Nanoporous polymers with periodic, ordered structures have attracted significant interest for their potential applications as drug delivery vehicles, biomaterials, separations membranes, and materials for energy storage. Inducing polymer nanostructure through lyotropic liquid crystal-templated (LLC-templated) cross-linking photopolymerizations offers a promising means for morphological control at smaller length scales, which are difficult to access by other established strategies. We report the synthesis of a gemini dicarboxylate surfactant that self-assembles in water to form various aqueous LLC mesophases over a broad range of amphiphile concentrations, with an especially strong propensity to form the coveted bicontinuous double gyroid (GI) network mesophase. Aqueous GI LLCs surprisingly persist upon incorporation of as much as 10–37 wt % hexane-1,6-diol dimethacrylate (HDDMA) into the hydrophobic domains of these supramolecular surfactant assemblies, and cross-linking photopolymerization of the HDDMA unexpectedly proceeds with retention of this intricate LLC nanostructure. The nanoporous nature of the resulting templated polymers remains after surfactant removal by solvent extraction, as manifested by increased swelling ratios in water and 2-propanol as compared to isotropic materials of similar compositions. The exquisite level of control over polymer network porosity provided by templating within GI phases furnishes a promising new route toward nanostructured hydrophobic polymers.
A delicate balance of noncovalent interactions directs the hierarchical self-assembly of molecular amphiphiles into spherical micelles that pack into three-dimensional periodic arrays, which mimic intermetallic crystals. Herein, we report the discovery that adding water to a mixture of an ionic surfactant and n-decane induces aperiodic ordering of oil-swollen spherical micelles into previously unrecognized, aqueous lyotropic dodecagonal quasicrystals (DDQCs), which exhibit local 12-fold rotational symmetry and no long-range translational order. The emergence of these DDQCs at the nexus of dynamically arrested micellar glasses and a periodic Frank–Kasper (FK) σ phase approximant sensitively depends on the mixing order of molecular constituents in the assembly process and on sample thermal history. Addition of n-decane to mixtures of surfactant and water instead leads only to periodic FK A15 and σ approximants with no evidence for aperiodic order, while extended ambient temperature annealing of the DDQC also reveals its transformation into a σ phase. Thus, these lyotropic DDQCs are long-lived metastable morphologies, which nucleate and grow from a stochastic distribution of micelle sizes formed by abrupt segregation of varied amounts of oil into surfactant micelles on hydration. These findings indicate that molecular building block complexity is not a prerequisite for the formation of aperiodic supramolecular order, while also establishing the generic nature of quasicrystalline states across metal alloys and self-assembled micellar materials.
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