Polymeric vesicles have attracted considerable attention in recent years, since they are a model for biological membranes and have versatile structures with several practical applications. In this study, we prepare vesicles from polystyrene-b-poly(acrylic acid) block copolymer in dioxane/water and dioxane/THF/water mixtures. We then examine the ability of additives (such as NaCl, HCl, or NaOH), solvent composition, and hydrophilic block length to control vesicle size. Using turbidity measurements and transmission electron microscopy (TEM) we show that larger vesicles can be prepared from a given copolymer by adding NaCl or HCl, while adding NaOH yields smaller vesicles. The solvent composition (ratio of dioxane to THF, as well as the water content) can also determine the vesicle size. From a given copolymer, smaller vesicles can be prepared by increasing the THF content in the THF/dioxane solvent mixture. In a given solvent mixture, vesicle size increases with water content, but such an increase is most pronounced when dioxane is used as the solvent. In THF-rich solutions, on the other hand, vesicle size changes only slightly with the water concentration. As to the effect of the acrylic acid block length, the results show that block copolymers with shorter hydrophilic blocks assemble into larger vesicles. The effect of additives and solvent composition on vesicle size is related to their influence on chain repulsion and aggregation number, whereas the effect of acrylic acid block length occurs because of the relationship among the block length, the width of the molecular weight distribution, and the stabilization of the vesicle curvature.
A series of disc-shaped molecules were prepared by the condensation of 1,2-diamines with 2,3,6,7-tetrakis(hexyloxy)phenanthrene-9,10-dione to investigate the relationship between changes in molecular structure and the self-assembly of columnar liquid crystalline phases. A comparison of compounds with different core sizes indicated that molecules with larger aromatic cores had a greater propensity to form columnar phases, as did compounds substituted with electron-withdrawing groups. In contrast, molecules with electron-donating substituents were nonmesogenic. The clearing temperature of columnar phases increased linearly with the electron-withdrawing ability of the substituents, as quantified by Hammett sigma-values. The observed trends can be rationalized in terms of the strength of pi-pi interactions between aromatic cores in the liquid crystalline phases and suggest that both electrostatic interactions and dispersion forces play important roles in the self-assembly of these materials.
The effect of hydrogen bonding on the phase behaviour of discotic mesogens was investigated with a series of dibenzophenazine carboxylic acids and their methyl ester analogues. The esters exhibit only columnar hexagonal phases, while the acids form columnar hexagonal, columnar rectangular and nematic mesophases. The acids have much higher transition temperatures and supercool to room temperature while maintaining the liquid crystalline ordering. These differences could be explained by the ability of the acids to form hydrogen-bonded dimers, which may also be regarded as supramolecular elliptically-shaped mesogens.
Multishape memory copolymers were prepared through copolymerization of two norbornene derivatives: one based on cholic acid and the other on triethylene glycol monomethyl ether. The glass transition temperature (T g ) of the copolymers can be tuned over a temperature range from −58 to 176 °C. Most of these copolymers displayed a very broad T g over a 20 °C range which can allow a multishape memory effect. The shape memory properties of the copolymer incorporating an equal molar amount of both monomers have been studied in detail. The multishape memory effect was investigated by dynamic mechanical analysis using a thermomechanical programming process, in which multiple steps created two, three, and four temporary shapes. The polymer displayed good shape fixing and recovery in different thermal processing stages over the broad glass transition range. This series of copolymers with broad and tunable T g 's may be useful as functional materials with multishape memory effect.
A series of random copolymers of various lengths was prepared by atom transfer radical polymerisation (ATRP) using two acrylate monomers with short pendant ethylene glycol side chains (ethylene glycol methyl ether acrylate, EGMEA, and methoxy ethoxy ethyl acrylate, MEEA). The end group was converted to an azide to enable bioconjugation through copper-catalysed azide-alkyne cycloaddition (CuAAC). All polymers were found to be thermoresponsive, with a cloud point between 25 and 35 degrees C depending on their molecular weight. They were conjugated to enhanced green fluorescent protein (EGFP) functionalised with a single alkyne moiety, as seen by fast performance liquid chromatography (FPLC) and gel electrophoresis (SDS-PAGE). The resulting biohybrid amphiphiles were thermoresponsive. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) were used to study their self-assembly at elevated temperatures, and they were found to form spherical structures with a diameter of approximately 60 nm upon slow heating
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