新型磷酸酯酶模型配体的合成及其Zn(Ⅱ)配合物催化PNPP水解反应研究

New Phosphatase Ligands with Imidazole Groups:Synthesis and Catalytic Activity of Zn(Ⅱ) Complexes toward Hydrolysis of PNPP

以N,O,O′-三(对甲苯磺酰基)-双(2-羟乙基)胺为起始物,经季铵化、Hoffmann消去,得到了含两个咪唑功能基的仿生配体1,1再经水解、亲核取代反应,合成了含两个咪唑功能基的仿生配体2;化合物1、2的结构经IR、1HNMR和MS谱证实.催化活性研究表明:pH=7时,配体2的Zn(II)配合物催化PNPP水解的表观速率常数是PNPP自身水解的3.004×103倍,其水解能很好地遵从一级反应的动力学行为.

Biomimetic ligand 1, containing two imidazole groups, has been synthesized via Quaternary Ammoniation and Hoffmann Type Elimination reaction started from N, O, O＇ -tri （p-toluenesulfonyl） -bis （2-hydroxyethyl） a- mine. Biomimetic ligand 2 was synthesized via hydrolysis and nucleophilic substitution reaction of ligand 1. The structures of compounds 1 and 2 were confirmed by IR, 1 HNMR and MS spectra. Ligand 2 was applied to catalyze the hydrolysis of bis （4 - nitrophenyl） phosphate （PNPP）. The experiment results have showed that the hydrolysis of PNPP, catalyzed by Ligand 2 - Zn（ Ⅱ ） complex, is obviously accelerated, and the apparent rate constant is 3. 004×10^3 times faster than that of natural hydrolysis of PNPP. Its hydrolysis complies well with kinetic behavior of first order reaction.