Glycopolymer vesicles with an asymmetric membrane.

Direct dissolution of glycosylated polybutadiene-poly(ethylene oxide) block copolymers can lead to the spontaneous formation of vesicles or membranes, which on the outside are coated with glucose and on the inside with poly(ethylene oxide).

Amphiphilic conjugated block copolymers: synthesis and solvent-selective photoluminescence quenching.

A novel, amphiphilic, conjugated block copolymer is described, which was prepared by a Suzuki-type cross-coupling of 2-bromo-[9,9-bis(2-ethylhexyl)fluorene]-7-pinacolato boronate as an AB-type monomer and monobromo-substituted poly[3-(6-bromohexyl)thiophene] (Br-P3BrHT) as a polymeric end capper in the key step. PF-P3PHT (P2; PF = poly(9,9-dialkylfluorene); P3PHT = poly[3-(6-diethylphosphonato-hexyl)thiophene]) as the amphiphilic target polymer was then generated in a polymer-analogous conversion of the alkyl bromide side chains of the PF-P3BrHT (P1) precursor into polar alkyl phosphonate groups by reaction with triethyl phosphite. P2 shows a strong influence of the solvent polarity on the optical spectra (absorption, emission). Treatment of solutions of P2 in tetrahydrofuran (THF), a nonselective solvent, with increasing amounts of solvents that are selective for the polar polythiophene blocks (water) or the nonpolar polyfluorene blocks (hexane), respectively, results in the formation of two different types of core-shell aggregates, which show rather different optical properties (photoluminescence quenching, excitation energy transfer).

Dynamics of amphiphilic diblock copolymers at the air-water interface.

Two polyisoprene-polyethyleneoxide diblock copolymers with different block length ratios adsorbed to the water surface were investigated by multiple angle of incidence ellipsometry, evanescent wave light scattering, and surface tension experiments. In a semidilute interfacial regime, the transition from a two-dimensional to a "mushroom" regime, in which polymer chains form loops and tails in the subphase, was discussed. A diffusion mechanism parallel to the interface was probed by evanescent wave dynamic light scattering. At intermediate concentrations, the interfacial diffusion coefficient D(∥) scales with the surface concentration Γ, as D(∥) ~ Γ(0.77) in agreement with the scaling observed for polymer solutions in a semidilute regime. At relatively high concentrations a decreasing of D(∥) is discussed in terms of increasing friction due to interactions between polyisoprene chains.

pH responsiveness of block copolymer vesicles with a polypeptide corona.

The aggregation behavior of polybutadiene165-block-poly(L-lysine)88 in saline solution was studied by combined static and dynamic light scattering analyses. Vesicles were observed if the polypeptide segment was in a 100% coil conformation (pH 7.0) or in an 80% alpha-helical conformation (pH 10.3). At the higher pH, aggregates were smaller in size (hydrodynamic radius: 364 nm --> 215 nm) and chains were more densely packed at the core-corona interface (interchain distance: 3.2 nm --> 2.4 nm). Changes in size and structure could be explained in basic terms of colloid stabilization without considering a secondary structure effect.