  A series of amphiphilic LC block copolymers, in which the hydrophobic block
is a smectic polymer poly(4-methoxyphenyl 4-(6-acryloyloxy-hexyloxy)-benzoate)
(PA6ester1) 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.
