Hisamatsu Yosuke, Miyazawa Yuya, Yoneda Kakeru, Miyauchi Miki, Zulkefeli Mohd, Aoki Shin
Faculty of Pharmaceutical Sciences, Tokyo University of Science.
Chem Pharm Bull (Tokyo). 2016;64(5):451-64. doi: 10.1248/cpb.c15-01014.
We previously reported on supramolecular complexes 4 and 5, formed by the 4 : 4 : 4 or 2 : 2 : 2 assembly of a dimeric zinc(II) complex (Zn2L(1)) having 2,2'-bipyridyl linker, dianion of cyanuric acid (CA) or 5,5-diethylbarbituric acid (Bar), and copper(II) ion (Cu(2+)) in an aqueous solution. The supermolecule 4 possesses Cu2(μ-OH)2 centers and catalyzes hydrolysis of phosphate monoester dianion, mono(4-nitrophenyl)phosphate (MNP), at neutral pH. In this manuscript, we report on design and synthesis of hydrophobic supermolecules 9 and 10 by 4 : 4 : 4 and 2 : 2 : 2 self-assembly of hydrophobic Zn2L(2) and Zn2L(3) containing long alkyl chains, CA or Bar, and Cu(2+) and their phosphatase activity for the hydrolysis of MNP and bis(4-nitrophenyl)phosphate (BNP) in two-phase solvent systems. We assumed that the Cu2(μ-OH)2 active sites of 9 and 10 would be more stable in organic solvent than in aqueous solution and that product inhibition of the supermolecules might be avoided by the release of HPO4(2-) into the aqueous layer. The findings indicate that 9 and 10 exhibit phosphatase activity in the two-phase solvent system, although catalytic turnover was not observed. Furthermore, the hydrolysis of BNP catalyzed by the hydrophobic 2 : 2 : 2 supermolecules in the two-phase solvent system is described.
我们之前报道过超分子配合物4和5，它们是由具有2,2'-联吡啶连接基的二聚锌（II）配合物（Zn2L(1)）、氰尿酸（CA）或5,5-二乙基巴比妥酸（Bar）的二价阴离子以及铜（II）离子（Cu(2+)）在水溶液中以4 : 4 : 4或2 : 2 : 2组装而成。超分子4具有Cu2(μ-OH)2中心，并在中性pH下催化磷酸单酯二价阴离子单（4-硝基苯基）磷酸酯（MNP）的水解。在本论文中，我们报道了通过含有长烷基链的疏水性Zn2L(2)和Zn2L(3)、CA或Bar以及Cu(2+)以4 : 4 : 4和2 : 2 : 2自组装设计合成疏水性超分子9和10，以及它们在两相溶剂体系中对MNP和双（4-硝基苯基）磷酸酯（BNP）水解的磷酸酶活性。我们推测9和10的Cu2(μ-OH)2活性位点在有机溶剂中比在水溶液中更稳定，并且通过将HPO4(2-)释放到水层中可能避免超分子的产物抑制。研究结果表明，9和10在两相溶剂体系中表现出磷酸酶活性，尽管未观察到催化周转。此外，还描述了疏水性2 : 2 : 2超分子在两相溶剂体系中催化BNP水解的情况。
