Potential-Induced Aggregation of Anionic Porphyrins at Liquid|Liquid Interfaces

The adsorption and self-aggregation of anionic porphyrins were studied at the polarized water|1,2-dichloroethane (DCE) interface by polarization-modulation total internal reflection fluorescence (PM-TIRF) spectroscopy. 5,10,15,20-Tetrakis(4-sulfonatophenyl)porphyrin diacid (H₄TPPS^2-) and protoporphyrin IX (H₂PP^2-) exhibited high surface activities at the interface. The selective excitation of interfacial species in PM-TIRF measurements elucidated the potential-induced aggregation mechanism of the porphyrins. The J-aggregates of H₄TPPS^2- were reversibly formed only at the water|DCE interface by applying appropriate potentials even when the porphyrins exist as monomers in the aqueous and organic solutions. In the H₂PP^2- system, the slow aggregation process was found in the negative potential region. The spectral characteristics and the signal phase of PM-TIRF indicated that the H₂PP^2- monomers were adsorbed with relatively standing orientation and that the long axis of the J-aggregates was nearly in plane of the interface. H₂PP^2- was also investigated at the biomimetic phospholipid-adsorbed water|DCE interface. The competitive adsorption of neutral glycerophospholipids effectively inhibited the potential-dependent adsorption and interfacial aggregation processes of H₂PP^2-. The results demonstrated that the aggregation state of the charged species can reversibly be controlled at liquid|liquid interfaces as a function of externally applied potential.