An amphiphilic tetraphenylporphyrinatometal (Zn, Fe) derivative having four dialkylglycerophosphocholine groups on one side of the ring plane (lipidporphyrin) was easily dispersed in an aqueous medium to give a red, stable dispersion. Based on electron microscopy, lipidporphyrins themselves produced spherical unilamellar vesicles with a diameter of ca. 100 nm. The thickness of the membrane (9.5 ± 0.5 nm) corresponded to a bilayer of the lipidporphyrin (4.6 nm); the ratio of the lipidporphyrin molecules in the outer and inner layers was 1.57. The lipidporphyrinatozinc(II) vesicle displayed some characteristics of a J-aggregate: (i) a red-shifted Soret band (425 → 438 nm), (ii) no fluorescence quenching, and (iii) a reduced triplet-state lifetime. Simple exciton calculations indicate that the porphyrin squares located in the outer and inner layers formed a J-aggregate with an average angle of 47°. A vesicle composed of the lipidporphyrinatoiron(II) coordinated with an alkylimidazole reversibly formed a stable dioxygen adduct. The O2-binding equilibrium and kinetic parameters were determined. This vesicle has the ability to act as a totally synthetic O2 carrier under physiological conditions (pH 7.4, 37°C).
|出版ステータス||Published - 1995|
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