A comparison of the heme electronic states in equilibrium and nonequilibrium protein conformations of high-spin ferrous hemoproteins. Low temperature magnetic circular dichroism studies

Biochim Biophys Acta. 1982 Dec 20;709(2):332-41. doi: 10.1016/0167-4838(82)90476-9.

Abstract

The visible and near infrared magnetic circular dichroism (MCD) spectra of equilibrium high-spin ferrous derivatives of myoglobin, hemoglobin, horseradish peroxidase and mitochondrial cytochrome c oxidase at 15 K are compared with those of the corresponding proteins in nonequilibrium conformations produced by low-temperature photodissociation of CO-complexes of these proteins as well as of O2-complexes of myoglobin and hemoglobin. Over all the spectral region (450-800 nm) the intensities of MCD bands of hemoproteins studied in equilibrium conformation are shown to be strongly temperature-dependent, including a negative band at ca. 630 nm and positive bands at ca. 690 nm and at ca. 760 nm. In contrast to the absorption spectra, the low-temperature MCD spectra of high-spin ferrous hemoproteins differ significantly, reflecting the peculiarities in the heme iron coordination sphere which are created by a protein conformation. The MCD spectra reveal clearly the structural changes in the heme environment which occur on ligand binding. On the basis of assignment of d leads to d and charge-transfer transitions in the near infrared region the correlation is suggested between the wavelength position of the MCD band at approx. 690 nm and the value of iron out-of-plane displacement as well as between the location of the band at approx. 760 nm and the Fe-N epsilon (proximal histidine) bond strength (length) in equilibrium and nonequilibrium conformations of the hemoproteins studied. The high sensitivity of low-temperature MCD spectra to geometry at heme iron is discussed.

MeSH terms

  • Animals
  • Carbon Monoxide
  • Cattle
  • Circular Dichroism
  • Electron Transport Complex IV
  • Heme*
  • Hemeproteins*
  • Hemoglobins
  • Horseradish Peroxidase
  • Humans
  • Kinetics
  • Mitochondria, Heart / enzymology
  • Myoglobin
  • Protein Binding
  • Protein Conformation
  • Whales

Substances

  • Hemeproteins
  • Hemoglobins
  • Myoglobin
  • Heme
  • Carbon Monoxide
  • Horseradish Peroxidase
  • Electron Transport Complex IV