Comparing the electronic properties of the low-spin cyano-ferric [Fe(N4)(Cys)] active sites of superoxide reductase and p450cam using ENDOR spectroscopy and DFT calculations.

Comparing the electronic properties of the low-spin cyano-ferric [Fe(N4)(Cys)] active sites of superoxide reductase and p450cam using ENDOR spectroscopy and DFT calculations. Research Abstract Details 

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Comparing the electronic properties of the low-spin cyano-ferric [Fe(N4)(Cys)] active sites of superoxide reductase and p450cam using ENDOR spectroscopy and DFT calculations. Abstract Text:

Tran-Chin Yang,Rebecca L McNaughton,Michael D Clay,Francis E Jenney,Rangan Krishnan,Donald M Kurtz,Michael W W Adams,Michael K Johnson,Brian M Hoffman,

Superoxide reductase (SOR) and P450 enzymes contain similar [Fe(N)4(SCys)] active sites and, although they catalyze very different reactions, are proposed to involve analogous low-spin (hydro)peroxo-Fe(III) intermediates in their respective mechanisms that can be modeled by cyanide binding. The equatorial FeN4 ligation by four histidine ligands in CN-SOR and the heme in CN-P450cam is directly compared by 14N ENDOR, while the axial Fe-CN and Fe-S bonding is probed by 13C ENDOR of the cyanide ligand and 1Hbeta ENDOR measurements to determine the spin density delocalization onto the cysteine sulfur. There are small, but notable, differences in the bonding between Fe(III) and its ligands in the two enzymes. The ENDOR measurements are complemented by DFT computations that support the semiempirical equation used to compute spin densities on metal-coordinated cysteinyl and shed light on bonding changes as the Fe-C-N linkage bends. They further indicate that H bonds to the cysteinyl thiolate sulfur ligand reduce the spin density on the sulfur in both active sites to a degree that exceeds the difference induced by the alternative sets of "in-plane" nitrogen ligands.

Comparing the electronic properties of the low-spin cyano-ferric [Fe(N4)(Cys)] active sites of superoxide reductase and p450cam using ENDOR spectroscopy and DFT calculations. Publishing Authors By Initials

TC Yang,RL McNaughton,MD Clay,FE Jenney,R Krishnan,DM Kurtz,MW Adams,MK Johnson,BM Hoffman,

For similar natural sciences: chemistry: chemistry, organic: isomerism: stereoisomerism research abstracts see: natural sciences: chemistry: chemistry, organic: isomerism: stereoisomerism research

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Comparing the electronic properties of the low-spin cyano-ferric [Fe(N4)(Cys)] active sites of superoxide reductase and p450cam using ENDOR spectroscopy and DFT calculations. Journal Published:

PUBLICATION TYPE: Research Support, N.I.H., Extr

Journal: Journal of the American Chemical Society

VOLUME: 128

Page Numbers: 16566-78

Journal Abbreviation: J. Am. Chem. Soc.

ISSN: 0002-7863

DAY: 27

MONTH: Dec

YEAR: 2006

Comparing the electronic properties of the low-spin cyano-ferric [Fe(N4)(Cys)] active sites of superoxide reductase and p450cam using ENDOR spectroscopy and DFT calculations. Information

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LANGUAGE: eng

NlmUniqueID: 7503056

Comparing the electronic properties of the low-spin cyano-ferric [Fe(N4)(Cys)] active sites of superoxide reductase and p450cam using ENDOR spectroscopy and DFT calculations. Keywords Mesh Terms:

KEYWORDS: Stereoisomerism

MESH TERMS: chemistry

Chemical & Substance for Abstract: Comparing the electronic properties of the low-spin cyano-ferric [Fe(N4)(Cys)] active sites of superoxide reductase and p450cam using ENDOR spectroscopy and DFT calculations. Information

Substance Name: Camphor 5-Monooxygenase

Registry Number: EC 1.14.15.1

Grant and Affiliation Information for Comparing the electronic properties of the low-spin cyano-ferric [Fe(N4)(Cys)] active sites of superoxide reductase and p450cam using ENDOR spectroscopy and DFT calculations.

AFFILIATION: Department of Chemistry and Biochemistry, Center for Metalloenzyme Studies, University of Georgia, Athens, GA 30602, USA

Country: United States

AGENCY: United States NHLBI

GRANT: HL 13531

ACRONYM: HL

MEDLINETA: J Am Chem Soc

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