Langmuir, Vol.26, No.8, 5726-5733, 2010
Light-Triggered Liposomal Release: Membrane Permeabilization by Photodynamic Action
Photosensitized damage to liposome membranes was studied by using different dye-leakage assays based on fluorescence dequenching of a series of dyes upon their release from liposomes. Irradiation of liposomes with red light in the presence of a photosensitizer, trisulfonated aluminum phthalocyanine (AIPcS(3)), resulted in the pronounced leakage of carboxyfluorescein, hut rather weak leakage of sulforhodamine B and almost negligible leakage of calcein from the corresponding dye-loaded liposomes. The same series of selectivity of liposome leakage was obtained with chlorin c6 that appeared to be more potent than AlPcS3 in bringing about the photosensitized liposome leakage. Electrically neutral zinc phthalocyanine tetrasubstituted with a glycerol moiety (ZnPcGlyc(4)) was less effective than negatively charged AlPcS3 in provoking the light-induced liposome permeabilization. On the contrary, both ZnPcGlyc(4) and AlPcS3 were much more effective than chlorin c6 in sensitizing gramicidin channel inactivation in planar bilayer lipid membranes, dos showing that relative photodynamic efficacy of sensitizers can differ substantially for damaging different membrane targets. The photosensitized liposome permeabilization was apparently associated with oxidation of lipid double bonds by singlet oxygen as evidenced by the mandatory presence of unsaturated lipids in the membrane composition for the photosensitized liposome leakage to occur and the sensitivity of the latter to sodium azide. The fluorescence correlation spectroscopy measurements revealed marked permeability of photodynamically induced pores in liposome membranes for such photosensitizer as AlPcS3.