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Peptide surfactants (PEPS) are studied to capture and retain rare earth elements (REEs) at air-water interfaces to enable REE separations. Peptide sequences, designed to selectively bind REEs, depend crucially on the position of ligands within their binding loop domain. These ligands form a coordination sphere that wraps and retains the cation. We study variants of lanthanide binding tags (LBTs) designed to complex strongly with Tb$^{3+}$. The peptide LBT$^{5-}$ (with net charge -5) is known to bind Tb$^{3+}$ and adsorb with more REE cations than peptide molecules, suggesting that undesired non-specific Coulombic interactions occur. Rheological characterization of interfaces of LBT$^{5-}$ and Tb$^{3+}$ solutions reveal the formation of an interfacial gel. To probe whether this gelation reflects chelation among intact adsorbed LBT$^{5-}$:Tb$^{3+}$ complexes or destruction of the binding loop, we study a variant, LBT$^{3-}$, designed to form net neutral LBT$^{3-}$:Tb$^{3+}$ complexes. Solutions of LBT$^{3-}$ and Tb$^{3+}$ form purely viscous layers in the presence of excess Tb$^{3+}$, indicating that each peptide binds a single REE in an intact coordination sphere. We introduce the variant RR-LBT$^{3-}$ with net charge -3 and anionic ligands outside of the coordination sphere. We find that such exposed ligands promote interfacial gelation. Thus, a nuanced requirement for interfacial selectivity of PEPS is proposed: that anionic ligands outside of the coordination sphere must be avoided to prevent the non-selective recruitment of REE cations. This view is supported by simulation, including interfacial molecular dynamics simulations, and interfacial metadynamics simulations of the free energy landscape of the binding loop conformational space.

The behavior of fluid interfaces far from equilibrium plays central roles in nature and in industry. Active swimmers trapped at interfaces can alter transport at fluid boundaries with far reaching implications. Swimmers can become trapped at interfaces in diverse configurations and swim persistently in these surface adhered states. The self-propelled motion of bacteria makes them ideal model swimmers to understand such effects. We have recently characterized the swimming of interfacially-trapped Pseudomonas aeruginosa PA01 moving in pusher mode. The swimmers adsorb at the interface with pinned contact lines, which fix the angle of the cell body at the interface and constrain their motion. Thus, most interfacially-trapped bacteria swim along circular paths. Fluid interfaces form incompressible two-dimensional layers, altering leading order interfacial flows generated by the swimmers from those in bulk. In our previous work, we have visualized the interfacial flow around a pusher bacterium and described the flow field using two dipolar hydrodynamic modes; one stresslet mode whose symmetries differ from those in bulk, and another bulk mode unique to incompressible fluid interfaces. Based on this understanding, swimmers-induced tracer displacements and swimmer-swimmer pair interactions are explored using analysis and experiment. The settings in which multiple interfacial swimmers with circular motion can significantly enhance interfacial transport of tracers or promotemixing of other swimmers on the interface are identified through simulations and compared to experiment. This study identifies important factors of general interest regarding swimmers on or near fluid boundaries, and in the design of biomimetic swimmers to enhance transport at interfaces, Comment: arXiv admin note: substantial text overlap with arXiv:2204.02300

Porous materials possess numerous useful functions because of their high surface area and ability to modulate the transport of heat, mass, fluids, and electromagnetic waves. Unlike highly ordered structures, disordered porous structures offer the advantages of ease of fabrication and high fault tolerance. Bicontinuous interfacially jammed emulsion gels (bijels) are kinetically trapped disordered biphasic materials that can be converted to porous materials with tunable features. Current methods of bijel fabrication result in domains that are micrometers or larger, and non-uniform in size, limiting their surface area, mechanical strength, and interaction with electromagnetic waves. In this work, scalable synthesis of bijels with uniform and sub-micrometer domains is achieved via a two-step solvent removal process. The resulting bijels are characterized quantitatively to verify the uniformity and sub-micrometer scale of the domains. Moreover, these bijels have structures that resemble the microstructure of the scale of the white beetle Cyphochilus. We find that such bijel films with relatively small thicknesses (< 150 um) exhibit strong solar reflectance as well as high brightness and whiteness in the visible range. Considering their scalability in manufacturing, we believe that VIPS-STRIPS bijels have great potential in large-scale applications including passive cooling, solar cells, and light emitting diodes (LEDs)., Comment: 20 pages, 4 figures in main text, 4 figures in Supporting information

Motile bacteria play essential roles in biology that rely on their dynamic behaviors, including their ability to navigate, interact, and self-organize. However, bacteria dynamics on fluid interfaces are not well understood. Swimmers adsorbed on fluid interfaces remain highly motile, and fluid interfaces are highly non-ideal domains that alter swimming behavior. To understand these effects, we study flow fields generated by Pseudomonas aeruginosa PA01 in the pusher mode. Analysis of correlated displacements of tracers and bacteria reveals dipolar flow fields with unexpected asymmetries that differ significantly from their counterparts in bulk fluids. We decompose the flow field into fundamental hydrodynamic modes for swimmers in incompressible fluid interfaces. We find an expected force-doublet mode corresponding to propulsion and drag at the interface plane, and a second dipolar mode, associated with forces exerted by the flagellum on the cell body in the aqueous phase that are countered by Marangoni stresses in the interface. The balance of these modes depends on the bacteria's trapped interfacial configurations. Understanding these flows is broadly important in nature and in the design of biomimetic swimmers.

Physically intelligent micro-robotic systems exploit information embedded in micro-robots, their colloidal cargo, and their milieu to interact, assemble and form functional structures. Nonlinear anisotropic fluids like nematic liquid crystals (NLCs) provide untapped opportunities to embed interactions via their topological defects, complex elastic responses, and their ability to dramatically restructure in dynamic settings. Here we design and fabricate a 4-armed ferromagnetic micro-robot to embed and dynamically reconfigure information in the nematic director field, generating a suite of physical interactions for cargo manipulation. The micro-robot shape and surface chemistry are designed to generate a nemato-elastic energy landscape in the domain that defines multiple modes of emergent, bottom-up interactions with passive colloids. Micro-robot rotation expands the ability to sculpt interactions; the energy landscape around a rotating micro-robot is dynamically reconfigured by complex far-from-equilibrium dynamics of the micro-robot's companion topological defect. These defect dynamics allow transient information to be programmed into the domain and exploited for top-down cargo manipulation. We demonstrate robust micro-robotic manipulation strategies that exploit these diverse modes of nemato-elastic interaction to achieve cargo docking, transport, release, and assembly of complex reconfigurable structures at multi-stable sites. Such structures are of great interest to future developments of LC-based advanced optical device and micro-manufacturing in anisotropic environments., Comment: 23 pages, 8 figures in the main text and 4 figures in the SI

Non-equilibrium dynamics of topological defects can be used as a fundamental propulsion mechanism in microscopic active matter. Here, we demonstrate swimming of topological defect-propelled colloidal particles in (passive) nematic fluids through experiments and numerical simulations. Dynamic swim strokes of the topological defects are driven by colloidal rotation in an external magnetic field, causing periodic defect rearrangement which propels the particles. The swimming velocity is determined by the colloid's angular velocity, sense of rotation and defect polarity. By controlling them we can locomote the particles along different trajectories. We demonstrate scattering -- that is, the effective pair interactions -- of two of our defect-propelled swimmers, which we show is highly anisotropic and depends on the microscopic structure of the defect stroke, including the local defect topology and polarity. More generally, this work aims to develop biomimetic active matter based on the underlying relevance of topology.

Nanocomposite films containing a high volume fraction (> 50vol%) of nanoparticles (NPs) in a polymer matrix are promising for their functionality and use as structural coatings, and also provide a unique platform to understand polymer behavior under strong confinement. Previously, we developed a novel technique to fabricate such nanocomposites at room temperature using solvent-driven infiltration of polymer (SIP) into NP packings. In the SIP process, a bilayer made of an underlying polymer film and a dense packing of NPs is exposed to solvent vapor which induces condensation of the solvent into the voids of the packing. The condensed solvent plasticizes the underlying polymer film, inducing polymer infiltration into the solvent-filled voids in the NP packing. In this work, we study the effect of confinement on the kinetics of SIP and the final partitioning of polymer into the interstices of the NP packing. We find that, while the dynamics of infiltration during SIP are strongly dependent on confinement, the final extent of infiltration is independent of confinement. The time for infiltration obeys a power law with confinement, as defined by the ratio of the chain size and the pore size. Qualitatively, the observed time scale is attributed to changes in concentration regimes as infiltration proceeds, which lead to shifting characteristic length scales in the system over time. When the concentration in the pore exceeds the critical overlap concentration, the characteristic length scale of the polymer is no longer that of the entire chain, but rather the correlation length, which is smaller than the pore size. Therefore, at long times, the extent of infiltration is independent of the confinement ratio. Furthermore, favorable surface interactions between the polymer and the nanoparticles enhance partitioning into the NP packing., Comment: 8 pages, 5 figures. Supporting Information: 4 pages, 3 figures

We derive expressions for the leading-order far-field flows generated by externally driven and active (swimming) colloids at planar fluid-fluid interfaces. We consider colloids adjacent to the interface or adhered to the interface with a pinned contact line. The Reynolds and capillary numbers are assumed much less than unity, in line with typical micron-scale colloids involving air- or alkane-aqueous interfaces. For driven colloids, the leading-order flow is given by the point-force (and/or torque) response of this system. For active colloids, the force-dipole (stresslet) response occurs at leading order. At clean (surfactant-free) interfaces, these hydrodynamic modes are essentially a restricted set of the usual Stokes multipoles in a bulk fluid. To leading order, driven colloids exert Stokeslets parallel to the interface, while active colloids drive differently oriented stresslets depending on the colloid's orientation. We then consider how these modes are altered by the presence of an incompressible interface, a typical circumstance for colloidal systems at small capillary numbers in the presence of surfactant. The leading-order modes for driven and active colloids are restructured dramatically. For driven colloids, interfacial incompressibility substantially weakens the far-field flow normal to the interface; the point-force response drives flow only parallel to the interface. However, Marangoni stresses induce a new dipolar mode, which lacks an analogue on a clean interface. Surface-viscous stresses, if present, potentially generate very long-ranged flow on the interface and the surrounding fluids. Our results have important implications for colloid assembly and advective mass transport enhancement near fluid boundaries., Comment: 36 pages, 9 figures. To be published in the Journal of Fluid Mechanics. Eq. (5.21) past versions (v1, v2) of this e-print contained a mathematical error that is corrected in this version. Discussion of our results has been amended appropriately. All corrections will be reflected in the published version of the article

The ability to dictate colloid motion is an important challenge in fields ranging from materials science to living systems. Here, by embedding energy landscapes in confined nematic liquid crystals, we design a versatile platform to define colloidal migration. This is achieved by placing a wavy wall, with alternating hills and wells, in nematic liquid crystals, to impose a smooth elastic energy field with alternating splay and bend distortions. This domain generates (meta) stable loci that act as attractors and unstable loci that repel colloids over distances large compared to the colloid radius. Energy gradients in the vicinity of these loci are exploited to dictate colloid trajectories. We demonstrate several aspects of this control, by studying transitions between defect configurations, propelling particles along well defined paths and exploiting multistable systems to send particles to particular sites within the domain. Such tailored landscapes have promise in reconfigurable systems and in microrobotics applications, Comment: 13 pages, 8 figures

The ordering of nanoparticles into predetermined configurations is of importance to the design of advanced technologies. In this work, we moderate the surface anchoring against the bulk elasticity of liquid crystals to dynamically shape nanoparticle assemblies at a fluid interface. By tuning the degree of nanoparticle hydrophobicity with surfactants that alter the molecular anchoring of liquid crystals, we pattern nanoparticles at the interface of cholesteric liquid crystal emulsions. Adjusting the particle hydrophobicity more finely further modifies the rigidity of assemblies. We establish that patterns are tunable by varying both surfactant and chiral dopant concentrations. Since particle assembly occurs at the interface with the desired structures exposed to the surrounding phase, we demonstrate that particles can be readily crosslinked and manipulated, forming structures that retain their shape under external perturbations. This study establishes the templating of nanomaterials into reconfigurable arrangements. Interfacial assembly is tempered by elastic patterns that arise from the geometric frustration of confined cholesterics. This work serves as a basis for creating materials with chemical heterogeneity and with linear, periodic structures, essential for optical and energy applications., Comment: 16 pages with 5 figures, 4 page supplementary with 5 supplementary figures

In directed assembly, small building clocks are assembled into an organized structures under the influence of guiding fields. Capillary interactions provide a versatile route for structure formation. Colloids adsorbed on fluid interfaces distort the interface, which creates an associated energy field. When neighboring distortions overlap, colloids interact to minimize interfacial area. Contact line pinning, particle shape and surface chemistry play important roles in structure formation. Interface curvature acts like an external field; particles migrate and assemble in patterns dictated by curvature gradients. We review basic analysis and recent findings in this rapidly evolving literature. Understanding the roles of assembly is essential for tuning the mechanical, physical, and optical properties of the structure., Comment: 14 pages, 9 figures

Colloidal particles at complex fluid interfaces and within films assemble to form ordered structures with high degrees of symmetry via interactions that include capillarity, elasticity, and other fields like electrostatic charge. Here we study microparticle interactions within free-standing smectic-A films, in which the elasticity arising from the director field distortion and capillary interactions arising from interface deformation compete to direct the assembly of motile particles. New colloidal assemblies and patterns, ranging from 1D chains to 2D aggregates, sensitive to the initial wetting conditions of particles at the smectic film, are reported. This work paves the way to exploiting LC interfaces as a means to direct spontaneously formed, reconfigurable, and optically active materials., Comment: 8 pages, 6 figures. Supplementary Materials: 3 pages, 3 figures

Bacteria at fluid interfaces endure physical and chemical stresses unique to these highly asymmetric environments. The responses of Pseudomonas aeruginosa PAO1 and PA14 to a hexadecane-water interface are compared. PAO1 cells form elastic films of bacteria, excreted polysaccharides and proteins, whereas PA14 cells move actively without forming an elastic film. Studies of PAO1 mutants show that, unlike solid-supported biofilms, elastic interfacial film formation occurs in the absence of flagella, pili, or certain polysaccharides. Highly induced genes identified in transcriptional profiling include those for putative enzymes and a carbohydrate metabolism enzyme, alkB2; this latter gene is not upregulated in PA14 cells. Notably, PAO1 mutants lacking the alkB2 gene fail to form an elastic layer. Rather, they form an active film like that formed by PA14. These findings demonstrate that genetic expression is altered by interfacial confinement, and suggest that the ability to metabolize alkanes may play a role in elastic film formation at oil-water interfaces.

Directed assembly of colloids is an exciting field in materials science to form structures with new symmetries and responses. Fluid interfaces have been widely exploited to make densely packed ordered structures. We have been studying how interface curvature can be used in new ways to guide structure formation. On a fluid interface, the area of the deformation field around adsorbed microparticles depends on interface curvature; particles move to minimize the excess area of the distortions that they make in the interface. For particles that are sufficiently small, this area decreases as particles move along principle axes to sites of high deviatoric curvature. We have studied this migration for microparticles on a curved host interface with zero mean curvature created by pinning an oil-water interface around a micropost. Here, on a similar interface, we demonstrate capillary curvature repulsion, that is, we identify conditions in which microparticles migrate away from high curvature sites. Using theory and experiment, we discuss the origin of these interactions and their relationship to the particle's undulated contact line. We discuss the implications of this new type of interaction in various contexts from materials science to microrobotics., Comment: 9 pages, 7 figures

Chirality, ubiquitous in complex biological systems, can be controlled and quantified in synthetic materials such as cholesteric liquid crystal (CLC) systems. In this work, we study spherical shells of CLC under weak anchoring conditions. We induce anchoring transitions at the inner and outer boundaries using two independent methods: by changing the surfactant concentration or by raising the temperature close to the clearing point. The shell confinement leads to new states and associated surface structures: a state where large stripes on the shell can be filled with smaller, perpendicular sub-stripes, and a focal conic domain (FCD) state, where thin stripes wrap into at least two, topologically required, double spirals. Focusing on the latter state, we use a Landau-de Gennes model of the CLC to simulate its detailed configurations as a function of anchoring strength. By abruptly changing the topological constraints on the shell, we are able to study the interconversion between director defects and pitch defects, a phenomenon usually restricted by the complexity of the cholesteric phase. This work extends the knowledge of cholesteric patterns, structures that not only have potential for use as intricate, self-assembly blueprints but are pervasive in biological systems., Comment: 27 pages, 10 figures

Colloids and proteins alike can bind to lipid bilayers and move laterally in these two-dimensional fluids. Inspired by proteins that generate membrane curvature, sense the underlying membrane geometry, and migrate to high curvature sites, we explore the question: Can colloids, adhered to lipid bilayers, also sense and respond to membrane geometry? We report the curvature migration of Janus microparticles adhered to giant unilamellar vesicles elongated to present well defined curvature fields. However, unlike proteins, which migrate to minimize membrane bending energy, colloids migrate by an entirely different mechanism. By determining the energy dissipated along a trajectory, the energy field mediating these interactions is inferred to be linear in the local deviatoric curvature, as reported previously for colloids trapped at curved interfaces between immiscible fluids. In this latter system, however, the energy gradients are far larger, so particles move deterministically, whereas the colloids on vesicles move with significant fluctuations in regions of weak curvature gradient. By addressing the role of Brownian motion, we show that the observed curvature migration of colloids on bilayers is indeed a case of curvature capillary migration, with membrane tension playing the role of interfacial tension. Furthermore, since this motion is mediated by membrane tension and shape, it can be modulated, or even turned "on" and "off", by simply varying these parameters. While particle-particle interactions on lipid membranes have been considered in many contributions, we report here an exciting and previously unexplored modality to actively direct the migration of colloids to desired locations on lipid bilayers., Comment: 24 pages, 12 figures

Systems with holes, such as colloidal handlebodies and toroidal droplets, have been studied in the nematic liquid crystal (NLC) 4-cyano-4'-pentylbiphenyl (5CB): both point and ring topological defects can occur within each hole and around the system, while conserving the system's overall topological charge. However, what has not been fully appreciated is the ability to manipulate the hole geometry with homeotropic (perpendicular) anchoring conditions to induce complex, saddle-like deformations. We exploit this by creating an array of holes suspended in an NLC cell with oriented planar (parallel) anchoring at the cell boundaries. We study both 5CB and a binary mixture of bicyclohexane derivatives (CCN-47 and CCN-55). Through simulations and experiments, we study how the bulk saddle deformations of each hole interact to create novel defect structures, including an array of disclination lines, reminiscent of those found in liquid crystal blue phases. The line locations are tunable via the NLC elastic constants, the cell geometry, and the size and spacing of holes in the array. This research lays the groundwork for the control of complex elastic deformations of varying length scales via geometrical cues in materials that are renowned in the display industry for their stability and easy manipulability., Comment: 9 pages, 7 figures, 1 supplementary figure

The ability to control the movement and assembly of particles in liquid crystals is not only an important route to design functional materials, but also sheds light on the mechanisms of colloidal interactions. In this study we place micron-sized particles with "Saturn ring" defects near a wall with hills and dales that impose perpendicular (homeotropic) molecular anchoring. The strong splay distortion at the wall interacts with the distortion around the particles in the near field and favors their migration towards the dales via the so-called "lock-and-key" mechanism. We demonstrate experimentally that the lock-and-key mechanism can robustly localize a particle at specific topographical features. We observe the complex trajectories traced by the particles as they dock on the dales, estimate the binding energy, and explore a range of parameters that favor or disfavor the docking event, thus exploiting the capabilities of our experimental system. We extend the study to colloids with homeotropic anchoring but with an associated point defect instead of a Saturn ring and show that they find a different preferred location, i.e. we can place otherwise identical particles at well defined sites according to their topological defect structure. Finally, for deep enough wells, confinement drives topological transitions of Saturn rings to dipoles. This ability to tailor wall geometry to guide colloids to well defined sites within nematic liquid crystals represents an important new tool in directed assembly., Comment: 18 pages, 6 figures

A particle placed in soft matter distorts its host and creates an energy landscape. This can occur, for example, for particles in liquid crystals, for particles on lipid bilayers or for particles trapped at fluid interfaces. Such energies can be used to direct particles to assemble with remarkable degrees of control over orientation and structure. These notes explore that concept for capillary interactions, beginning with particle trapping at fluid interfaces, addressing pair interactions on planar interfaces and culminating with curvature capillary migration. Particular care is given to the solution of the associated boundary value problems to determine the energies of interaction. Experimental exploration of these interactions on planar and curved interfaces is described. Theory and experiment are compared. These interactions provide a rich toolkit for directed assembly of materials, and, owing to their close analogy to related systems, pave the way to new explorations in materials science., Comment: 37 pages, 28 figures

We have studied microparticle migration on curved fluid interfaces in experiment and derived an expression for the associated capillary energy $E$ for two cases, i.e., pinned contact lines and equilibrium contact lines, which differ from expressions derived by others in the literature. In this problem, a particle of radius $a$ makes a disturbance in a large domain characterized by principal radii of curvature $R_1$ and $R_2$. Since $a$ is smaller than all associated geometric and physico-chemical length scales, analysis calls for a singular perturbation approach. We recapitulate these concepts, identify conceptual errors in the Comments about our work, and provide evidence from experiment and simulation that supports our view., Comment: 6 pages, 2 figures

Confined smectic A liquid crystals (SmA LCs) form topological defects called focal conic domains (FCDs) that focus light as gradient-index lenses. Here, we exploit surface curvature to self-assemble FCDs in a single step into a hierarchical structure (coined "flower pattern") molded by the fluid interface that is pinned at the top of a micropillar. The structure resembles the compound eyes of some invertebrates, which consist of hundreds of microlenses on a curved interface, able to focus and construct images in three dimensions. Here we demonstrate that these flowers are indeed "compound eyes" with important features which have not been demonstrated previously in the literature. The eccentric FCDs gradually change in size with radial distance from the edge of the micropillar, resulting in a variable microlens focal length that ranges from a few microns to a few tens of microns within a single "flower". We show that the microlenses can construct a composite 3D image from different depth of field. Moreover, the smectic "compound eye" can be reconfigured by heating and cooling at the LC phase transition temperature; its field of view can be manipulated by tuning the curvature of the LC interface, and the lenses are sensitive to light polarization., Comment: 17 pages, 9 figures (4 supplementary), 3 supplementary movies. This is the pre-peer reviewed version of the article which has been published in its final form in Advanced Optical Materials and is available at http://onlinelibrary.wiley.com/doi/10.1002/adom.201500153/abstract

We address the question: How does capillarity propel microspheres along curvature gradients? For a particle on a fluid interface, there are two conditions that can apply at the three phase contact line: Either the contact line adopts an equilibrium contact angle, or it can be pinned by kinetic trapping, e.g. at chemical heterogeneities, asperities or other pinning sites on the particle surface. We formulate the curvature capillary energy for both scenarios for particles smaller than the capillary length and far from any pinning boundaries. The scale and range of the distortion made by the particle are set by the particle radius; we use singular perturbation methods to find the distortions and to rigorously evaluate the associated capillary energies. For particles with equilibrium contact angles, contrary to the literature, we find that the capillary energy is negligible, with the first contribution bounded to fourth order in the product of the particle radius and the deviatoric curvature. For pinned contact lines, we find curvature capillary energies that are finite, with a functional form investigated previously by us for disks and microcylinders on curved interfaces. In experiments, we show microsphere migrate along deterministic trajectories toward regions of maximum deviatoric curvature with curvature capillary energies ranging from $6 \times10^3 - 5 \times 10^4~k_BT$. These data agree with the curvature capillary energy for the case of pinned contact lines. The underlying physics of this migration is a coupling of the interface deviatoric curvature with the quadrupolar mode of nanometric disturbances in the interface owing to the particle's contact line undulations. This work is an example of the major implications of nanometric roughness and contact line pinning for colloidal dynamics., Comment: 9 pages, 8 figures

The capillary energy landscape for particles on curved fluid interfaces is strongly influenced by the particle wetting conditions. Contact line pinning has now been widely reported for colloidal particles, but its implications in capillary interactions have not been addressed. Here, we present experiment and analysis for disks with pinned contact lines on curved fluid interfaces. In experiment, we study microdisk migration on a host interface with zero mean curvature; the microdisks have contact lines pinned at their sharp edges and are sufficiently small that gravitational effects are negligible. The disks migrate away from planar regions toward regions of steep curvature with capillary energies inferred from the dissipation along particle trajectories which are linear in the deviatoric curvature. We derive the curvature capillary energy for an interface with arbitrary curvature, and discuss each contribution to the expression. By adsorbing to a curved interface, a particle eliminates a patch of fluid interface and perturbs the surrounding interface shape. Analysis predicts that perfectly smooth, circular disks do not migrate, and that nanometric deviations from a planar circular, contact line, like those around a weakly roughened planar disk, will drive migration with linear dependence on deviatoric curvature, in agreement with experiment.

We study the assembly of colloids in a two phase water-water system that provides an environment that can sustain bacteria, providing a new structure with rich potential to confine and structure living colloids. The water-water system, formed via phase separation of a casein and xanthan mixture, forms a 3-D structure of coexisting casein-rich and xanthan-rich phases. Fluorescent labelling and confocal microscopy reveal the attachment of these living colloids, including Escherichia coli and Pseudomonas aeruginosa, at the interface between the two phases. Inert colloids also become trapped at the interfaces, suggesting that the observed attachment can be attributed to capillarity. Over time, these structures coarsen and eventually degrade, illustrating the dynamic nature of these systems. This system lays the foundation for future studies of the interplay of physicochemical properties of the fluid interfaces and bulk phases and microbial responses they provoke to induce complex spatial organization, to study species which occupy distinct niches, and to optimize efficient microbial cross-feeding or protection from competitors., Comment: 13 pages, 8 figures (includes supplementary)

We explore micropatterned director structures of aqueous lyotropic chromonic liquid crystal (LCLC) films created on square lattice cylindrical-micropost substrates. The structures are manipulated by modulating the LCLC mesophases and their elastic properties via concentration through drying. Nematic LCLC films exhibit preferred bistable alignment along the diagonals of the micropost lattice. Columnar LCLC films, dried from nematics, form two distinct director and defect configurations: a diagonally aligned director pattern with local squares of defects, and an off-diagonal configuration with zig-zag defects. The formation of these states appears to be tied to the relative splay and bend free energy costs of the initial nematic films. The observed nematic and columnar configurations are understood numerically using a Landau-de Gennes free energy model. Among other attributes, the work provide first examples of quasi-2D micropatterning of LC films in the columnar phase and lyotropic LC films in general, and it demonstrates alignment and configuration switching of typically difficult-to-align LCLC films via bulk elastic properties., Comment: 9 pages; 9 figures; accepted for publication in Soft Matter

Focal conic domains (FCDs) in smectic-A liquid crystals have drawn much attention both for their exquisitely structured internal form and for their ability to direct the assembly of micro- and nanomaterials in a variety of patterns. A key to directing FCD assembly is control over the eccentricity of the domain. Here, we demonstrate a new paradigm for creating spatially varying FCD eccentricity by confining a hybrid-aligned smectic with curved interfaces. In particular, we manipulate interface behavior with colloidal particles in order to experimentally produce two examples of what has recently been dubbed the flower texture, where the focal hyperbolae diverge radially outward from the center of the texture, rather than inward as in the canonical eventail or fan texture. We explain how this unconventional assembly can arise from appropriately curved interfaces. Finally, we present a model for this system that applies the law of corresponding cones, showing how FCDs may be embedded smoothly within a "background texture" of large FCDs and concentric spherical layers, in a manner consistent with the qualitative features of the smectic flower. Such understanding could potentially lead to disruptive liquid crystal technologies beyond displays, including patterning, smart surfaces, microlens arrays, sensors and nanomanufacturing.

We exploit the long-ranged elastic fields inherent to confined nematic liquid crystals to assemble colloidal particles trapped at the liquid crystal interface into reconfigurable structures with complex symmetries and packings. Spherical colloids with homeotropic anchoring trapped at the interface between air and the nematic liquid crystal 5CB create quadrupolar distortions in the director field causing particles to repel and consequently form close-packed assemblies with a triangular habit. Here we report on complex, open structures organized via interactions with defects in the bulk. Specifically, by confining the nematic liquid crystal in an array of microposts with homeotropic anchoring conditions, we cause defect rings to form at well-defined locations in the bulk of the sample. These defects source elastic deformations that direct the assembly of the interfacially-trapped colloids into ring-like assemblies, which recapitulate the defect geometry even when the microposts are completely immersed in the nematic. When the surface density of the colloids is high, they form a ring near the defect and a hexagonal lattice far from it. Since topographically complex substrates are easily fabricated and liquid crystal defects are readily reconfigured, this work lays the foundation for a new, robust mechanism to dynamically direct assembly over large areas by controlling surface anchoring and associated bulk defect structure., Comment: 11 pages, 5 figures, submitted to PNAS

In this work, we show that Janus washers, genus-one colloids with hybrid anchoring conditions, form topologically required defects in nematic liquid crystals. Experiments under crossed polarizers reveal the defect structure to be a rigid disclination loop confined within the colloid, with an accompanying defect in the liquid crystal. When confined to a homeotropic cell, the resulting colloid-defect ring pair tilts relative to the far field director, in contrast to the behavior of toroidal colloids with purely homeotropic anchoring. We show that this tilting behavior can be reversibly suppressed by the introduction of a spherical colloid into the center of the toroid, creating a new kind of multi-shape colloidal assemblage., Comment: 5 pages, 4 figures, accepted for publication in Soft Matter

Microbullet particles, cylinders with one blunt and one spherical end, offer a novel platform to study the effects of anisotropy and curvature on colloidal assembly in complex fluids. Here, we disperse microbullets in 4-cyano-4'-pentylbiphenyl (5CB) nematic liquid crystal (NLC) cells and form oriented elastic dipoles with a nematic point defect located near the curved end. This feature allows us to study particle interactions as a function of dipole alignment. By careful control of the surface anchoring at the particle surface and the confining boundaries, we study the interactions and assembly of microbullets under various conditions. When microbullets with homeotropic surface anchoring are dispersed in a planar cell, parallel dipoles form linear chains parallel to the director, similar to the observations of spherical particles in a planar cell, while antiparallel dipoles orient side-to-side. In a homeotropic cell, however, particles rotate to orient their long axis parallel to the director. When so aligned, parallel dipoles repel and form 2D ordered assemblies with hexagonal symmetry that ripen over time owing to attraction between antiparallel neighbors. Further, we show that the anchoring conditions inside the cell can be altered by application of an electrical field, allowing us to flip microbullets to orient parallel to the director, an effect driven by an elastic torque. Finally, we detail the mechanisms that control the formation of 1D chains and hexagonal lattices with respect to the elasticity of the NLC., Comment: 12 pages, 8 figures, the full catastrophe, version to be published