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Faraday Discuss. 2009;143:235-50; discussion 265-75.

Self-assembly of liquid crystal block copolymer PEG-b-smectic polymer in pure state and in dilute aqueous solution.

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  • 1Institut Curie, Centre de Recherche, CNRS, UMR 168, Université Pierre et Marie Curie, 26 rue d'Ulm, 75248 Paris CEDEX 05, France.


A series of amphiphilic LC block copolymers, in which the hydrophobic block is a smectic polymer poly(4-methoxyphenyl 4-(6-acryloyloxy-hexyloxy)-benzoate) (PA6esterl) and the hydrophilic block is polyethyleneglycol (PEG), were synthesized and characterized. The self-assembly of one of them in both the pure state and the dilute aqueous solution was investigated in detail. Nano-structures in the pure state were studied by SAXS and WAXS on samples aligned by a magnetic field. A hexagonal cylindrical micro-segregation phase was observed with a lattice distance of 11.2 nm. The PEG blocks are in the cylinder, while the smectic polymer blocks form a matrix with layer spacing 2.4 nm and layer normal parallel to the long axis of the cylinders. Faceted unilamellar polymer vesicles, polymersomes, were formed in water, as revealed by cryo-TEM. In the lyotropic bilayer membrane of these polymersomes, the thermotropic smectic order in the hydrophobic block is clearly visible with layer normal parallel to the membrane surface.

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