Structural and functional studies on model compounds of purple acid phosphatases and catechol oxidases

Structural and functional studies on model compounds of purple acid phosphatases and catechol oxidases
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紫色酸性磷酸酶和儿茶酚氧化酶模型化合物的结构和功能研究

DOI:
10.1016/s0010-8545(98)00234-3
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发表时间:
1999
影响因子:
20.6
通讯作者:
B. Krebs
B. Krebs
中科院分区:
化学1区
文献类型:
--
作者:
R. Than;Arnold A. Feldmann;B. Krebs

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报道了作为 PAP 活性位点结构模型化合物的八种代表性对称和不对称配合物的合成、单晶 X 射线晶体学、磁性和电化学表征。合成并表征了混合价二铁和铁(III)-锌(II)络合物,分别作为哺乳动物和植物 PAP 活性还原形式的模型。报道了五种二铁 (III) 化合物作为氧化子宫铁蛋白-磷酸和胂复合物的结构模型以及来自牛脾的 PAP 氧化形式的模型。除了结构相关性之外,还介绍了这些模型复合物之一的过氧化氢酶和过氧化物酶活性。我们进一步总结了我们最近关于儿茶酚氧化酶和合成铜配位络合物的协同研究的研究。儿茶酚氧化酶是激活双氧的重要 3 型铜蛋白。低分子量催化剂的开发应有助于O2氧化有机物。特别是,所报道的铜(II)络合物可以分别作为分子氧结合和分子氧激活铜蛋白的活性位点的结构和功能生物无机模型化合物。这些研究提供了一种新的 X 射线晶体学表征类型的具有 μ4-(η1)4 配位模式的过氧化铜 (II) 配合物。
The synthesis, single crystal X-ray crystallographic, magnetic and electrochemical characterization of eight representative symmetric and unsymmetric complexes as structural model compounds for active sites in PAPs is reported. A mixed valent diiron as well as an iron(III)–zinc(II) complex as models for the active, reduced form of mammalian and plant PAPs, respectively, were synthesized and characterized. Five diiron(III) compounds as structural models for the oxidized uteroferrin-phosphato and -arsenato complex and a model for the oxidized form of PAP from beef spleen are reported. In addition to the structural relevance the catalase and peroxidase activity of one of these model complexes is introduced. Further we summarize our recent research concerning synergistic investigations on catechol oxidase and on synthetic copper coordination complexes. The catechol oxidase is an important type 3 copper protein for the activation of dioxygen. The development of low-molecular weight catalysts should facilitate the oxidation of organic substances by O2. In particular the reported copper(II) complexes may serve as structural and functional bioinorganic model compounds for the active sites of dioxygen binding and dioxygen activating copper proteins, respectively. These investigations provided a new X-ray crystallographically characterized type of peroxo copper(II) complexes with a μ4-(η1)4coordination mode.