氯过氧化物酶化合物0的结构与量子化学表征，多种血红素酶的常见反应中间体
Structure and quantum chemical characterization of chloroperoxidase compound 0, a common reaction intermediate of diverse heme enzymes.
作者信息
Kühnel Karin, Derat Etienne, Terner James, Shaik Sason, Schlichting Ilme
机构信息
Department of Biomolecular Mechanisms, Max Planck Institute for Medical Research, Jahnstrasse 29, 69120 Heidelberg, Germany.
出版信息
Proc Natl Acad Sci U S A. 2007 Jan 2;104(1):99-104. doi: 10.1073/pnas.0606285103. Epub 2006 Dec 26.
Abstract
We have determined the crystal structure of the chloroperoxidase (CPO) hydroperoxo reaction intermediate (CPO compound 0) at 1.75-A resolution. The intermediate was generated through controlled photoreduction of the CPO oxygen complex during x-ray data collection, which was monitored by recording of the crystal absorption spectra. Initially, the peroxo-anion species was formed and then protonated to yield compound 0. Quantum chemical calculations indicate that the peroxo-anion species is not stable and collapses instantaneously to compound 0. Compound 0 is present in the ferric low-spin doublet ground state and is characterized by a long O O bond length of 1.5 A and a Fe O bond distance of 1.8 A, which is also observed in the crystal structure.
摘要
我们已确定氯过氧化物酶（CPO）氢过氧反应中间体（CPO化合物0）在1.75埃分辨率下的晶体结构。该中间体是在X射线数据收集过程中通过对CPO氧复合物进行可控光还原生成的，这一过程通过记录晶体吸收光谱进行监测。最初，过氧阴离子物种形成，然后质子化生成化合物0。量子化学计算表明，过氧阴离子物种不稳定，会瞬间分解为化合物0。化合物0以三价铁低自旋双重态基态存在，其特征是O—O键长为1.5埃，Fe—O键距为1.8埃，这在晶体结构中也有观察到。
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