Porphyrin effect on the surface morphology of amphiphilic polymers as observed by atomic force microscopy

Complexes of porphyrin photosensitizers (PPS) with triblock copolymers of ethylene- and propylene oxide - Pluronics(®) - exhibit markedly increased activity in the generation of singlet oxygen in aqueous media, as compared to pure porphyrins. Pluronics are amphiphilic polymers with surfactant properties suitable for a number of medical applications. PPS-Pluronic systems are considered as promising agents for photodynamic therapy which implies generation of singlet oxygen in the water-based human tissue. Importantly, Pluronics are capable of solubilization of not only water-soluble, but also hydrophobic PPS providing their transfer into the aqueous phase. It has been shown earlier that specific interactions of PPS with Pluronics must play a primary role for the photocatalytic properties of PPS-Pluronic systems. In the process of solubilization of a hydrophobic porphyrin by a Pluronic, both components are dissolved in an organic solvent, which is then removed, and the dry film is re-dissolved in water. Apparently, the initial binding between the porphyrin and the lipophilic part of the polymer takes place already at the stage of the film formation. We applied atomic force microscopy (AFM) to visualize structures formed by Pluronics upon their interactions with meso-tetraphenylporphyrin (TPP). We studied the surface structure of Pluronics(®) F87, F108 and F127 crystallized alone or together with TPP on silicon substrates from chloroform solutions. We found Pluronics to form similar dendritic structures independently of their molecular weight and degree of hydrophobicity. In the presence of TPP, though, we observed formation of distinct convex structures on top of the Pluronic dendrites. These structures appeared to consist of multiple flat layers placed on top of each other. Their sizes varied among the three Pluronics. We believe that TPP aggregates interact with the hydrophobic units of Pluronics causing the polymer chains to pack themselves in a distinct manner around those TPP-containing "cores". These interactions apparently direct formation of complexes between the porphyrin and the polymer upon their dissolution in water, thus resulting in the encapsulation of TPP aggregates inside a Pluronic micelle. A single mechanism for the TPP solubilization by Pluronics is consistent with the same catalytic activity of the three TPP-Pluronic systems observed in the photooxidation of tryptophan.