Synthesis of artificial phosphatases for the purpose of controling protein function

我们已经合成了双核锌（II）的穴具有新的功能，可能是相关的双核含金属的磷酸酶的性质。在水溶液中，作为底物磷酸单酯二价阴离子的方法来桥接两个锌（II）离子，顶端NH的解离和其中一个攻击磷酸盐进行磷酰基转移反应，产生一个新的含磷酰胺穴状化合物。本工作合成了一种亲脂性的锌（II）配合物，并对其结构进行了表征。结果表明，在中性表面活性剂TritonX-100存在下，锌络合物在碱性条件下形成锌氢氧化物，锌氢氧化物在共胶束中对乙酸对硝基苯酯、磷酸三酯和磷酸二酯单阴离子的水解具有亲核催化作用。本研究合成了新型的双核和三核大环多胺锌（II）配合物作为含锌（II）磷酸酶的活性中心模型。这些配合物对磷酸单酯二价阴离子具有很强的结合亲和力。

We have synthesized dinuclear zinc (II) crypate having novel functions that may be relevant to the properties of dinuclear metal-containing phosphatases. In aqueous solution, as a substrate phosphomonoester dianion approaches to bridge both zinc (II) ions, the apical NH's dissociate and one of them attacks the phosphate to perform a phosphoryl-transfer reaction, yielding a new phosphoramide-containing cryptate. The present new findings may serve to rationalize the essence of dinuclear metallophosphatases, inhibition by inorgganic phosphate, or stabilization of the phosphoryl-transfered intermediates.A lipophilic zinc (II) complex has been synthesized and fully characterized. It was demonstrated that in co-micellar solution with a neutral surfactant Triton X-100, the zinc complex forms Zn-hydroxideat alkaline pH.The Zn-hydroxide is the nucleophilic catalyst in the co-micelle for hydrolysis of 4-nitrophenyl acetate, phosphotriester and phosphodiester monoanion. This study suggests that the lipophilic zinc complex in the presence of the surfactant may be an extremely promosing candidate for disposal of nerve gases.We have syntehsized novel di- and tri-nuclear macrocyclic polyamine zinc (II) complexes as active center models for zinc (II) -containing phosphatase. Those complexes have strong binding affinity to phosphomonoester dianions.