The coordination of imidazole and substituted pyridines by the hemeoctapeptide N-acetyl-ferromicroperoxidase-8 (FeIINAcMP8)

Journal of Inorganic Biochemistry
Preeti R Vashi, Helder M. Marques

Abstract

The N-terminus acetylated ferric hemeoctapeptide from cytochrome c, N-acetylmicroperoxidase-8 (Fe(III)-NAcMP8) can be reduced by dithionite in aqueous solution to produce Fe(II)-NAcMP8. The UV-Vis spectrum has a broad Soret band and relatively poorly defined Q bands which is consistent with a mixture of a five-coordinate high spin species with His as the axial ligand and a six-coordinate, predominantly high spin species with His/H(2)O as axial ligands. There are two spectroscopically observable pK(a)s at 8.7+/-0.1 and 10.9+/-0.2 which are attributed to ionization of a heme propionic acid group and coordinated H(2)O, respectively; a pK(a) > or = 14 is due to ionization of the proximal His ligand. Equilibrium constants were determined by UV-Vis spectrophotometry at 25.0+/-0.2 degrees C and 0.5 M ionic strength (NaClO(4)) for the coordination of imidazole and a number of substituted pyridines, and complement available data for the ferric hemepeptide, allowing a comparison to be made of the affinity of an iron porphyrin with Fe in the +2 and +3 oxidation states towards these ligands. Imidazole is coordinated more strongly by the ferric porphyrin (log K=4.08) than by the ferrous porphyrin (log K=3.40). The equilibrium constants for ...Continue Reading

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Citations

Jul 31, 2008·Journal of Medicinal Chemistry·Sanjeev KumarAlexander J Muller
Nov 13, 2008·Proteins·Zhong Zheng, M R Gunner
Mar 20, 2013·Biochimica Et Biophysica Acta·M R GunnerJianxun Lu
Aug 1, 2006·Biophysical Journal·Enrica DroghettiGiulietta Smulevich
May 23, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Marcus C Durrant
Oct 3, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Helder M Marques
Jul 25, 2017·Israel Journal of Chemistry·Edward I SolomonBenjamin E R Snyder

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