QUANTUM YIELD OF PRODUCTION OF SINGLET MOLECULAR OXYGEN (^xδ_g) IN AQUEOUS DISPERSIONS OF SMALL UNILAMELLAR LIPID VESICLES. A TIME‐RESOLVED NEAR‐IR PHOSPHORESCENCE STUDY*,†

The quantum yield of formation and kinetic behaviour of O₂(¹δ_g) in D₂O dispersions of small unilamellar vesicles (SUVs) of dipalmitoyl phosphatidylcholine were studied by time‐resolved detection of near‐IR phosphorescence. At a SUV concentration of 26 nM, O₂(¹δ_g) is not quenched by the vesicles. It diffuses quickly through the lipid bilayer and a partition equilibrium of O₂(¹δ_g) between the lipid bilayer and the buffer is attained before decay occurs. In this equilibrium situation O₂(¹δg/sb>) is mostly located in the buffer phase, which permits the determination of absolute quantum yields for O₂(¹δ_g) production, φ_δ, by comparison of the luminescence in the dispersions with that in neat D₂O. The maximal φ_δ values for the sensitizers incorporated in the SUV bilayer were 0.47 ± 0.09 for the dipyridyl complex of zinc(II) phthalocyanine (ZnPc), 0.35 ± 0.08 for porphycene, and 0.36 ± 0.08 for 2,7,12,17‐tetra‐H‐propylporphycene. These values are equal to those in neat organic solvents but lower than those previously obtained in SUVs by using chemical trapping agents. The high degree of organization of the environment around the sensitizers does not influence their efficiency of producing O₂(¹δ_g). While no concentration dependence is observed for ZnPc (at least up to a local concentration of 20 mM in the bilayer), φ_δ for both porphycenes significantly decreases above a local concentration of 4 mM in the bilayer. This result is expected in view of previous observations on the concentration dependence of other photophysical parameters of the porphycenes in such microheterog‐eneous media.