arXiv subjects

Kathleen J. Stebe

Publications and source records attributed to Kathleen J. Stebe.

At least 19 recordsLinked to original sources

arXiv2026

Gelation of functional peptides by trivalent cations at the air-water interface

We report a mechanism for gelation at fluid interfaces driven by multivalent-cation-mediated bridging. At the air-water interface, peptides with bound lanthanide cations undergo a coordination-geometry transition that converts the metal from a single-peptide bound state to a multi-peptide bridging state, driving charge inversion and gel formation. Surface adsorption and non-ideal interfacial electrostatics are implicated in this transition. The gel is stabilized by reversible metal-ligand coordination bonds that resist bulk salt screening, fundamentally distinct from electrostatic charge-inversion gelation in proteins. This reveals the breakdown of the peptide's coordinating sphere as a distinct pathway for interfacial gelation, independent of the diffuse electrostatic mechanisms governing bulk protein aggregation.

cond-mat.soft↗

arXiv2026

A sweeping twist defect as a topological flagellum that drives colloid motion

Nematic liquid crystals can dramatically reconfigure under dynamic forcing, providing exciting opportunities in active matter. Here, we study a hybrid disk colloid rotated by an external field which generates a dynamic companion topological defect. The disk moves faster when the defect sweeps across the disk's face. We identify the defect as a non-singular twist wall, characterize the twist energy landscape, and identify the sweeping motion as a topological instability. As the defect sweeps, it reverses the handedness of twist and lowers the free energy in the fluid in the gap above the disk. Landau-de Gennes modeling shows that the sweeping wall behaves as a propagating director texture: the director field is nearly stationary in the wall frame, while nematogens rotate locally as the wall passes. The nematogens' rotation generates a viscous stress on the surface of the disk that hastens its propulsion. Thus, the defect acts as a flagellum that powers colloid swimming, providing an example of a dissipative topological structure whose dynamics can be harnessed to perform useful work.

cond-mat.soft↗

arXiv2025

Scallop Theorem for Swimming in Anisotropic Fluids

In isotropic fluids like water, micrometer-scale swimmers have evolved swim strokes to translate despite their tiny size. As described by Purcell in his Scallop Theorem, reciprocal motions, like those performed by a scallop, cannot drive swimming when inertial effects are absent, as is typical at micrometer length scales. Thus, microswimmers have evolved complex structures that can perform non-reciprocal swim strokes or body displacements to generate motion. Microswimmer dynamics in structured fluids differ fundamentally from those in isotropic fluids because of their inherent asymmetry. The orientation of elongated constituents and the topological defects that spontaneously form near microswimmers provide broken symmetries, even atequilibrium. This is sufficient for the dynamic disturbance of even the simplest isotropic swimmers to generate propulsion. We combine experiments on magnetically rotated colloids in nematic liquid crystals with analytic non-equilibrium solutions to formulate propulsion strategies for microswimmers in nematic fluids and determine how swimming velocity depends on the rotation rate, materials parameters, and forcing regimes. For example, we find that micro-scale spherical colloids swim effectively under continuous rotation and under reciprocal forcing.Thus, swim strokes that are ineffective in isotropic fluids are highly effective in nematic liquid crystals. In light of these observations, the Scallop Theorem is extended for structured fluids.

cond-mat.soft↗

arXiv2024

Interfacial Rheology of Lanthanide Binding Peptide Surfactants at the Air-Water Interface

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.

cond-mat.soft↗

arXiv2024

Swimmers at Interfaces Enhance Interfacial Transport

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

cond-mat.soft↗

arXiv2023

Interfacial flow around a pusher bacterium

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.

physics.bio-ph↗

arXiv2022

Bicontinuous interfacially jammed emulsion gels with nearly uniform sub-micrometer domains via regulated co-solvent removal

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).

cond-mat.soft↗

arXiv2022

Nematic colloidal micro-robots as physically intelligent systems

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.

cond-mat.soft↗

arXiv2021

Topological defect-propelled swimming of nematic colloids

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.

cond-mat.soft↗

arXiv2020

Driven and active colloids at fluid interfaces

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.

cond-mat.soft↗

arXiv2020

Effect of Confinement on Solvent-driven Infiltration of Polymer (SIP) into Nanoparticle Packings

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.

cond-mat.mtrl-sci↗

arXiv2018

Tunable colloid trajectories in nematic liquid crystals near wavy walls

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

cond-mat.soft↗

arXiv2018

Shaping nanoparticle fingerprints at the interface of cholesteric droplets

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.

cond-mat.soft↗

arXiv2018

Elastocapillary driven assembly of particles at free-standing smectic-A films

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.

cond-mat.soft↗

arXiv2017

Capillary Assembly of Colloids: Interactions on Planar and Curved Interfaces

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.

cond-mat.soft↗

arXiv2017

Films of Bacteria at Interfaces (FBI): Remodeling of Fluid Interfaces by Pseudomonas aeruginosa

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.

cond-mat.soft↗

arXiv2017

Curvature capillary repulsion

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.

cond-mat.soft↗

arXiv2017

A change in stripes for cholesteric shells via anchoring in moderation

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.

cond-mat.soft↗