Time-resolved visible and infrared study of the cyano complexes of myoglobin and of hemoglobin I from Lucina pectinata

Biophys J. 2004 Sep;87(3):1881-91. doi: 10.1529/biophysj.103.036236.

Abstract

The dynamics of the ferric CN complexes of the heme proteins Myoglobin and Hemoglobin I from the clam Lucina pectinata upon Soret band excitation is monitored using infrared and broad band visible pump-probe spectroscopy. The transient response in the UV-vis spectral region does not depend on the heme pocket environment and is very similar to that known for ferrous proteins. The main feature is an instantaneous, broad, short-lived absorption signal that develops into a narrower red-shifted Soret band. Significant transient absorption is also observed in the 360-390 nm range. At all probe wavelengths the signal decays to zero with a longest time constant of 3.6 ps. The infrared data on MbCN reveal a bleaching of the C triple bond N stretch vibration of the heme-bound ligand, and the formation of a five-times weaker transient absorption band, 28 cm(-1) lower in energy, within the time resolution of the experiment. The MbC triple bond N stretch vibration provides a direct measure for the return of population to the ligated electronic (and vibrational) ground state with a 3-4 ps time constant. In addition, the CN-stretch frequency is sensitive to the excitation of low frequency heme modes, and yields independent information about vibrational cooling, which occurs on the same timescale.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Animals
  • Electrons
  • Heme / chemistry
  • Hemoglobins / chemistry*
  • Horses
  • Iron / chemistry
  • Kinetics
  • Lasers
  • Mollusca
  • Muscle, Skeletal / metabolism
  • Myoglobin / chemistry*
  • Spectrophotometry
  • Spectrophotometry, Infrared / methods*
  • Spectroscopy, Fourier Transform Infrared
  • Time Factors
  • Ultraviolet Rays

Substances

  • Hemoglobins
  • Myoglobin
  • Heme
  • Iron