Topological defects in liquid crystals (LCs) have been widely used to organize colloidal dispersions and template polymerization, leading to a range of assemblies, elastomers and gels. However, little is understood about molecular-level assembly processes within defects. Here, we report that nanoscopic environments defined by LC topological defects can selectively trigger processes of molecular self-assembly. By using fluorescence microscopy, cryogenic transmission electron microscopy and super-resolution optical microscopy, we observed signatures of molecular self-assembly of amphiphilic molecules in topological defects, including cooperativity, reversibility and controlled growth. We also show that nanoscopic o-rings synthesized from Saturn-ring disclinations and other molecular assemblies templated by defects can be preserved by using photocrosslinkable amphiphiles. Our results reveal that, in analogy to other classes of macromolecular templates such as polymer-surfactant complexes, topological defects in LCs are a versatile class of three-dimensional, dynamic and reconfigurable templates that can direct processes of molecular self-assembly.

Liquid crystals (LCs) are anisotropic fluids that combine the long-range order of crystals with the mobility of liquids. This combination of properties has been widely used to create reconfigurable materials that optically report information about their environment, such as changes in electric fields (smart-phone displays) , temperature (thermometers) or mechanical shear , and the arrival of chemical and biological stimuli (sensors). An unmet need exists, however, for responsive materials that not only report their environment but also transform it through self-regulated chemical interactions. Here we show that a range of stimuli can trigger pulsatile (transient) or continuous release of microcargo (aqueous microdroplets or solid microparticles and their chemical contents) that is trapped initially within LCs. The resulting LC materials self-report and self-regulate their chemical response to targeted physical, chemical and biological events in ways that can be preprogrammed through an interplay of elastic, electrical double-layer, buoyant and shear forces in diverse geometries (such as wells, films and emulsion droplets). These LC materials can carry out complex functions that go beyond the capabilities of conventional materials used for controlled microcargo release, such as optically reporting a stimulus (for example, mechanical shear stresses generated by motile bacteria) and then responding in a self-regulated manner via a feedback loop (for example, to release the minimum amount of biocidal agent required to cause bacterial cell death).

Liquid crystals (LCs) are widely known for their use in liquid crystal displays (LCDs). Indeed, LCDs represent one of the most successful technologies developed to date using a responsive soft material: An electric field is used to induce a change in ordering of the LC and thus a change in optical appearance. Over the past decade, however, research has revealed the fundamental underpinnings of potentially far broader and more pervasive uses of LCs for the design of responsive soft material systems. These systems involve a delicate interplay of the effects of surface-induced ordering, elastic strain of LCs, and formation of topological defects and are characterized by a chemical complexity and diversity of nano- and micrometer-scale geometry that goes well beyond that previously investigated. As a reflection of this evolution, the community investigating LC-based materials now relies heavily on concepts from colloid and interface science. In this context, this review describes recent advances in colloidal and interfacial phenomena involving LCs that are enabling the design of new classes of soft matter that respond to stimuli as broad as light, airborne pollutants, bacterial toxins in water, mechanical interactions with living cells, molecular chirality, and more. Ongoing efforts hint also that the collective properties of LCs (e.g., LC-dispersed colloids) will, over the coming decade, yield exciting new classes of driven or active soft material systems in which organization (and useful properties) emerges during the dissipation of energy.

Nanoparticles adsorbed at the interface of nematic liquid crystals are known to form ordered structures whose morphology depends on the orientation of the underlying nematic field. The origin of such structures is believed to result from an interplay between the liquid crystal orientation at the particles' surface, the orientation at the liquid crystal's air interface, and the bulk elasticity of the underlying liquid crystal. In this work, we consider nanoparticle assembly at the interface of nematic droplets. We present a systematic study of the free energy of nanoparticleladen droplets in terms of experiments and a Landau-de Gennes formalism. The results of that study indicate that, even for conditions under which particles interact only weakly at flat interfaces, particles aggregate at the poles of bipolar droplets and assemble into robust, quantized arrangements that can be mapped onto hexagonal lattices. The contributions of elasticity and interfacial energy corresponding to different arrangements are used to explain the resulting morphologies, and the predictions of the model are shown to be consistent with experimental observations. The findings presented here suggest that particle-laden liquid crystal droplets could provide a unique and versatile route toward building blocks for hierarchical materials assembly.growing body of theoretical and experimental work has sought to direct the assembly of molecules and nanoparticles at interfaces by exploiting the elastic forces that arise in liquid crystals (LCs) (1-5). Nematic LCs possess orientational order along a unit vector, the so-called nematic director. They also exhibit defects-regions of low order whose morphology and position depends on a delicate balance between elastic, enthalpic, and interfacial contributions to the free energy. The orientation of nematic LCs and any corresponding defects can be perturbed by introducing particles. The symmetry and structure of the director field around a particle also depends on the interaction between the LC and the particle, often referred to as anchoring. Particles with perpendicular (homeotropic) anchoring induce either dipolar or quadrupolar symmetry in the LC, leading to formation of point defects or Saturn-ring defects, respectively (6). Particles with planar anchoring induce quadrupolar symmetry, which is accompanied by two surface defects, generally referred to as boojums (6). Distortions of the nematic field cost elastic energy and therefore give rise to anisotropic, long-range interactions between particles. Indeed, particles in nematic LCs aggregate and "bind," thereby minimizing the volume of defects and the large free energy that is associated with their elastic strain. Equilibrium particle arrangements in nematic LCs depend strongly on the topology of the underlying defects. Homeotropic particles with point, dipolar defects form chains along the nematic director, whereas quadrupolar, Saturn-ring defects form kinked chains that are perpendicular to the nematic director (7). Particles with planar anchor...