液液界面におけるポルフィリン集合体のラマン分光と第二高調波円二色性に関する研究
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Ion-association adsorption and interfacial aggregation of ionic-porphyrin at a liquid/liquid interface was investigated by means of two spectroscopic techniques; total-internal reflection (TIR) Raman microspectroscopy and second harmonic generation-circular dichroism (SHG-CD). In a TIR-Raman study, the electrostatic adsorption of meso-tetrakis(N-methylpyridyl)porphyrinato manganese(III){Mn(TMPyP)^<5+>} with dihexadecylphosphate (DHP) was analyzed. Polarized Raman spectra suggested that the average tilt angle of the porphyrin plane of the Mn(TMPyP)^<5+> molecule to the interface normal was 65° at the interface adsorbed with the DHP anion. The interfacial ion-association adsorption of Mn(TMPyP)^<5+> with DHP was analyzed by the Langmuir isotherm, and the adsorption parameters were obtained. On the other hand, interfacial adsorption and aggregation of Tetrakis-(4-sulfonatephenyl) porphyrin (TPPS) diacid, promoted by cetyltrimethylammonium(CTA^+), was studied by SHG spectroscopy. The aggregation of TPPS at the heptane/water interface was elucidated by the linearly polarized SH spectrum compared with the transmission absorption spectrum of TPPS in aqueous solution. Also, the non-linear optical activity for the TPPS aggregate was also measured by means of SHG-CD and SHG-linear dichroism (SHG-LD). SHG-CD spectra indicated bisignate sign similar to that of the ordinary CD spectra for the aggregate. SHG-LD elucidated a magnetic-dipole contribution to some chiral structure of the TPPS aggregate.
- 社団法人日本分析化学会の論文
- 2005-07-05
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