond, the
vacant coordination site that is formed after the eliminaꢀ
tion of NO can be occupied as a result of the transformaꢀ
tion of the terminal thiolate ligand into the bridging
ligand. These facts, on the one hand, are responsible for
the secondꢀorder kinetic curve and, on the other hand,
cause an increase in the rate constant for reaction (19)
compared to the rate constant for the formation of NO in
the bimolecular reaction of the unoxidized complexes
[Fe(SR)(H2O)(NO)2].
* * *
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In summary, we made an attempt to explain the effect
of Hb on the kinetics of the formation of NO. In the
absence of Hb, nitric oxide is accumulated in a solution as
a result of the secondꢀorder reaction accompanied by the
reduction of NO, in our opinion, by the iron nitrosyl comꢀ
plex, resulting in a decrease in the yield of NO. In the
presence of Hb, the rapid and irreversible binding of NO
molecules leads to such a substantial decrease in the NO
concentration that further transformations of NO can be
ignored. In addition, the reversible binding of iron nitrosyl
complexes to the surface functional groups of Hb leads to
a reduction in their concentration in a solution and a deꢀ
crease in the rate of the formation of NO. Therefore, Hb
has a dual effect. On the one hand, the accumulation of
nitric oxide in the form of Hb(NO)4 ensures its complete
assimilation in further steps in the NO metabolism. On
the other hand, Hb is a carrier (reservoir) of iron nitrosyl
complexes stabilized on the surface of the Hb globule, and
these complexes can directly act as NO donors after the
desorption.
We thank B. L. Psikha for a deep and fruitful discussion.
This study was financially supported by the Division of
Chemistry and Materials Science of the Russian Academy
of Sciences (Program No. 9 "Medicinal and Biomolecular
Chemistry").
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