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| - Estimation of the Orientation of Heme in Cytochrome c Immobilized on aCarboxylate-Terminated Alkanethiol Monolayer on a Au Electrode by theUse of Electroreflectance Spectroscopy with Polarized Light Incidence
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| - Electroreflectance (ER) spectroscopy was used for the estimation of the orientation of heme in a horse heartcytochrome c molecule immobilized on a self-assembled monolayer of 11-mercaptoundecanoic acid on bothpolycrystalline gold (Au) and single crystalline Au(111) electrodes. The intensity ratio of the ER signal ofp-polarized incident light against s-polarized incident light as a function of the incident angle of the light wasanalyzed in two ways: a doubly degenerate transition for the Soret absorption band of the heme was assumedin one, and the anisotropy of the two orthogonal transitions was taken into account in the other. The doublydegenerate model failed in the expression of the experimental data, pointing to the existence of the anisotropy.Two orthogonal in-plane linear electric dipoles with different magnitudes were assumed to be responsible forthe Soret band absorption in a new analysis procedure. This enabled us to fit the experimental data closelyto the simulated data. The result revealed that the heme plane is near-vertical to the electrode surface. Theneed of clarification of the anisotropic heme transition was invoked.
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