Nuclear resonance vibrational spectroscopic and computational study of high-valent diiron complexes relevant to enzyme intermediates.
Nuclear resonance vibrational spectroscopic and computational study of high-valent diiron complexes relevant to enzyme intermediates.
复制标题
与酶中间体相关的高价二铁配合物的核共振振动光谱和计算研究。
DOI：
10.1073/pnas.1304238110
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发表时间：
2013
影响因子：
11.1
通讯作者：
Solomo
中科院分区：
文献类型：
--
作者：
Park,Kiyoung;Bell3rd,CalebB;Liu,LeiV;Wang,Dong;Xue,Genqiang;Kwak,Yeonju;Wong,ShaunD;Light,KennethM;Zhao,Jiyong;Alp,EErcan;Yoda,Yoshitaka;Saito,Makina;Kobayashi,Yasuhiro;Ohta,Takehiro;Seto,Makoto;QueJr,Lawrence;Solomo
双核非血红素铁酶的高价中间体的结构是未知的，尽管它们的重要性，了解酶的反应性。核共振振动光谱结合密度泛函理论计算已被应用到结构良好的特点，高价的单和二氧桥双核铁模型配合物。低频振动模式的这些高价二铁配合物涉及Fe运动已被观察和分配。这些都是独立的Fe的氧化态，并表现出强烈的依赖于自旋状态。重要的是要注意，它们是敏感的Fe2核心桥的性质，并提供了解释平行的核共振振动光谱数据的基础上的高价氧代中间体的双核nonheme铁酶。
High-valent intermediates of binuclear nonheme iron enzymes are structurally unknown despite their importance for understanding enzyme reactivity. Nuclear resonance vibrational spectroscopy combined with density functional theory calculations has been applied to structurally well-characterized high-valent mono- and di-oxo bridged binuclear Fe model complexes. Low-frequency vibrational modes of these high-valent diiron complexes involving Fe motion have been observed and assigned. These are independent of Fe oxidation state and show a strong dependence on spin state. It is important to note that they are sensitive to the nature of the Fe2core bridges and provide the basis for interpreting parallel nuclear resonance vibrational spectroscopy data on the high-valent oxo intermediates in the binuclear nonheme iron enzymes.