异双核配合物金属胶束模拟磷酸酯酶催化磷酸单酯水解

Metallomicelles Made of Heterobinuclear Complexes as Phosphoesterase Mimic to Catalyze Phosphate Monoester Hydrolysis

合成和表征了四种含过渡金属离子Cu(Ⅱ )和Ni(Ⅱ )的草酰胺桥联异双核配合物 ,并将这些配合物与Brij35表面活性剂胶束构成金属胶束作为金属水解酶模拟物用于催化对硝基苯酚磷酸单酯 (NPP)水解 .研究了金属胶束对NPP水解反应的催化机理 ,建立了异双核配合物催化NPP水解的动力学数学模型 .结果表明 ,四种草酰胺桥联异双核配合物在NPP水解反应中表现出较高的催化活性 ,随着胶束溶液 pH的增大 ,配合物催化NPP水解的速率提高 .配合物中的两个金属离子在催化NPP水解过程中表现出较好的协同效应 .

Four oxamido-bridged heterobinuclear complexes containing transition metal ions Ni(Ⅱ) and Cu(Ⅱ) were synthesized and characterized. Metallomicelles made from the heterobinuclear complexes and micelle were used as mimetic metal hydrolytic enzyme for the hydrolysis of p-nitrophenyl phosphate (NPP). According to the kinetic results of NPP hydrolysis, the mechanism of NPP hydrolysis catalyzed by the metallomicelles was proposed. Based on the mechanism, a kinetic mathematical model of NPP cleavage catalyzed by the heterobinuclear complexes was suggested and the relative kinetic constants were calculated by using this model. The results indicate that the four oxamido-bridged heterobinuclear complexes all show high activity for the NPP catalytic hydrolysis in the miceller solution of surfactant Brij35. The rate of the NPP catalytic hydrolysis increases with increasing pH value of the micelle solution. There is a synergistic effect between the two transition metal ions of the heterobinuclear complexes in the NPP catalytic hydrolysis. The bigger the ligand electronegativity of complex is, the higher the catalytic activity of the metallomicelle made from the complex is.