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Iron ligand recognition by monomeric hemoglobins
Journal article   Peer reviewed

Iron ligand recognition by monomeric hemoglobins

Joseph J. Stephanos, Scott A. Farina and Anthony W. Addison
Biochimica et biophysica acta, Protein structure and molecular enzymology, v 1295(2)
1996
PMID: 8695648

Abstract

Ambidentate Electron paramagnetic resonance Heterocyclic amine Histidine Morpholine Myoglobin Thermodynamics
Binding affinities of monomeric Glycera dibranchiata hemoglobin for some anions and heterocyclic amines, including imidazoles, pyrazole, triazole and tetrazole have been evaluated and compared with those of sperm whale and horse heart myoglobin. The proteins' affinities for substituted heterocyclic amines are strongly influenced by the steric bulk and flexibility of the aromatic ring. The ligand coordination mode depends on the heme oxidation state, iron(III) amine adducts being more stable than the iron(II) adducts, the higher affinities of stronger Brønsted-Lowry bases reflecting their essentially σ-donor character. The bifunctional molecule morpholinoethylisocyanide acts as a redox-state-dependent ambidentate ligand, binding as an N-donor to iron(III), but as a C-donor to iron(II). pH-Dependences of the ESR and optical spectra of the azole adducts reveal iron-linked ionisations and spin-equilibria in the heme pocket. Enthalpy and entropy changes for the binding process were estimated for several ligands, and mutually compensatory behaviour is observed globally for ΔH° and ΔS°. At the compensation temperature θ, the binding affinities of monomeric Glycera dibranchiata hemoglobin and sperm whale myoglobin are similar and associated with free energy changes ΔG°( θ) ≈ −9 ± 1 kJ mol −1 for the heterocyclic and anionic ligands.

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Domestic collaboration
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Web of Science research areas
Biochemistry & Molecular Biology
Biophysics
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