H. Ringsdorf et al., INTERACTIONS OF LIPOSOMES AND HYDROPHOBICALLY-MODIFIED POLY-(N-ISOPROPYLACRYLAMIDES) - AN ATTEMPT TO MODEL THE CYTOSKELETON, Biochimica et biophysica acta, 1153(2), 1993, pp. 335-344
The interactions of small unilamellar vesicles (SUV) and water-soluble
copolymers were studied by fluorescence spectroscopy, differential sc
anning calorimetry (DSC) and quasi-elastic light scattering (QELS). Th
e anchoring onto liposomal bilayer membranes of copolymers of N-isopro
pylacrylamide, N-(2-(1-naphthyl)ethyl)-N-n-octadecylacrylamide and or
N-[4-(1-pyrenyl)butyl]-N-n-octadecylacrylamide (0.5 mol% of the octade
cylacrylamide comonomer) was monitored by non-radiative energy transfe
r between excited naphthalene and pyrene. The anchoring process occurr
ed on zwitterionic lecithin liposomes and on negatively charged phosph
atidic acid liposomes, whether the bilayer was in the crystalline or t
he liquid-crystalline phase. Insertion of the copolymer octadecyl grou
ps within crystalline bilayers was attributed to the presence of packi
ng defects. Aqueous solutions of poly-(N-isopropylacrylamide) and of i
ts hydrophobically-modified copolymers exhibit a lower critical soluti
on temperature (LCST). The coil to globule collapse of the polymer cha
ins which is known to occur as the aqueous solution is heated through
the LCST, also took place when the copolymers were anchored onto vesic
ular bilayers. The copolymers remained anchored during this collapse a
nd the liposomes were not destroyed. The process was thermo-reversible
. Detailed aspects of the reversibility of the phenomenon depended on
the relative values of the phase transition temperatures of the liposo
mes and of the polymer LCST.