Department of Chemical Physics and Optics, Faculty of Mathematics and Physics, Charles University, Ke Karlovu 3, 121 16, Prague 2, Czech Republic.
J Mol Model. 2013 Nov;19(11):4669-80. doi: 10.1007/s00894-012-1442-z. Epub 2012 May 30.
Hydration reactions of two anticancer Pt(IV) complexes JM149 and JM216 (Satraplatin) were studied computationally together with the hydration of the Pt(II) complex JM118, which is a product of the Satraplatin reduction. Thermodynamic and kinetic parameters of the reactions were determined at the B3LYP/6-311++G(2df.2pd)//B3LYP/6-31 + G(d)) level of theory. The water solution was modeled using the COSMO implicit solvation model, with cavities constructed using Klamt's atomic radii. It was found that hydration of the Pt(IV) complexes is an endergonic/endothermic reaction. It follows the (pseudo)associative mechanism is substantially slower (k ≈ 10(-11) s(-1)) than the corresponding reaction of Pt(II) analogues ((k ≈ 10(-5) s(-1)). Such a low value of the reaction constant signifies that the hydration of JM149 and Satraplatin is with high probability a kinetically forbidden reaction. Similarly to JM149 and Satraplatin, the hydration of JM118 is an endothermic/endoergic reaction. On the other hand, the kinetic parameters are similar to those of cisplatin Zimmermann et al. (J Mol Model 17:2385-2393, 2011), allowing the hydration reaction to occur at physiological conditions. These results suggest that in order to become active Satraplatin has to be first reduced to JM118, which may be subsequently hydrated to yield the active species.
两种抗癌 Pt(IV) 配合物 JM149 和 JM216(Satraplatin)以及 Satraplatin 还原产物 Pt(II) 配合物 JM118 的水合反应通过计算进行了研究。在 B3LYP/6-311++G(2df.2pd)//B3LYP/6-31 + G(d)) 理论水平上确定了反应的热力学和动力学参数。水溶液使用 COSMO 隐式溶剂化模型进行建模,使用 Klamt 的原子半径构建空腔。结果表明,Pt(IV) 配合物的水合是一个吸热/吸热反应。它遵循(准)缔合机制,比相应的 Pt(II) 类似物的反应(k ≈ 10(-5) s(-1)) 慢得多。反应常数如此低的值表明,JM149 和 Satraplatin 的水合很可能是动力学上禁止的反应。与 JM149 和 Satraplatin 类似,JM118 的水合也是一个吸热/吸热反应。另一方面,动力学参数与顺铂的相似 Zimmerman 等人(J Mol Model 17:2385-2393, 2011),允许在生理条件下发生水合反应。这些结果表明,为了变得活跃,Satraplatin 必须首先还原为 JM118,然后可能进一步水合生成活性物质。