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钌(III)聚胺羧酸配合物与生物相关配体相互作用的热力学。硫醇配体使配合物作为 NO 清除剂失活。

Thermodynamics of the interaction of ruthenium(III) polyaminecarboxylate complexes with bio-relevant ligands. Deactivation of the complexes as NO scavengers by thiol ligands.

机构信息

Department of Chemistry, Faculty of Science, Cairo University, Giza, Egypt.

出版信息

Dalton Trans. 2012 Nov 21;41(43):13447-53. doi: 10.1039/c2dt31730c.

Abstract

The acid-base and complex-formation equilibria of [Ru(H(2)dtpa)(H(2)O)], where dtpa = diethylenetriaminepentaacetate, with a series of bio-relevant ligands having various functional groups, viz. thiol, amine, imidazole and carboxylate, were investigated using potentiometric and spectrophotometric techniques. The pK(a) values for [Ru(H(2)dtpa)(H(2)O)] were found to be 2.28 and 3.48 for the uncoordinated carboxylic acid groups and 8.83 for the coordinated water molecule. The complexes formed are of 1:1 stoichiometry and their formation-constants were determined. The effect of dioxane on the acid-base and complex-formation equilibria of the Ru(III) complex was studied. The displacement reaction of coordinated NO by the investigated ligands showed that thiols can compete with NO in their reaction with Ru(III)(dtpa)(H(2)O). The results reveal that the Ru(III) complex is deactivated as a NO scavenger by thiolate ligands.

摘要

使用电位法和分光光度法研究了[Ru(H(2)dtpa)(H(2)O)](其中 dtpa = 二乙烯三胺五乙酸)与一系列具有各种官能团(如巯基、胺、咪唑和羧酸盐)的生物相关配体的酸碱和络合平衡。发现[Ru(H(2)dtpa)(H(2)O)]中未配位羧酸基团的 pK(a) 值为 2.28 和 3.48,配位水分子的 pK(a) 值为 8.83。形成的配合物为 1:1 化学计量比,并确定了其形成常数。研究了二氧六环对 Ru(III)配合物酸碱和络合平衡的影响。研究表明,与配合的 NO 相比,所研究的配体可以与Ru(III)(dtpa)(H(2)O)发生反应,取代配位的 NO。结果表明,硫醇配体使 Ru(III)配合物作为 NO 清除剂失活。

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