X-ray Absorption Spectroscopy of Chloroperoxidase Compound I: Insight into the Reactive Intermediate of P450 Chemistry

We report the structural characterization of a thiolate-ligated ferryl radical. Using x-ray absorption spectroscopy, we examined chloroperoxidase (CPO) compound I (CPO-I). Our results indicate that CPO-I is an authentic ferryl species with an Fe-O bond of 1.65 Å. Axial-ligand interactions result in...

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Published inProceedings of the National Academy of Sciences - PNAS Vol. 102; no. 46; pp. 16563 - 16565
Main Authors Kari L. Stone, Rachel K. Behan, Green, Michael T.
Format Journal Article
LanguageEnglish
Published United States National Academy of Sciences 15.11.2005
National Acad Sciences
Subjects
Absorption spectra
Absorption spectroscopy
Biological Sciences
Chemical bonding
Chemical reactions
Chloride Peroxidase - chemistry
Cytochrome P-450 Enzyme System - chemistry
Cytochromes
Data lines
Enzymes
Green chemistry
Iron
Ligands
Oxidation
Oxygen
Physical Sciences
Protein Conformation
Spectrum Analysis
Sulfur
X-Rays
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Summary:We report the structural characterization of a thiolate-ligated ferryl radical. Using x-ray absorption spectroscopy, we examined chloroperoxidase (CPO) compound I (CPO-I). Our results indicate that CPO-I is an authentic ferryl species with an Fe-O bond of 1.65 Å. Axial-ligand interactions result in a remarkably long 2.48-Å Fe-S bond. Analogous forms of cytochrome P450 and CPO have been shown to possess virtually identical coordination environments. Thus, it seems likely that our findings provide a good structural description of the elusive P450-I.
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To whom correspondence should be addressed. E-mail: mtg10@psu.edu.
Conflict of interest statement: No conflicts declared.
This paper was submitted directly (Track II) to the PNAS office.
Abbreviations: CPO, chloroperoxidase; CPO-I, chloroperoxidase compound I; EXAFS, extended x-ray absorption fine structure; QM/MM, quantum mechanics/molecular mechanics.
Author contributions: K.L.S., R.K.B., and M.T.G. performed research; K.L.S. and M.T.G. analyzed data; K.L.S. and M.T.G. wrote the paper; and M.T.G. designed research.
Edited by Harry B. Gray, California Institute of Technology, Pasadena, CA, and approved October 5, 2005
ISSN:0027-8424
1091-6490
DOI:10.1073/pnas.0507069102