By combining three mutually immiscible polymeric components in a mixed-arm star block terpolymer architecture, we have observed the formation of a previously unknown class of multicompartment micelles in dilute aqueous solution. Connection of water-soluble poly(ethylene oxide) and two hydrophobic but immiscible components (a polymeric hydrocarbon and a perfluorinated polyether) at a common junction leads to molecular frustration when dispersed in aqueous solution. The incompatible hydrophobic blocks form cores that are protected from the water by the poly(ethylene oxide) blocks, but both are forced to make contact with the poly(ethylene oxide) by virtue of the chain architecture. The structures that emerge depend on the relative lengths of the blocks and can be tuned from discrete multicompartment micelles to extended wormlike structures with segmented cores.

Four amphiphilic poly((1,2-butadiene)-block-ethylene oxide) (PB-PEO) diblock copolymers were shown to aggregate strongly and form micelles in an ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF(6)]). The universal micellar structures (spherical micelle, wormlike micelle, and bilayered vesicle) were all accessed by varying the length of the corona block while holding the core block constant. The nanostructures of the PB-PEO micelles formed in an ionic liquid were directly visualized by cryogenic transmission electron microscopy (cryo-TEM). Detailed micelle structural information was extracted from both cryo-TEM and dynamic light scattering measurements, with excellent agreement between the two techniques. Compared to aqueous solutions of the same copolymers, [BMIM][PF(6)] solutions exhibit some distinct features, such as temperature-independent micellar morphologies between 25 and 100 degrees C. As in aqueous solutions, significant nonergodicity effects were also observed. This work demonstrates the flexibility of amphiphilic block copolymers for controlling nanostructure in an ionic liquid, with potential applications in many arenas.

Several new multicompartment micellar structures have been identified by cryogenic transmission electron microscopy (cryoTEM) from the aqueous self-assembly of mu-[poly(ethylethylene)][poly(ethylene oxide)][poly(perfluoropropylene oxide)] (mu-EOF) miktoarm star terpolymers. This work extends our previous studies, in which it was found that, upon decreasing the length of the hydrophilic block (O), the resulting micelles evolved from "hamburger" micelles to segmented worms and ultimately to nanostructured bilayers and vesicles. In the terpolymers examined here segmented ribbons and bilayers were found at an intermediate composition between segmented worms and nanostructured bilayers, provided that the fluoropolymer (F) was the minority component in the micelle core. On the other hand, when the F block exceeded the chain length of the hydrocarbon block (E), the superhydrophobic F block imposed a "double frustration" on the self-assembly of the mu-EOF(2-9-5) terpolymer; while F prefers to minimize its interfacial contact with the O corona, it must occupy the majority of the micellar core. Therefore, a richer variety of multicompartment micelles, including well-defined segmented worms, raspberry-like micelles, and multicompartmentalized worms, were formed from one terpolymer, as revealed by cryoTEM. Despite the complexity and variety of the observed aggregate morphologies, a small number of common structural elements can be invoked to interpret the observed micelles and to relate a given structure to the terpolymer composition.

An asymmetric poly(styrene-b-isoprene) diblock copolymer with block molecular weights of 13 000 and 71 000 g/mol, respectively, was dissolved at 1 vol % in a series of solvents with varying selectivity for styrene: dibuthyl phthalate (DBP), diethyl phthalate (DEP), and dimethyl phthalate (DMP). The degree of solvent selectivity was adjusted by mixing DBP/DEP and DEP/DMP in various proportions. With increasing solvent selectivity, the predominant micellar shape changes from spheres to cylinders to vesicles, reflecting the changing interfacial curvature. The detailed micellar morphologies were characterized by small-angle X-ray scattering (SAXS) and cryogenic transmission electron microscopy (cryo-TEM). Recently developed form factors were used to characterize the micellar structures in detail, and a vesicle form factor was derived for this system. From the core dimensions, the packing properties, such as the interfacial area per chain and the core chain stretching, were determined. The cryo-TEM results demonstrate the suitability of the technique for these glass-forming solvents and gave micellar core dimensions in quantitative agreement with those from SAXS. The universality of the shape sequence sphere/cylinder/vesicle, well-established for aqueous solutions of surfactants and block copolymers, is thus confirmed for organic systems.