PMID: 5156Jan 1, 1975

Magnetic and spectroscopic probes for FeOFe linkages in hemin systems

Bioinorganic Chemistry
D H O'KeeffeW S Caughey

Abstract

Magnetic and spectroscopic properties of mu-oxo-bis-hemins from natural and structurally related porphyrins were investigated as probes for ascertaining the presence or absence of FeIII-O-FeIII linkages between hemin moieties of hemeproteins. Magnetic susceptibilities of solids from 2.2 to 293 degrees K were investigated. The data fit the temperature variations expected for a pair of antiferromagnetically coupled S = 5/2, iron (III) porphyrins with J values of 175, 190, 195, 205, and 210 degrees K for deuterohemins with hydrogen, vinyl, 2'-ethoxycarbonylcyclopropyl, acetyl, propionyl, and ethyl 2,4-substituents, respectively. This magnetic character is reflected in PMR spectra that exhibit resonances with far less broadening and paramagnetic shift than is the case for monomeric high-spin hemins. Only impurities are seen in EPR spectra, which serve effectively in monitoring the magnetic purity of preparations. An infrared active asymmetric stretching frequency characteristic of the FeOFe linkage can be identified by substitution of 160 by 180. Electronic spectra are highly characteristic with poorly resolved absorption bands. The substituents on the porphyrin ring exert significant, but usually not large, electronic and steric e...Continue Reading

References

Apr 15, 1975·Annals of the New York Academy of Sciences·W S CaugheyW J Wallace
Jul 1, 1975·Bioinorganic Chemistry·W H FuchsmanW S Caughey
May 1, 1972·Archives of Biochemistry and Biophysics·D F Wilson, J S Leigh
Jan 1, 1973·Annals of the New York Academy of Sciences·W S CaugheyM C O'Toole
Jun 19, 1973·Biochemistry·T H MossH S Mason
Jun 28, 1972·Journal of the American Chemical Society·M WicholasD Jayne
Jun 14, 1972·Journal of the American Chemical Society·M A TorrénsL M Epstein
Jun 30, 1971·Journal of the American Chemical Society·E B FleischerA Chatterjee
Apr 1, 1969·European Journal of Biochemistry·P Mohr, W Scheler
Aug 1, 1966·The Journal of Organic Chemistry·W S CaugheyJ L York
Jun 1, 1967·Journal of Medical Education·J L Caughey
Sep 1, 1962·Biochemistry·W S Caughey, W S KOSKI
Feb 1, 1950·American Journal of Surgery·E E JEMERIN

Citations

Feb 1, 1981·Journal of Inorganic Biochemistry·T A WalshC Greenwood
Apr 1, 1977·CRC Critical Reviews in Food Science and Nutrition·G G Giddings
Sep 15, 2006·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Katherine A de VilliersH M Marques
Sep 28, 2017·Physical Chemistry Chemical Physics : PCCP·Arpita NathS Mazumdar
Jun 27, 2019·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Jeremie RossierFabio Zobi
Sep 1, 1987·Magnetic Resonance in Medicine : Official Journal of the Society of Magnetic Resonance in Medicine·J A HelpernK M Welch

Related Concepts

Heme
Panhematin
Hydrogen-Ion Concentration
Iron
In Vivo NMR Spectroscopy
Dioxygen

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