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[含硫醇配体的二亚硝酰基铁配合物的二聚体和单体形式:物理化学性质及血管舒张活性]

[Dimeric and monomeric forms of dinitrosyl iron complexes with thiol-containing ligands: physico-chemical properties and vasodilator activity].

作者信息

Vanin A F, Stukan R A, Manukhina E B

出版信息

Biofizika. 1997 Jan-Feb;42(1):10-21.

PMID:9181782
Abstract

When studying the vasodilator activity of dinitrosyl iron complexes (DNIC) with thiol-containing ligands as NO donors, it should be taken into consideration that these complexes depending on the content of thiols in the environment can occur in either form that differ by their EPR, gamma-resonance and optical characteristics and also by their vasodilator effect on isolated blood vessels. The more stable diamagnetic form appears at the ratio Fe2+:RS(-)-1:2. It reversibly dissociates to the monomeric paramagnetic form [(RS-)2Fe+(NO+)2] on increasing the thiol content to the level 20 times and more exceeding the quantity of iron. It is suggested that stabilization of the dimeric form is provided by formation of RS(-)-NO+ bonds between monomeric components of the dimer. This process is favored by a corresponding orientation of the monomers relative to each other. A high stability of the DNIC dimeric form correlates with more prolonged vasodilator effect of this complex as an NO source. Replacement of cysteine by reduced glutathione in dimeric and monomeric forms of DNIC increases both stability of the complexes and the duration of their vasodilator effect.

摘要

在研究以含硫醇配体作为一氧化氮供体的二亚硝酰基铁配合物(DNIC)的血管舒张活性时,应考虑到这些配合物会根据环境中硫醇的含量以两种形式存在,这两种形式在电子顺磁共振(EPR)、γ共振和光学特性以及对离体血管的血管舒张作用方面都有所不同。更稳定的抗磁性形式在Fe2+与RS(-)的比例为1:2时出现。当硫醇含量增加到超过铁含量20倍及更多时,它会可逆地解离为单体顺磁性形式[(RS-)2Fe+(NO+)2]。有人认为,二聚体形式的稳定是通过二聚体单体成分之间形成RS(-)-NO+键来实现的。这个过程有利于单体彼此之间的相应取向。DNIC二聚体形式的高稳定性与其作为一氧化氮源时更持久的血管舒张作用相关。在DNIC的二聚体和单体形式中,用还原型谷胱甘肽替代半胱氨酸会增加配合物的稳定性及其血管舒张作用的持续时间。

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