Institute of Crystallography, CNR, Montelibretti Rome, Italy.
J Inorg Biochem. 2010 Feb;104(2):111-7. doi: 10.1016/j.jinorgbio.2009.10.002. Epub 2009 Oct 9.
A novel ruthenium(II) compound, trans-cis-cis-[Ru(II)Cl(2)(DMSO)(2)(2-amino-5-methyl-thiazole)(2)], (I), PMRu52 hereafter, that may be obtained from the previously described (cis and trans)-[Ru(II)Cl(2)(DMSO)(4)] complexes, was designed, synthesized and characterised. The single crystal X-ray structure shows a roughly regular octahedral environment for the ruthenium(II) center with the two chloride ligands in trans and the other two pairs of identical ligands in cis. The behaviour of PMRu52 in phosphate buffer, at pH=7.4, was characterised spectroscopically as well as its interactions with a few representative biomolecules. Tight ruthenium binding to serum albumin was established by joint use of spectroscopic and separation methods. Afterward, the reactions of PMRu52 with the model proteins ubiquitin and cytochrome c were monitored through electrospray ionisation mass spectrometry (ESI-MS) methods: the formation of metallodrug-protein adducts was documented in detail and the fragmentation patterns of PMRu52 were defined. Finally, the ability of PMRu52 to affect the activity of cathepsin B, a well known cysteine protease, was evaluated in vitro and a pronounced enzyme inhibition highlighted, with an IC(50) value of 5.5 muM. This latter finding is of particular interest as cathepsin B constitutes an attractive "druggable" target for cancer, rheumatoid arthritis and other important diseases.
一种新型钌(II)化合物,反式-顺式-顺式-[Ru(II)Cl2(DMSO)2(2-氨基-5-甲基噻唑)(2)],(I),简称 PMRu52,可从先前描述的(顺式和反式)-[Ru(II)Cl2(DMSO)4]配合物获得,设计、合成并进行了表征。单晶 X 射线结构显示,钌(II)中心的环境大致为规则的八面体,两个氯配体处于反式,另外两对相同的配体处于顺式。PMRu52 在磷酸盐缓冲液中的行为在 pH=7.4 时通过光谱学进行了表征,以及其与一些代表性生物分子的相互作用。通过光谱学和分离方法的联合使用,确定了 PMRu52 与血清白蛋白的紧密结合。随后,通过电喷雾电离质谱(ESI-MS)方法监测 PMRu52 与模型蛋白泛素和细胞色素 c 的反应:详细记录了金属药物-蛋白质加合物的形成,并确定了 PMRu52 的碎裂模式。最后,评估了 PMRu52 对组织蛋白酶 B 活性的影响,组织蛋白酶 B 是一种已知的半胱氨酸蛋白酶,体外实验结果表明具有明显的酶抑制作用,IC50 值为 5.5 μM。这一发现特别有趣,因为组织蛋白酶 B 是癌症、类风湿关节炎和其他重要疾病的有吸引力的“可药物化”靶标。