PMID: 3756147Jul 29, 1986Paper

Alternative carbon monoxide binding modes for horseradish peroxidase studied by resonance Raman spectroscopy

Biochemistry
R Evangelista-KirkupT G Spiro

Abstract

Resonance Raman (RR) spectroscopy and infrared spectroscopy have been used to characterize the three vibrational modes, CO and FeC stretching and FeCO bending, for carbon monoxide bound to reduced horseradish peroxidase, with the aid of 13CO and C18O isotope shifts. At high pH, one species, I, is observed, with nu FeC = 490 cm-1 and nu CO = 1932 cm-1. The absence of a band attributable to delta FeCO suggests a linear FeCO unit normal to the heme plane. The data were consistent with I having a strongly H-bonded proximal histidine, as shown by a comparison with imidazole and imidazolate adducts of FeIIPPDME(CO) (PPDME = protoporphyrin IX dimethyl ester), with nu FeC = 497 and 492 cm-1 and nu CO = 1960 and 1942 cm-1. At low pH an additional species, II, is observed, with nu FeC = 537 cm-1, nu CO = 1904 cm-1, and delta FeCO = 587 cm-1; it is attributed to FeCO that is H bonded to a protonated distal histidine, the H bond strongly lowering nu CO and raising nu FeC. The appearance of delta FeCO in the RR spectrum suggests that the FeCO unit in II is tilted with respect to the heme plane. At low pH, the population of I and II depends on the CO concentration. I dominates at low CO/protein levels but is replaced by II as the amount of C...Continue Reading

Citations

Mar 20, 1987·Journal of Molecular Biology·W DosterE Shyamsunder
Jun 1, 2000·Journal of Inorganic Biochemistry·C G KalodimosA Troganis
Nov 15, 2007·Inorganic Chemistry·Thomas G Spiro
Sep 19, 2006·Biophysical Journal·Andras D KaposiSolomon S Stavrov
Feb 6, 1999·The Journal of Biological Chemistry·T K DasJ B Wittenberg
Feb 17, 2006·The Journal of Biological Chemistry·Tapan K DasDenis L Rousseau
May 5, 1995·The Journal of Biological Chemistry·J al-MustafaJ R Kincaid
Mar 9, 2013·Coordination Chemistry Reviews·Thomas G SpiroGurusamy Balakrishnan
Jul 18, 2001·Journal of the American Chemical Society·T DengS G Sligar
Aug 7, 2008·Journal of the American Chemical Society·Francesco P NicolettiGiulietta Smulevich
Jul 18, 2001·Journal of the American Chemical Society·T TomitaM Ikeda-Saito

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