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Proc Natl Acad Sci U S A. 2003 Apr 1;100(7):3589-94. Epub 2003 Feb 21.

Non-heme iron enzymes: contrasts to heme catalysis.

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1
Department of Chemistry, Stanford University, Stanford, CA 94305, USA. edward.solomon@stanford.edu

Abstract

Non-heme iron enzymes catalyze a wide range of O(2) reactions, paralleling those of heme systems. Non-heme iron active sites are, however, much more difficult to study because they do not exhibit the intense spectral features characteristic of the porphyrin ligand. A spectroscopic methodology was developed that provides significant mechanistic insight into the reactivity of non-heme ferrous active sites. These studies reveal a general mechanistic strategy used by these enzymes and differences in substrate and cofactor interactions dependent on their requirement for activation by iron. Contributions to O(2) activation have been elucidated for non-heme relative to heme ligand sets, and major differences in reactivity are defined with respect to the heterolytic and homolytic cleavage of O-O bonds.

PMID:
12598659
PMCID:
PMC152966
DOI:
10.1073/pnas.0336792100
[Indexed for MEDLINE]
Free PMC Article
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