Direct spectroscopic evidence for a high-spin Fe(IV) intermediate in tyrosine hydroxylase

Direct spectroscopic evidence for a high-spin Fe(IV) intermediate in tyrosine hydroxylase
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DOI:
10.1021/ja074446s
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发表时间:
2007-09-19
影响因子:
15
通讯作者:
Fitzpatrick, Paul F.
Fitzpatrick, Paul F.
中科院分区:
化学1区
文献类型:
--
作者:
Eser, Bekir E.;Barr, Eric W.;Fitzpatrick, Paul F.

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酪氨酸羟化酶是芳香族氨基酸羟化酶家族的成员,使用单核Fe(H)和四氢翅蛋白氢氧化氢酶将酪氨酸羟基化对二羟基苯基丙氨酸的羟基化。快速冻结摩斯鲍尔光谱学现已为酪氨酸羟化酶催化的反应中的Fe(IV)中间存在直接证据。快速淬灭技术为该物种的动力学能力提供了支持。这是在酶芳族羟基化反应中中间的单核Fe(IV)中间体的第一个直接证据。
Tyrosine hydroxylase, a member of the aromatic amino acid hydroxylase family, uses a mononuclear Fe(H) and tetrahydropterin for hydroxylation of tyrosine to dihydroxyphenylalanine. Rapid-freeze quench Mossbauer spectroscopy has now provided direct evidence for the presence of an Fe(IV) intermediate in the reaction catalyzed by tyrosine hydroxylase. Rapid-quench techniques provide support for the kinetic competence of this species as the hydroxylating intermediate. This is the first direct evidence for a mononuclear Fe(IV) intermediate in an enzymatic aromatic hydroxylation reaction.