大环Schiff碱配合物金属胶束催化羧酸酯水解的动力学研究

文章合成和表征了两种大环Schiff碱过渡金属配合物NiL和CuL(L:高氯酸-5,7,7,12,14,14-六甲基-1,4,8,11-四氮杂环-4,11-二烯),并且将NiL或CuL与表面活性剂(LSS,CTAB)组成的金属胶束作为模拟水解金属酶用于催化羧酸酯(PNPP)水解。催化反应系统的特征光谱分析表明,在PNPP催化水解过程中形成了由Ni(II)或Cu(II)配合物与PNPP组成的中间物种,并由此提出PNPP催化水解的机理。依据本文提出的PNPP催化水解机理建立了用于计算动力学常数的动力学模型,并讨论了不同胶束和配合物结构对PNPP催化水解的影响。

Kinetic Study on Carboxylic Ester Hydrolysis Catalyzed by the Metallomicelle Made up of Macrocyclic Schiff Base Complex

Two transitional metal ion macrocyclic Schiff base complexes,NiL and CuL were synthesized and characterized,and the metallomicelles made up of the nickel(II) and copper(II) complexes and surfactants(LSS,CTAB),as mimic hydrolytic metalloenzyme,were used in catalytic hydrolysis of carboxylic ester(PNPP).The analysis of specific absorption spectrums of the hydrolytic reaction systems indicates that key intermediates,made up of PNPP and Ni(II) or Cu(II) complexes,have formed in the reaction processes of the PNPP catalytic hydrolysis.In this,based on the analytic result of specific absorption spectrum,the mechanism of PNPP catalytic hydrolysis has been proposed;a kinetic mathematical model,applied to the calculation of the kinetic parameter of PNPP catalytic hydrolysis,has been established on the foundation of the mechanism proposed;structure effect of the complexes and effects of micelle on the rate of PNPP hydrolysis catalyzed by the complexes have also been discussed.