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A Short Fe-Fe Distance in Peroxodiferric Ferritin: Control of Fe Substrate Versus Cofactor Decay?
Abstract
The reaction of oxygen with protein diiron sites is important in bioorganic syntheses and biomineralization. An unusually short Fe-Fe distance of 2.53 angstroms was found in the diiron (μ-1,2 peroxodiferric) intermediate that forms in the early steps of ferritin biomineralization. This distance suggests the presence of a unique triply bridged structure. The Fe-Fe distances in the μ-1,2 peroxodiferric complexes that were characterized previously are much longer (3.1 to 4.0 angstroms). The 2.53 angstrom Fe-Fe distance requires a small Fe-O-O angle (∼106° to 107°). This geometry should favor decay of the peroxodiferric complex by the release of H 2 O 2 and μ-oxo or μ-hydroxo diferric biomineral precursors rather than by oxidation of the organic substrate. Geometrical differences may thus explain how diiron sites can function either as a substrate (in ferritin biomineralization) or as a cofactor (in O 2 activation).
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Cited by
Merkx, M., Kopp, D. A., Sazinsky, M. H., Blazyk, J. L., Müller, J., & Lippard, S. J. (2001) · Angewandte Chemie International Edition · doi:10.1002/1521-3773(20010803)40:15<2782::aid-anie2782>3.3.co;2-g · Cited by 659
Jasniewski, A. J., & Que, L. (2018) · Chemical Reviews · doi:10.1021/acs.chemrev.7b00457 · Cited by 474
Bis(μ-oxo)dimetal “Diamond” Cores in Copper and Iron Complexes Relevant to Biocatalysis
Que, Jr., & Tolman, W. B. (2002) · Angewandte Chemie International Edition · doi:10.1002/1521-3773(20020402)41:7<1114::aid-anie1114>3.0.co;2-6 · Cited by 416
Unity in the Biochemistry of the Iron-Storage Proteins Ferritin and Bacterioferritin
Honarmand Ebrahimi, K., Hagedoorn, P.-L., & Hagen, W. R. (2015) · Chemical Reviews · doi:10.1021/cr5004908 · Cited by 297
NEW EMBO MEMBER'S REVIEW: Ferritins, iron uptake and storage from the bacterioferritin viewpoint
Carrondo, M. A. (2003) · The EMBO Journal · doi:10.1093/emboj/cdg215 · Cited by 283
Metadata
- Authors
- Hwang, J., Krebs, C., Huynh, B. H., Edmondson, D. E., Theil, E. C., & Penner-Hahn, J. E.
- Venue
- Science
- Published
- 2000-01-07
- Volume
- 287
- Issue
- 5450
- Pages
- 122-125
- ISSN
- 0036-8075 (ISSN-L)
- 1095-9203
- OpenAlex
- W2015197751
- Cited by
- 185
- References
- 0
- FWCI
- 13.95
- Type
- journal article
- Language
- en
- Open access
- closed
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- Hwang, J., Krebs, C., Huynh, B. H., Edmondson, D. E., Theil, E. C., & Penner-Hahn, J. E. (2000). A Short Fe-Fe Distance in Peroxodiferric Ferritin: Control of Fe Substrate Versus Cofactor Decay? Science. https://doi.org/10.1126/science.287.5450.122
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Contains information from the Semantic Scholar Academic Graph Datasets, made available under the ODC Attribution License (ODC-BY 1.0).
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