Self-Organized Lipid-Porphyrin Bilayer Membranes in Vesicular Form: Nanostructure, Photophysical Properties, and Dioxygen Coordination

摘要

An amphiphilic tetraphenylporphyrin and its iron complex bearing four phospholipid substituents, in which a trimethylolethane residue connects the two acyl chains (lipid-porphyrins), have been synthesized. The free-base lipidporphyrin 6a self-organizes in aqueous media to form spherical unilamellar vesicles with a diameter of 100 nm and a uniform thickness of 10 nm, which corresponds to twice the length of the molecule. In the visible absorption spectrum, the porphyrin Sorest band was significantly red-shifted (12 nm) relative to that of the monomer in benzene/MeOH solution due to the excitonic interaction of the porphyrin chromophores. The #PI#-A isotherm of 6a gave an area per molecule of 2.2 nm~2, which allowed the estimation of the number of molecules in a single vesicle (2.3 X 10~4). Double-layered Langmuir-Blodgett (LB) films of 6a on a glass surface exhibited an absorption spectrum identical to that of the 6a vesicles in bulk aqueous solution, and this suggests that they contain similar geometric arrangements of the porphyrin moieties. Exciton calculations on the basis of our structural model reproduced the bathochromic shift of the Soret band well. In the photophysical properties of the 6a vesicles, the characteristics of J-aggregated porphyrins substantially predominate: strong fluorescence and extremely short triplet lifetime. The iron complex 6b with a small molar excess of 1-dodecylimidazole (DIm) also formed spherical unilamellar vesicles (100 nm #PHI#). Scanning force microscopy after evaporation on a graphite surface revealed 6b/DIm vesicles with a vertical height of 19.8 nm, which coincided with the thickness of the double bilayer membranes. The ferrous 6c formed a bis(DIm)coordinated low-spin Fe~(II) complex under an N_2 atmosphere. Upon addition of O_2 to this solution, a kinetically stable O_2 adduct was formed at 37 deg C with a half-life of 17 h. Distinct gel-phase (liquid-crystal) transitions of the lipid-porphyrin membranes were clearly observed; the free base 6a displayed a higher transition temperature (56 deg C) than the iron complex Magnetic circular dichroism and infrared spectroscopic studies proved that molecular O_2 coordinates to the self-organized lipid-porphyrinatoiron(II) vesicles in aqueous media.