Electron-nuclear coupling in nitrosyl heme proteins and in nitrosyl ferrous and oxy cobaltous tetraphenylporphyrin complexes
Electron spin echo envelope modulation (ESEEM) spectroscopy has been used to study electron-nuclear interactions in the following isoelectronic S = 1/2 complexes: NO-Fe/sup II/(TPP) (TPP = tetraphenylporphyrin) with and without axial nitrogenous base, nitrosylhemoglobin in R and T states, and O/sub 2/-Co/sup II/(TPP) with and without axial base. Only the porphyrin pyrrole nitrogens contribute to the ESEEM of the 6-coordinate nitrosyl Fe/sup II/(TPP) complexes, nitrosylhemoglobin (R-state), and the nitrosyl complexes of ..cap alpha.. and ..beta.. chains. Pyrrole nitrogens in the 5-coordinate complex NO-Fe/sup II/(TPP) are coupled to weakly to unpaired spin and therefore do not contribute to the ESEEM. A partially saturated T-state nitrosyl-hemoglobin does not exhibit echo envelope modulations characteristic of 6-coordinate nitrosyl species, which confirms that the proximal imidazole bond to heme iron is disrupted. Study of 6-coordinate O/sub 2/-Co/sup II/(TPP)(L) complexes (L = nitrogenous base) using /sup 14/N- and /sup 15/N-labeled ligands and porphyrins enabled a detailed analysis of coupling parameters for both pyrrole and axial nitrogens. The pyrrole /sup 14/N coupling frequencies are similar to those in NO-Fe/sup II/(TPP)(L). The Fermi contact couplings for axially bound nitrogen, calculated from simulation of ESEEM spectra for a series of O/sub 2/-Co/sup II/(TPP)(L) complexes (L = pyridine, 4-picoline, 4-cyanopyridine, 4-carboxypyridine, and 1-, 2-, and 4-methylimidazole) illustrate a trend toward stronger hyperfine interactions with weaker bases.
- Research Organization:
- Albert Einstein College of Medicine, Bronx, NY
- OSTI ID:
- 5436029
- Journal Information:
- Biochemistry; (United States), Vol. 26:24
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
PORPHYRINS
ELECTRON SPIN RESONANCE
HEME
NITROGEN 14
NITROGEN 15
NITROSO COMPOUNDS
CARBOXYLIC ACIDS
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
NITROGEN ISOTOPES
NUCLEI
ODD-EVEN NUCLEI
ODD-ODD NUCLEI
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PIGMENTS
RESONANCE
STABLE ISOTOPES
550601* - Medicine- Unsealed Radionuclides in Diagnostics