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Development of metallosupramolecular phosphatases based on the combinatorial self-assembly of metal complexes and organic building blocks for the catalytic hydrolysis of phosphate monoesters
Results in Chemistry Pub Date : 2021-04-22 , DOI: 10.1016/j.rechem.2021.100133
Shin Aoki , Akib Bin Rahman , Yosuke Hisamatsu , Yuya Miyazawa , Mohd Zulkefeli , Yutaka Saga , Tomohiro Tanaka

The phosphorylation and dephosphorylation of proteins and other intracellular molecules are important reactions in living systems and are generally controlled by the action of kinases and phosphatases. The design and synthesis of artificial mimics of natural enzymes are important research subjects in bioorganic and bioinorganic chemistry. A supramolecular strategy based on the three-dimensional self-assembly of molecular building blocks would be useful for the construction of artificial supramolecular complexes. The main focus of this review is on artificial mimics of natural phosphatases that contain dimetallic cores in their active sites. Previous examples of artificial mimics of alkaline phosphatases (AP) constructed covalently are initially presented, then followed by a description of artificial metallosupramolecular complexes formed by the combinatorial self-assembly of different bis(Zn2+-cyclen) complexes containing 2,2′-bipyridyl (bpy) linker (cyclen = 1,4,7,10-tetraazacyclododecane), cyanuric acid or barbital (Bar) units, and Cu2+ ion in single or two-phase solvent systems. It is now thought that the appropriate combination of the various building blocks and solvent systems (single- and two-phase solvent systems) can strongly assist in developing the artificial systems that accelerate and catalyze the hydrolysis of a phosphate monoester, mono(p-nitrophenyl) phosphate (MNP). Such approaches would be useful in terms of understanding the mechanism of action of naturally occurring enzymes and to develop biologically active, bioorthogonal, and versatile supramolecular catalysts.



中文翻译:

基于金属配合物和有机结构单元的组合自组装用于磷酸单酯催化水解的金属超分子磷酸酶的开发

蛋白质和其他细胞内分子的磷酸化和去磷酸化是生命系统中的重要反应,通常受激酶和磷酸酶的作用控制。天然酶的人工模拟物的设计和合成是生物有机和生物无机化学领域的重要研究课题。基于分子结构单元的三维自组装的超分子策略将对构建人工超分子复合物有用。这篇综述的主要重点是在其活性位点包含双金属核的天然磷酸酶的人工模拟物。首先介绍了共价构建的碱性磷酸酶(AP)人工模拟物的先前示例,2+三环萜)含有2,2'-联吡啶(BPY)接头(环烯= 1,4,7,10-四),氰尿酸或巴比妥(BAR)单位,和Cu络合物2+离子在单或双相溶剂系统。现在认为,各种结构单元和溶剂体系(单相和两相溶剂体系)的适当组合可以极大地帮助开发可加速和催化磷酸单酯单(硝基苯酚)水解的人工体系。)磷酸盐(MNP)。就理解天然酶的作用机理以及开发具有生物活性的,生物正交的和多用途的超分子催化剂而言,这样的方法将是有用的。

更新日期:2021-05-02
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