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金属胶束催化:CTAB胶束溶液中吡啶基配体的Cu(II)、Zn(II)配合物对磷酸单酯和磷酸二酯的水解作用

Metallomicellar catalysis: hydrolysis of phosphate monoester and phosphodiester by Cu(II), Zn(II) complexes of pyridyl ligands in CTAB micellar solution.

作者信息

Jiang Fubin, Huang Liya, Meng Xiangguang, Du Juan, Yu Xiaoqi, Zhao Yufen, Zeng Xiancheng

机构信息

Department of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China.

出版信息

J Colloid Interface Sci. 2006 Nov 1;303(1):236-42. doi: 10.1016/j.jcis.2006.07.050. Epub 2006 Sep 8.

Abstract

The catalytic hydrolysis of bis(p-nitrophenyl) phosphate (BNPP) and p-nitrophenyl phosphate (NPP) by metallomicelles composed of Cu(II) or Zn(II) complexes of bispyridine-containing alkanol ligands in CTAB micellar solution was investigated at 30 degrees C. The experimental results indicate that the complexes with a 1:1 ratio of ligands to metal ions for ligands 1 (1,7-bis(6-hydroxymethyl-2-pyridyl)-2,6-dioxaheptane) and 3 (1,4-bis[(6-hydroxymethyl-2-pyridyl)-2-oxapropyl]benzene) and a 1:2 ratio of ligands to metal ions for ligand 2 (1,14-bis(6-hydroxymethyl-2-pyridyl)-2,13-dioxatetradecane) in CATB micellar solution are the active species for the catalytic hydrolysis of BNPP and NPP, respectively. The ternary complex kinetic model for metallomicellar catalysis was employed to obtain the relative kinetic and thermodynamic parameters, which demonstrated the catalytic mechanism for the hydrolysis of BNPP and NPP by metallomicelles.

摘要

在30℃下研究了由含双吡啶的链烷醇配体的Cu(II)或Zn(II)配合物在CTAB胶束溶液中组成的金属胶束对双(对硝基苯基)磷酸酯(BNPP)和对硝基苯基磷酸酯(NPP)的催化水解作用。实验结果表明,在CATB胶束溶液中,配体1(1,7-双(6-羟甲基-2-吡啶基)-2,6-二氧杂庚烷)和配体3(1,4-双[(6-羟甲基-2-吡啶基)-2-氧杂丙基]苯)的配体与金属离子比例为1:1的配合物以及配体2(1,14-双(6-羟甲基-2-吡啶基)-2,13-二氧杂十四烷)的配体与金属离子比例为1:2的配合物分别是催化BNPP和NPP水解的活性物种。采用金属胶束催化的三元络合物动力学模型来获得相关的动力学和热力学参数,这证明了金属胶束催化BNPP和NPP水解的机理。

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