Analysis by partial reflection spectrometry of protonated tetraphenylporphyrin adsorbed at a liquid–liquid interface

Moriya, Yoshio; Hasegawa, Takeshi; Hayashi, Kotaro; Maruyama, Machiko; Nakata, Shinichi; Ogawa, Nobuaki
June 2003
Analytical & Bioanalytical Chemistry;Jun2003, Vol. 376 Issue 3, p374
Academic Journal
Visible reflection spectra of diprotonated meso-tetraphenylporphyrin adsorbates spontaneously formed at a dodecane–aqueous sulfuric acid interface have been measured using a home-made device comprising a prism-cell and variable-angle optics. The tilt angle of the pyrrole ring plane was estimated to be 47° from the interface normal by use of an experimentally evaluated molecular density (1.20×10-10 mol cm-2) of the diprotonated molecule in a monolayer form at the liquid–liquid interface. Positive and negative bands have been observed in the p-polarized partial internal reflection (p-PIR) spectra, whose band locations correspond to those in p-polarized external reflection (p-ER) spectra. Nevertheless, the bands in the p-PIR exhibited reversed sign to those of p-ER spectra. These suggest that the surface selection rule of the p-PIR spectrometry has a reversal rule of p-ER and p-PIR can also be used for the analysis of molecular orientation.


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