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Catalytic Hydrolysis of Phosphate Monoester by Supramolecular Phosphatases Formed from a Monoalkylated Dizinc(II) Complex, Cyclic Diimide Units, and Copper(II) in Two-Phase Solvent System
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2019-04-10 00:00:00 , DOI: 10.1021/acs.inorgchem.8b03586 Akib Bin Rahman , Hiroki Imafuku , Yuya Miyazawa , Ananda Kafle , Hideki Sakai , Yutaka Saga , Shin Aoki
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2019-04-10 00:00:00 , DOI: 10.1021/acs.inorgchem.8b03586 Akib Bin Rahman , Hiroki Imafuku , Yuya Miyazawa , Ananda Kafle , Hideki Sakai , Yutaka Saga , Shin Aoki
Design and synthesis of enzyme mimic with programmed molecular interaction among several building blocks including metal complexes and metal chelators is of intellectual and practical significance. The preparation of artificial enzymes that mimic the natural enzymes such as hydrolases, phosphatases, etc. remains a great challenge in the field of supramolecular chemistry. Herein we report on the design and synthesis of asymmetric (nonsymmetric) supermolecules by the 2:2:2 self-assembly of an amphiphilic zinc(II)–cyclen complex containing a 2,2′-bipyridyl linker and one long alkyl chain (Zn2L3), barbital analogues, and Cu2+ as model compounds of an enzyme alkaline phosphatase that catalyzes the hydrolysis of phosphate monoesters such as mono(4-nitrophenyl)phosphate at neutral pH in two-phase solvent system (H2O/CHCl3) in pH 7.4 and 37 °C. Hydrolytic activity of these complexes was found to be catalytic, and their catalytic turnover numbers are 3–4. The mechanistic studies based on the UV/vis and emission spectra of the H2O and CHCl3 phases of the reaction mixtures suggest that the hydrophilicity/hydrophobicity balance of the supramolecular catalysts is an important factor for catalytic activity.
中文翻译:
在两相溶剂体系中,由单烷基化的Dizinc(II)配合物,环状二酰亚胺单元和Cu(II)形成的超分子磷酸酯催化水解磷酸单酯
在包括金属配合物和金属螯合剂在内的多个结构单元之间具有程序化分子相互作用的酶模拟物的设计和合成具有智力和实践意义。模仿天然酶如水解酶,磷酸酶等的人造酶的制备仍然是超分子化学领域中的巨大挑战。本文中,我们通过两亲性锌(II)-环素络合物的2:2:2自组装,设计和合成了不对称(非对称)超分子,该两性化合物含有2,2'-联吡啶基接头和一条长烷基链(锌2 L 3),巴比妥类似物和Cu 2+作为碱性磷酸酶的模型化合物,该酶在中性pH下在两相溶剂系统(H 2 O / CHCl 3)中在pH 7.4和37°C下催化磷酸单酯(例如单(4-硝基苯基)磷酸酯)的水解。发现这些复合物的水解活性具有催化作用,其催化转换数为3-4。基于反应混合物的H 2 O和CHCl 3相的UV / vis和发射光谱的机理研究表明,超分子催化剂的亲水性/疏水性平衡是催化活性的重要因素。
更新日期:2019-04-10
中文翻译:
在两相溶剂体系中,由单烷基化的Dizinc(II)配合物,环状二酰亚胺单元和Cu(II)形成的超分子磷酸酯催化水解磷酸单酯
在包括金属配合物和金属螯合剂在内的多个结构单元之间具有程序化分子相互作用的酶模拟物的设计和合成具有智力和实践意义。模仿天然酶如水解酶,磷酸酶等的人造酶的制备仍然是超分子化学领域中的巨大挑战。本文中,我们通过两亲性锌(II)-环素络合物的2:2:2自组装,设计和合成了不对称(非对称)超分子,该两性化合物含有2,2'-联吡啶基接头和一条长烷基链(锌2 L 3),巴比妥类似物和Cu 2+作为碱性磷酸酶的模型化合物,该酶在中性pH下在两相溶剂系统(H 2 O / CHCl 3)中在pH 7.4和37°C下催化磷酸单酯(例如单(4-硝基苯基)磷酸酯)的水解。发现这些复合物的水解活性具有催化作用,其催化转换数为3-4。基于反应混合物的H 2 O和CHCl 3相的UV / vis和发射光谱的机理研究表明,超分子催化剂的亲水性/疏水性平衡是催化活性的重要因素。