EXAFS spectroscopic evidence for an Fe=O unit in the Fe(IV) intermediate observed during oxygen activation by taurine:α-ketoglutarate dioxygenase
EXAFS spectroscopic evidence for an Fe=O unit in the Fe(IV) intermediate observed during oxygen activation by taurine:α-ketoglutarate dioxygenase
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DOI：
10.1021/ja048255q
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发表时间：
2004-07-07
影响因子：
15
通讯作者：
Krebs, C
中科院分区：
文献类型：
--
作者：
Riggs-Gelasco, PJ;Price, JC;Krebs, C
Fe（II）-和α-酮戊二酸依赖性双加氧酶催化具有重要生物医学和环境意义的羟基化反应。最近，在该家族的一个成员牛磺酸：α-酮戊二酸双加氧酶（TauD）的反应中，第一个氧化的铁中间体被检测到，并且被证明是高自旋Fe（IV）络合物。在这项研究中，我们已经使用X-射线吸收光谱来证明存在一个短（1.62欧姆）之间的相互作用的铁和它的配体之一的Fe（IV）的中间体，但不是在Fe（II）的起始络合物。这种相互作用的检测有力地证实了中间体含有Fe-2 O结构基序的假设。
The Fe(II)- and α-ketoglutarate-dependent dioxygenases catalyze hydroxylation reactions of considerable biomedical and environmental significance. Recently, the first oxidized iron intermediate in the reaction of a member of this family, taurine:α-ketoglutarate dioxygenase (TauD), was detected and shown to be a high-spin Fe(IV) complex. In this study we have used X-ray absorption spectroscopy to demonstrate the presence of a short (1.62 Å) interaction between the iron and one of its ligands in the Fe(IV) intermediate but not in the Fe(II) starting complex. The detection of this interaction strongly corroborates the hypothesis that the intermediate contains an FeO structural motif.