New functional models for catechol oxidases

New functional models for catechol oxidases
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DOI:
10.1016/s0020-1693(99)00553-8
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发表时间:
2000-04-30
影响因子:
2.8
通讯作者:
Krebs, B
Krebs, B
中科院分区:
化学3区
文献类型:
--
作者:
Gentschev, P;Möller, N;Krebs, B

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新的双核铜(II)配合物[Cu-2(L1)(mu-OAc)](ClO 4)(2). CH3CN(1),[Cu-2(L2)(CH3CN)(2)](ClO4)(4)。C2H5OH(2)、[Cu-2(L3)(2)(CH3CN)(2)](PF6)(2)(3)和[Cu-2(L4)(2)](PF6)(2)。以配体N,N,N ',N'-四((N-2-羟乙基)-2-苯并咪唑甲基)-2-羟基-1,3-丙二胺HL 1、N,N,N ',N'-四(2-甲基咪唑基)-2-羟基-1,3-丙二胺HL 2、(2-吡啶基甲基)(1-羟丙基)胺HL 3和(2-羟苄基)(N,N-二甲基丙基)胺HL 4为原料合成了CH 2Cl 2(4)。所有的配合物,其特征在于通过X-射线结构测定,揭示双核阳离子和高氯酸盐或六氟磷酸盐抗衡离子。在配合物阳离子中,两个铜(II)原子与N4 O,N3 O2或N2 O2供体组和不同的桥接系统显示出不同的配位球。我的... Cu距离从2.918(2)到4.756(2)埃变化。采用紫外-可见吸收光谱法研究了3,5-二叔丁基邻苯二酚氧化制醌的催化性能。配合物3表现出最高的活性,周转数为32 h(-1),而其他化合物显示较低的氧化速率。应用基于Michaelis-Menten模型的动力学处理。(C)2000 Elsevier Science S.A. All rights reserved.
The new dinuclear copper(II) complexes [Cu-2(L1)(mu-OAc)](ClO4)(2). CH3CN (1), [Cu-2(L2)(CH3CN)(2)](ClO4)(4). C2H5OH (2), [Cu-2(L3)(2)(CH3CN)(2)](PF6)(2) (3) and [Cu-2(L4)(2)](PF6)(2). CH2Cl2 (4) were prepared with the ligands N,N,N',N'-tetrakis((N-2-hydroxy-ethyl)-2-benzimidazolylmethyl)-2-hydroxy-1,3-diaminopropane HL1, N,N,N',N'-tetrakis (2-methylimidazolyl)-2-hydroxy-1,3-diaminopropane HL2, (2-pyridylmethyl)(1-hydroxypropyl)amine HL3 and (2-hydroxybenzyl)(N,N-dimethylpropyl)amine HL4. All complexes were characterized by X-ray structure determination, revealing dinuclear cations and perchlorate or hexafluorophosphate counter ions. In the complex cations the two copper(II) atoms show different coordination spheres with N4O, N3O2 or N2O2 donor sets and different bridging systems. The Cu ... Cu distances vary from 2.918(2) to 4.756(2) Angstrom. The catalytic performance of the oxidation of 3,5-di-tert-butylcatechol to quinone was studied using UV-Vis absorption spectra methods. Complex 3 exhibits the highest activity with a turnover number of 32 h(-1) while the other compounds show lower rates of oxidation. A kinetic treatment on the basis of the Michaelis-Menten model was applied. (C) 2000 Elsevier Science S.A. All rights reserved.