DFT analysis of axial and equatorial effects on heme-CO vibrational modes: applications to CooA and H-NOX heme sensor proteins

Biochemistry. 2008 Feb 26;47(8):2379-87. doi: 10.1021/bi702254y. Epub 2008 Jan 25.

Abstract

Determinants of the Fe-CO and C-O stretching frequencies in (imidazole)heme-CO adducts have been investigated via density functional theory (DFT) analysis, in connection with puzzling characteristics of the heme sensor protein CooA and of the H-NOX (Heme-Nitric Oxide and/or OXygen binding) family of proteins, including soluble guanylate cyclase (sGC). The computations show that two mechanisms of Fe-histidine bond weakening have opposite effects on the nuFeC/nuCO pattern. Mechanical tension is expected to raise nuFeC with little change in nuCO whereas the weakening of H-bond donation from the imidazole ligand has the opposite effect. Data on CooA indicate imidazole H-bond weakening associated with heme displacement, as part of the activation mechanism. The computations also reveal that protein-induced distortion of the porphyrin ring, a prominent structural feature of the H-NOX protein TtTar4H (Thermoanaerobacter tengcongensis Tar4 protein heme domain), has surprisingly little effect on nuFeC or nuCO. However, another structural feature, strong H-bonding to the propionates, is suggested to account for the weakened back bonding that is evident in sGC. TtTar4H-CO itself has an elevated nuFeC, which is successfully modeled as a compression effect, resulting from steric crowding in the distal pocket. nuFeC/nuCO data, in conjunction with modeling, can provide valuable insight into mechanisms for heme-protein modulation.

Publication types

  • Research Support, N.I.H., Extramural

MeSH terms

  • Bacterial Proteins / chemistry
  • Biosensing Techniques*
  • Carbon / chemistry*
  • Carbon Dioxide / chemistry*
  • Heme / analysis*
  • Heme / chemistry*
  • Heme / metabolism
  • Histidine / chemistry
  • Hydrogen Bonding
  • Imidazoles / chemistry
  • Models, Biological
  • Models, Molecular
  • Molecular Conformation
  • Nitric Oxide / chemistry*
  • Nitric Oxide / metabolism
  • Oxides / chemistry
  • Oxygen / chemistry*
  • Oxygen / metabolism
  • Porphyrins / chemistry
  • Propionates / chemistry
  • Protein Folding
  • Quantum Theory
  • Thermoanaerobacter
  • Vibration

Substances

  • Bacterial Proteins
  • Imidazoles
  • Oxides
  • Porphyrins
  • Propionates
  • Carbon Dioxide
  • carboxyl radical
  • Nitric Oxide
  • Heme
  • Histidine
  • Carbon
  • imidazole
  • Oxygen