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Inorg Chem. 2013 Jul 1;52(13):7323-5. doi: 10.1021/ic4011339. Epub 2013 Jun 10.

Generation of high-spin iron(I) in a protein environment using cryoreduction.

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1
Department of Chemistry, Northwestern University, Evanston, Illinois 60208, USA.

Abstract

High-spin Fe(1+) sites are potentially important in iron-sulfur proteins but are rare in synthetic compounds and unknown in metalloproteins. Here, we demonstrate a spectroscopically characterized example of high-spin non-heme Fe(1+) in a protein environment. Cryoreduction of Fe(2+)-substituted azurin at 77 K with (60)Co γ radiation generates a new species with a S = (3)/2 (high-spin) Fe(1+) center having D > 0 and E/D ~ 0.25. This transient species is stable in a glycerol-water glass only up to ~170 K. A combination of electron paramagnetic resonance and Mössbauer spectroscopies provides a powerful means of identifying a transient high-spin Fe(1+) site in a protein scaffold.

PMID:
24004284
PMCID:
PMC3767189
DOI:
10.1021/ic4011339
[Indexed for MEDLINE]
Free PMC Article
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