Understanding the copper-phenoxyl radical array in galactose oxidase: contributions from synthetic modeling studies

被引:284
作者
Jazdzewski, BA [1 ]
Tolman, WB [1 ]
机构
[1] Univ Minnesota, Ctr Met Biocatalysis, Dept Chem, Minneapolis, MN 55455 USA
基金
美国国家科学基金会; 美国国家卫生研究院;
关键词
galactose oxidase; phenoxyl radicals; copper; oxidation; phenolate complexes;
D O I
10.1016/S0010-8545(00)00342-8
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The two-electron oxidation of primary alcohols with dioxygen to yield aldehyde and hydrogen peroxide that is catalyzed by galactose oxidase (GAO) occurs at an intriguing active site comprising of a copper ion ligated by an unusual cysteine-modified tyrosine group. Both the metal ion and the tyrosinate undergo 1-electron redox interconversions during catalysis, the Cu(II)-tyrosyl radical form being a critical species. Due to the novelty of this coupled metal-radical cofactor unit in chemistry and biology and its importance within the more general context of radical-enzyme biochemistry, chemists have attempted to prepare model complexes for this and other redox-related states of GAG. The primary goals of such research are to better understand the enzyme active site spectral properties, structural attributes, and reactivity. In this review article, progress toward these goals is surveyed, beginning with a discussion of the synthesis and structural and spectroscopic characterization of model complexes of the CAO active site and ending with a description of more recent discoveries of catalytic reactivity by Cu(II)-phenoxyl radical species that replicate and provide insights into GAO function. (C) 2000 Elsevier Science S.A. All rights reserved.
引用
收藏
页码:633 / 685
页数:53
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