Journal of Physical Chemistry, Vol.98, No.38, 9374-9379, 1994
Revisited Depolarization Ratio Dispersion of Raman Fundamentals from Heme-C in Ferrocytochrome-C Confirms That Asymmetric Perturbations Affect the Electronic and Vibrational Structure of the Chromophores Macrocycle
We have remeasured the depolarization ratio of some high-frequency Raman fundamentals from heme c in horse heart ferrocytochrome c at different excitation wavelengths provided by an argon ion laser. AU investigated Raman lines exhibit a significant dispersion of their depolarization ratios. These results contradict recent suggestions by Hu et al. (J. Am. Chem. Soc. 1993, 115, 12466) made on the basis of Raman experiments on various isotopomers of the heme c group in yeast ferrocytochrome c and confirm earlier studies by Schweitzer-Stenner et al. (J. Raman Spectrosc. 1991, 22, 65). The depolarization ratio reflects asymmetric distortions of the heme symmetry imposed by the central Met 80 ligand, the peripheral thioether bonds, and the protein environment. The latter gives rise to nonplanar distortions which are reflected by antisymmetric and symmetric contributions to the Raman tenser to A(2g) and A(1g) modes of the heme c macrocycle, respectively.
Keywords:RESONANCE RAMAN;EXCITATION PROFILES;ISOTOPE SHIFTS;SPECTRA;SPECTROSCOPY;HEMOGLOBIN;PROTEINS;SCATTERING;STATE