Heating-Induced Switching to Hierarchical Liquid Crystallinity Combining Colloidal and Molecular Order in Zwitterionic Molecules.

Hierarchical self-assemblies of soft matter involving triggerable or switchable structures at different length scales have been pursued toward multifunctional behaviors and complexity inspired by biological matter. They require several and balanced competing attractive and repulsive interactions, which provide a grand challenge in particular in the "bulk" state, i.e., in the absence of plasticizing solvents. Here, we disclose that zwitterionic bis-n-tetradecylphosphobetaine, as a model compound, shows a complex thermally switchable hierarchical self-assembly in the solvent-free state. It shows polymorphism and heating-induced reversible switching from low-temperature molecular-level assemblies to high-temperature hierarchical self-assemblies, unexpectedly combining colloidal and molecular self-assemblies, as inferred by synchrotron small-angle X-ray scattering (SAXS). The high-temperature phase sustains birefringent flow, indicating a new type of hierarchical thermotropic liquid crystallinity. The high-temperature colloidal-level SAXS reflections suggest indexation as a 2D oblique pattern and their well-defined layer separation in the perpendicular direction. We suggest that the colloidal self-assembled motifs are 2D nanoplatelets formed by the lateral packing of the molecules, where the molecular packing frustration between the tightly packed zwitterionic moieties and the coiled alkyl chains demanding more space limits the lateral platelet growth controlled by the alkyl stretching entropy. An indirect proof is provided by the addition of plasticizing ionic liquids, which relieve the ionic dense packings of zwitterions, thus allowing purely smectic liquid crystallinity without the colloidal level order. Thus, molecules with a simple chemical structure can lead to structural hierarchy and tunable complexity in the solvent-free state by balancing the competing long-range electrostatics and short-range nanosegregations.

Electroferrofluids with nonequilibrium voltage-controlled magnetism, diffuse interfaces, and patterns.

It has been recognized that driving matter to nonequilibrium states can lead to emergent behaviors and functionalities. Here, we show that uniform colloidal dispersions can be driven into dissipative nonuniform states with emerging behaviors. We experimentally demonstrate this with electrically driven weakly charged superparamagnetic iron oxide nanoparticles in a nonpolar solvent. The driving leads to formation of nonequilibrium concentration gradients that further translate to nonequilibrium magnetism, including voltage-controlled magnetization and susceptibility. The concentration gradients also serve as diffuse interfaces that respond to external magnetic fields, leading to novel dissipative patterns. We identify the closest nondissipative analogs, discuss the differences, and highlight the ability to directly quantify the dissipation and link it to the pattern formation. Beyond voltage-controlled magnetism, we foresee that the concept can be generalized to other functional colloids to create, e.g., optical, electrical, catalytic, and mechanical responses that are not possible in thermodynamic equilibrium.

Magnetic and Mössbauer Studies on Nanostructured CoCrxFe2-xO4 (0 = x = 1) Spinel Ferrites Prepared by Sol-Gel Auto-Combustion Method.

Low temperature preparation of nanostructured CoCrxFe2-xO4 (0