Self-assembly of amphiphilic meso-aryl-substituted porphyrin derivatives in the presence of surfactants

Surfactant-assisted self-assembly of porphyrin molecules in aqueous solutions sometimes leads to the formation of hybrid supramolecular structures with unusual photophysical properties resulting from the dipole–dipole interactions between the neighboring aromatic systems. The macrocycle orientation and interchromophore distance in such assemblies are determined by the dye–surfactant interactions, and hence, strongly depend on the molecular structure of both surfactant and porphyrin molecules. In this paper we studied the influence of the number and position of the peripheral alkyl chains of amphiphilic meso-aryl-substituted porphyrins on their aggregation behavior and intermolecular interactions with different surfactants in aqueous solutions. The studies revealed a crucial role of the local acidity on the micellar surface in the protolytic equilibrium of the porphyrin derivatives, as well as the influence of the macrocycle hydrophilic–lipophilic balance on its solubilization site within a micellar system. These findings enable prediction of the photophysical properties of amphiphilic porphyrin derivatives in the presence of different solubilizing agents and membrane-mimetic systems, and hence, selection the most suitable drug delivery systems for the novel amphiphilic porphyrin-based photosensitizers.