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在水溶液中,通过双(Zn(2+)-环)配合物、氰尿酸和铜的自组装形成超分子磷酸酶,选择性水解磷酸单酯(cyclen = 1,4,7,10-四氮杂环十二烷)。

Selective hydrolysis of phosphate monoester by a supramolecular phosphatase formed by the self-assembly of a bis(Zn(2+)-cyclen) complex, cyanuric acid, and copper in an aqueous solution (cyclen = 1,4,7,10-tetraazacyclododecane).

机构信息

Faculty of Pharmaceutical Sciences, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510, Japan.

出版信息

Inorg Chem. 2011 Oct 17;50(20):10113-23. doi: 10.1021/ic201072q. Epub 2011 Sep 21.

Abstract

In Nature, organized nanoscale structures such as proteins and enzymes are formed in aqueous media via intermolecular interactions between multicomponents. Supramolecular and self-assembling strategies provide versatile methods for the construction of artificial chemical architectures for controlling reaction rates and the specificities of chemical reactions, but most are designed in hydrophobic environments. The preparation of artificial catalysts that have potential in aqueous media mimicking natural enzymes such as hydrolases remains a great challenge in the fields of supramolecular chemistry. Herein, we describe that a dimeric Zn(2+) complex having a 2,2'-bipyridyl linker, cyanuric acid, and a Cu(2+) ion automatically assembles in an aqueous solution to form a 4:4:4 complex, which is stabilized by metal-ligand coordination bonds, π-π-stacking interactions, and hydrogen bonding and contains μ-Cu(2)(OH)(2) cores analogous to the catalytic centers of phosphatase, a dinuclear metalloenzyme. The 4:4:4 complex selectively accelerates the hydrolysis of a phosphate monoester, mono(4-nitrophenyl)phosphate, at neutral pH.

摘要

在自然界中,通过多组分之间的分子间相互作用,蛋白质和酶等组织良好的纳米结构在水介质中形成。超分子和自组装策略为控制反应速率和化学反应的特异性提供了构建人工化学结构的多种方法,但大多数都是在疏水环境中设计的。在模拟水解酶等天然酶的水相环境中制备具有潜在应用的人工催化剂仍然是超分子化学领域的一大挑战。在此,我们描述了一种具有 2,2'-联吡啶连接体、氰尿酸和 Cu(2+)离子的二聚 Zn(2+)配合物,可在水溶液中自动组装形成 4:4:4 配合物,该配合物通过金属-配体配位键、π-π堆积相互作用和氢键稳定,并包含类似于磷酸酶(二核金属酶)催化中心的 μ-Cu(2)(OH)(2)核。该 4:4:4 配合物在中性 pH 下选择性加速磷酸单酯(单(4-硝基苯基)磷酸酯)的水解。

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