含4-乙基吡啶的抗转移NAMI、NAMI-A衍生物的水解动力学及稳定性研究 |
Hydrolytic Kinetics and Stability of Antimetastasis NAMI and NAMI-A Derivatives Containing 4-Ethyl Pyridine |
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摘要: 制备了trans-[RuCl4(DMSO)(4-EtPy)]Na·2DMSO(4-EtPy=4-乙基吡啶)(化合物1)和trans-[RuCl4(DMSO)(4-EtPy)][(4-EtPy)H](化合物2)。用UV、NMR研究了化合物在pH 7.40及5.00(0.15 mol·L-1 NaCl,37 ℃)缓冲液中的水解机理-动力学和溶液稳定性。测得各水解反应表观速率常数、半衰期。研究结果表明:两个化合物的Ⅰ氯、Ⅱ氯及DMSO水解反应机理均与NAMI-A相似,但其各级水解速率比NAMI-A略快,即用4-EtPy取代咪唑环,可加快NAMI-A衍生物的Ⅰ氯、Ⅱ氯及DMSO水解反应速率。在含氮配体相同时,NAMI-A衍生物比相应NAMI衍生物的稳定性稍好。化合物在酸性溶液中的稳定性高于中性溶液。提供了用核磁法定量测定NAMI-A衍生物的水解机理-动力学。 |
关键词: 钌化合物 4-乙基吡啶 水解动力学 稳定性 核磁法 |
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Abstract: trans-[RuCl4(DMSO)(4-EtPy)]Na·2DMSO (4-EtPy=4-Ethyl pyridine) (compound 1) and trans-[RuCl4(DMSO)(4-EtPy)][(4-EtPy)H] (compound 2) were synthesized. Their hydrolytic mechanism-kinetics in pH 7.40/5.00 buffer solution and solution stabilities were studied by UV and NMR spectroscopy. Observed rate constant (kobs) and half-life time (t1/2) of the compounds were measured and calculated respectively. The result shows that the 1st and 2nd chloro-hydrolysis as well as DMSO-hydrolysis mechanisms for two compounds are very similar to that for NAMI-A. However, the measured hydrolytic rates of two compounds are somewhat faster than that of related NAMI-A, which means that replacing imidazole ring by 4-EtPy containing electron donating group would accelerate hydrolytic rate of NAMI-A derivatives. With the same nitrogen-donor ligand, NAMI-A derivative seems a little bit more stable than related NAMI derivative. The NMR method to quantitatively determine the mechanism-kinetics of NAMI-A derivatives was also provided. |
Keywords: ruthenium complexes 4-ethyl pyridine hydrolytic kinetics stabilities NMR |
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梁曜华,毕 葳,梁国刚,张启伟.含4-乙基吡啶的抗转移NAMI、NAMI-A衍生物的水解动力学及稳定性研究[J].无机化学学报,2012,28(10):2049-2058. |
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