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首页> 外文期刊>Journal of Inorganic Biochemistry: An Interdisciplinary Journal >Preparation, stability, and photoreactivity of thiolato ruthenium polypyridyl complexes: Can cysteine derivatives protect ruthenium-based anticancer complexes?
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Preparation, stability, and photoreactivity of thiolato ruthenium polypyridyl complexes: Can cysteine derivatives protect ruthenium-based anticancer complexes?

机译：硫醇基钌多吡啶基复合物的制备，稳定性和光反应性：半胱氨酸衍生物可以保护基于钌的抗癌复合物吗？

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Ruthenium polypyridyl complexes may act as light-activatable anticancer prodrugs provided that they are protected by well-coordinated ligands that i) prevent coordination of other biomolecules to the metal center in the dark and ii) can be removed by visible light irradiation. In this paper, the use of monodentate thiol ligands RSH as light-cleavable protecting groups for the ruthenium complex [Ru(tpy)(bpy)(OH2)](RF6)(2) ([1](PF6)(2); tpy = 2,2';6',2 ''-terpyridine, bpy = 2,2'-bypyridine), is investigated. The reaction of [1](2+) with RSH = H(2)Cys (L-cysteine), H(2)Acys (N-acetyl-L-cysteine), and HAcysMe (N-acetyl-L-cysteine methyl ester), is studied by UV-visible spectroscopy, NMR spectroscopy, and mass spectrometry. Coordination of the monodentate thiol ligands to the ruthenium complex takes place upon heating to 353 K, but full conversion to the protected complex [Ru(tpy)(bpy)(SR)]PF6 is only possible when a large excess of ligand is used. Isolation and characterization of the two new thiolato complexes [Ru(tpy)(bpy)(kappa S-HCys)]PF6 ([2]PF6) and [Ru(tpy)(bpy)(kappa S-HAcys)]PF6 ([3]PF6) is reported. [3]PF6 shows a metal-to-ligand charge-transfer absorption band that is red shifted (lambda(max) = 492 nm in water) compared to its methionine analogue [Ru(tpy)(bpy)(kappa S-HAmet)](Cl)(2) ([5](Cl)(2), lambda(max) = 452 nm; HAmet = N-acetyl-methionine). In the dark the thiolate ligand coordinated to ruthenium is oxidized even by traces of oxygen, which first leads to the sulfenato, sulfinato, and disulfide ruthenium complexes, and finally to the formation of the aqua complex [1](2+). [3]PF6 showed slow photosubstitution of the thiolate ligand by water under blue light irradiation, together with faster photooxidation of the thiolate ligand compared to dark conditions. The use of thiol vs. thioether monodentate ligands is discussed for the protection of anticancer ruthenium-based prodrugs. (C) 2015 Elsevier Inc. All rights reserved.
机译：钌多吡啶基配合物可以用作光激活的抗癌前药，只要它们受到配位良好的配体的保护即可：i）在黑暗中防止其他生物分子与金属中心的配位，并且ii）可以通过可见光照射除去。在本文中，使用单齿硫醇配体RSH作为钌络合物[Ru（tpy）（bpy）（OH2）]（RF6）（2）（[1]（PF6）（2）;研究了tpy = 2,2'; 6'，2''-叔吡啶，bpy = 2,2'-bypyridine）。 [1]（2+）与RSH = H（2）Cys（L-半胱氨酸），H（2）Acys（N-乙酰-L-半胱氨酸）和HAcysMe（N-乙酰基-L-半胱氨酸甲基）的反应通过紫外可见光谱，NMR光谱和质谱研究。加热至353 K时，单齿硫醇配体与钌配合物发生配位，但只有在使用大量过量的配体时，才能完全转化为受保护的配合物[Ru（tpy）（bpy）（SR）] PF6。两种新硫脲基配合物[Ru（tpy）（bpy）（kappa S-HCys）] PF6（[2] PF6）和[Ru（tpy）（bpy）（kappa S-HAcys）] PF6（[ 3] PF6）。 [3] PF6显示出一个金属到配体的电荷转移吸收带，与蛋氨酸类似物[Ru（tpy）（bpy）（kappa S-HAmet）相比，发生了红移（在水中的λ（最大）= 492 nm）。 ]（Cl）（2）（[5]（Cl）（2），λ（max）= 452 nm; HAmet = N-乙酰基甲硫氨酸）。在黑暗中，与钌配位的硫醇盐配体甚至被微量的氧气氧化，这首先导致了磺胺基，磺胺基和二硫键钌络合物，最后导致了水基络合物的形成[1]（2+）。 [3] PF6显示了在蓝光照射下水对硫醇盐配体的光解慢，并且与黑暗条件相比，硫醇盐配体的光氧化更快。讨论了使用硫醇对硫醚单齿配体来保护基于钌的抗癌前药。 （C）2015 Elsevier Inc.保留所有权利。

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