Pair Interactions of Self-Propelled SiO2-Pt Janus Colloids: Chemically Mediated Encounters.

Driven by the necessity to achieve a thorough comprehension of the bottom-up fabrication process of functional materials, this experimental study investigates the pairwise interactions or collisions between chemically active SiO2-Pt Janus colloids. These collisions are categorized based on the Janus colloids' orientations before and after they make physical contact. In addition to the hydrodynamic interactions, the Janus colloids are also known to affect each other's chemical field, resulting in chemophoretic interactions, which depend on the degree of surface anisotropy in reactivity of Janus colloid and the solute-surface interaction at play. Our study reveals that these interactions lead to a noticeable decrease in particle speed and changes in orientation that correlate with the contact duration and yield different collision types. Distinct configurations of contact during collisions were found, whose mechanisms and likelihood are found to be dependent primarily on the chemical interactions. Such estimates of collision and their characterization in dilute suspensions shall have a key impact in determining the arrangement and time scales of dynamical structures and assemblies of denser suspensions and potentially the functional materials of the future.

Acute Gastric Volvulus With Wandering Spleen in a Two-Year-Old Child: A Rare Association.

Gastric volvulus is a rare clinical condition characterized by a pathological rotation of the stomach greater than 180º around its axis. The wandering spleen is also an exceptional clinical entity characterized by the absence or laxity of splenic ligaments which lead to splenic mobility in the abdominal cavity from its normal anatomical site. Wandering spleen and gastric volvulus association is unusual. Both can be life-threatening if left untreated. We herein present a rare, unusual association of mesenteroaxial gastric volvulus with wandering spleen in a two-year-old child and interpret the radiological findings to ensure correct and early diagnosis.

Mode switching of active droplets in macromolecular solutions.

Typical bodily and environmental fluids encountered by biological swimmers consist of dissolved macromolecules such as proteins or polymers, rendering them even non-Newtonian at times. Active droplets mimic the essential propulsive characteristics of several biological swimmers, and serve as ideal model systems to widen our understanding of their locomotive strategies. Here, we investigate the motion of a micellar solubilization driven active oil droplet in an aqueous medium consisting of polymers as macromolecular solutes. Experiments reveal extreme sensitivity of the droplet motion to the presence of macromolecules in its ambient medium. Through in situ visualization of the self-generated chemical field around the droplet, we notice unexpectedly high diffusivity of the filled micelles in the presence of high molecular weight polymeric solutes. This highlights the breakdown of continuum approximation due to a significant size difference between the macromolecular solutes and the micelles. It is shown that the Péclet number, defined based on the experimentally determined filled micelle diffusivity (taking into account the local solvent viscosity) successfully captures the transition from smooth to jittery propulsion mode for both molecular and macromolecular solutes. With an increase in macromolecular solute concentration, particle image velocimetry reveals another mode switching from the conventional pusher mode to puller mode of propulsion, characterized by a more persistent droplet motion. By doping the ambient medium with suitable choice of macromolecules, our experiments unveil a novel route to orchestrate complex transitions in active droplet propulsion.

Dynamics of Active SiO2-Pt Janus Colloids in Dilute Poly(ethylene oxide) Solutions.

Self-propelled Janus colloids (JCs) have recently gained much attention due to their ability to move autonomously and mimic biological microswimmers. This ability makes them suitable for prospective drug/cargo-delivery applications in microscopic domains. Understanding their dynamics in surroundings doped with macromolecules such as polymers is crucial, as most of the target application media are complex in nature. In this study, we investigate the self-diffusiophoretic motion of hydrogen peroxide-fuelled SiO2-Pt JCs in the presence of dilute amounts of poly(ethylene oxide) (PEO). Despite the addition of PEO chains producing a Newtonian behavior with negligible increase in viscosity, the ballistic movement and rotational fluctuations of active JCs are observed to be significantly suppressed. With an increase in the polymer concentration, this leads to a transition from smooth to jittery to cage-hopping to the arrested motion of active JCs. We further propose that the anisotropic interaction of the polymers with the JC increases the "local drag" of the medium, resulting in the unusual impediment of the active motion.

Deforming active droplets in viscoelastic solutions.

The motion of biological swimmers in typical bodily fluids is modelled using a system of micellar solubilization driven active droplets in a viscoelastic polymeric solution. The viscoelastic nature of the medium, as perceived by the moving droplet, characterized by the Deborah number (De), is tuned by varying the surfactant (fuel) and polymer concentration in the ambient medium. At moderate De, the droplet exhibits a steady deformed shape, markedly different from the spherical shape observed in Newtonian media. A theoretical analysis based on the normal stress balance at the interface is shown to accurately predict the droplet shape. With a further increase in De, time-periodic deformation accompanied by an oscillatory transition in swimming mode is observed. The study unveils the hitherto unexplored rich complexity in the motion of active droplets in viscoelastic fluids.

Interaction of Active Janus Colloids with Tracers.

Understanding the motion of artificial active swimmers in complex surroundings, such as a dense bath of passive particulate matter, is essential for their successful utilization as cargo (drug) carriers and sensors or for medical imaging, under microscopic domains. In this study, we experimentally investigated the motion of active SiO2-Pt Janus particles (JPs) in a two-dimensional bath of smaller silica tracers dispersed with varying areal densities. Our observations indicate that when an active JP undergoes a collision with an isolated tracer, their interaction can have a significant impact on the swimmer's motion. However, the overall impact of tracers on the active JPs' motion (translation and rotation) depends on the frequency of collisions and also on the nature of the collision, which is marked by the time-duration for which the particles maintain contact during the collisions. Further, in the high-density tracer bath, our experiments reveal that the motion of the active JP results in a novel organizational behavior of the tracers on the trailing Pt (depletion of tracers) and the leading SiO2 (accumulation of tracers) side. In laboratory frame the emergence and the subsequent vanishing of the depletion zone are discussed in detail.

Impurity-induced nematic-isotropic transition of liquid crystals.

Complex fluids made of liquid crystals (LCs) and small molecules, surfactants, nanoparticles or 1D/2D nanomaterials show novel and interesting features, making them suitable materials for various applications starting from optoelectronics to biosensing. While these additives (impurities) introduce new features in the complex fluids, they may also alter the phase transition behaviour of LCs depending on the physiochemical properties of the added impurity. This article reports on the phase transition of 4-cyano-4'-alkylbiphenyl (nCB) LCs in the presence of an associative impurity, i.e., water and a non-associative impurity, i.e., hexane employing computational methods and experiments. In particular, all-atom (AA) simulations and coarse-grained (CG) models were designed for two complex systems, i.e., 6CB + water and 6CB + hexane and corresponding spectrophotometry experiments were performed using a homologous LC, i.e., 5CB. Results from the simulations and experiments elucidate that the phase transition of LCs depends on the mixing/demixing phenomenon of the impurity in the LC. While associative liquids like water which do not mix with LCs do not influence the nematic-to-isotropic phase transition of LCs, hexane, being a non-associative liquid, mixes well with LCs and induces a sharp impurity-induced nematic-to-isotropic phase transition. Upon application of both AA and CG simulations, we could reach the conclusion that the mixing/demixing phenomenon in an LC + impurity system influences the entropy of the system and hence the observed phase transitions are entropy-driven.

Self-Propelled Janus Colloids in Shear Flow.

To fully harness the potential of artificial active colloids, investigation of their response to various external stimuli including external flow is of great interest. Therefore, in this study, we perform experiments on SiO2-Pt Janus particles suspended in an aqueous medium in a capillary subjected to different shear flow rates. Particles were propelled using varied H2O2 (fuel) concentrations. For a particular propulsion speed, with increasing shear flow, a continuous transition in the motion of active Janus particles (JPs) from the usual random active motion to preferential movement along the vorticity direction and then finally to migration along the flow was observed. This transition was accompanied by a significant decline in in-plane fluctuations of the particle trajectories. Another key observation is that the activity of JPs produces a delay in shear-induced rolling, which at moderate flow, allows the JPs to adopt a specific orientation, facilitating their migration along the vorticity direction. At higher flow rates, once shear flow overcomes the activity-induced resistance and initiates rolling, the probability of JPs adopting such preferred orientations reduces. Our analysis further revealed that these transitions are governed by a nondimensional quantity λ, which compares the relative strength of the shear-induced particle flow to the propulsion speed.

Dynamics of Nanoparticles in Entangled Polymer Solutions.

The mean square displacement ⟨r2⟩ of nanoparticle probes dispersed in simple isotropic liquids and in polymer solutions is interrogated using fluorescence correlation spectroscopy and single-particle tracking (SPT) experiments. Probe dynamics in different regimes of particle diameter (d), relative to characteristic polymer length scales, including the correlation length (ξ), the entanglement mesh size (a), and the radius of gyration (Rg), are investigated. In simple fluids and for polymer solutions in which d ≫ Rg, long-time particle dynamics obey random-walk statistics ⟨r2⟩:t, with the bulk zero-shear viscosity of the polymer solution determining the frictional resistance to particle motion. In contrast, in polymer solutions with d < Rg, polymer molecules in solution exert noncontinuum resistances to particle motion and nanoparticle probes appear to interact hydrodynamically only with a local fluid medium with effective drag comparable to that of a solution of polymer chain segments with sizes similar to those of the nanoparticle probes. Under these conditions, the nanoparticles exhibit orders of magnitude faster dynamics than those expected from continuum predictions based on the Stokes-Einstein relation. SPT measurements further show that when d > a, nanoparticle dynamics transition from diffusive to subdiffusive on long timescales, reminiscent of particle transport in a field with obstructions. This last finding is in stark contrast to the nanoparticle dynamics observed in entangled polymer melts, where X-ray photon correlation spectroscopy measurements reveal faster but hyperdiffusive dynamics. We analyze these results with the help of the hopping model for particle dynamics in polymers proposed by Cai et al. and, on that basis, discuss the physical origins of the local drag experienced by the nanoparticles in entangled polymer solutions.

Active Janus Particles at Interfaces of Liquid Crystals.

We report an investigation of the active motion of silica-palladium Janus particles (JPs) adsorbed at interfaces formed between nematic liquid crystals (LCs) and aqueous phases containing hydrogen peroxide (H2O2). In comparison to isotropic oil-aqueous interfaces, we observe the elasticity and anisotropic viscosity of the nematic phase to change qualitatively the active motion of the JPs at the LC interfaces. Although contact line pinning on the surface of the JPs is observed to restrict out-of-plane rotational diffusion of the JPs at LC interfaces, orientational anchoring of nematic LCs on the silica (planar) and palladium (homeotropic) hemispheres biases JP in-plane orientations to generate active motion almost exclusively along the director of the LC at low concentrations of H2O2 (0.5 wt %). In contrast, displacements perpendicular to the director exhibit the characteristics of Brownian diffusion. At higher concentrations of H2O2 (1-3 wt %), we observe an increasing population of JPs propelled parallel and perpendicular to the LC director in a manner consistent with active motion. In addition, under these conditions, we also observe a subpopulation of JPs (approximately 10%) that exhibit active motion exclusively perpendicular to the LC director. These results are discussed in light of independent measurements of the distribution of azimuthal orientations of the JPs at the LC interfaces and calculations of the elastic energies that bias JP orientations. We also contrast our observations at LC interfaces to past studies of self-propulsion of particles within and at the interfaces of isotropic liquids.

Enthalpy-Driven Stabilization of Dispersions of Polymer-Grafted Nanoparticles in High-Molecular-Weight Polymer Melts.

Phase stability of polymer nanocomposites (PNCs) composed of polymer-grafted SiO2 nanoparticles (NPs) blended with high-molar-mass host polymer chains is investigated. We focus on blends in which the particle-grafted polymer, polyethylene glycol (PEG), and the host-atactic poly(methylmethacrylate) (PMMA) or PMMA/oligo-PEG blends-exhibit favorable enthalpic interactions. Small-angle X-ray scattering measurements are used to evaluate the phase stability of the blends and to report on the structure of the materials at intermediate and long length scales. By exploring SiO2-PEG/PMMA and SiO2-PEG/PMMA-PEG systems covering a wide range of molecular weights (Mw) of PMMA (1.1 kDa ≤ Mw,PMMA ≤ 1.1 × 103 kDa) and tethered PEG (0.5 kDa ≤ Mw, PEG ≤ 2 kDa), we are able to develop a comprehensive stability map for PNCs based on hairy NPs. At low Mw,PEG, the phase behavior is dominated by entropic effects and the negative Flory-Huggins χ parameter between PEG and PMMA plays no role in phase stability. For higher Mw,PEO and intermediate Mw,PMMA, a crossover from entropy- to enthalpy-dominated behavior is observed, which leads to the phase stability in PNCs well beyond the conventional limits reported for SiO2-PEG/PEG mixtures. This enhanced mixing ceases above a critical Mw,PMMA, where it is found that PMMA chains wet a sufficiently large number of SiO2-PEG particles to bridge and thereby destabilize the composites.

Size-Dependent Particle Dynamics in Entangled Polymer Nanocomposites.

Polymer-grafted nanoparticles with diameter d homogeneously dispersed in entangled polymer melts with varying random coil radius R0, but fixed entanglement mesh size a(e), are used to study particle motions in entangled polymers. We focus on materials in the transition region between the continuum regime (d > R0), where the classical Stokes-Einstein (S-E) equation is known to describe polymer drag on particles, and the noncontinuum regime (d < a(e)), in which several recent studies report faster diffusion of particles than expected from continuum S-E analysis, based on the bulk polymer viscosity. Specifically, we consider dynamics of particles with sizes d ≥ a(e) in entangled polymers with varying molecular weight M(w) in order to investigate how the transition from noncontinuum to continuum dynamics occur. We take advantage of favorable enthalpic interactions between SiO2 nanoparticles tethered with PEO molecules and entangled PMMA host polymers to create model nanoparticle-polymer composites, in which spherical nanoparticles are uniformly dispersed in entangled polymers. Investigation of the particle dynamics via X-ray photon correlation spectroscopy measurements reveals a transition from fast to slow particle motion as the PMMA molecular weight is increased beyond the entanglement threshold, with a much weaker M(w) dependence for M(w) > M(e) than expected from S-E analysis based on bulk viscosity of entangled PMMA melts. We rationalize these observations using a simple force balance analysis around particles and find that nanoparticle motion in entangled melts can be described using a variant of the S-E analysis in which motion of particles is assumed to only disturb subchain entangled host segments with sizes comparable to the particle diameter.

A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles.

Rough electrodeposition, uncontrolled parasitic side-reactions with electrolytes and dendrite-induced short-circuits have hindered development of advanced energy storage technologies based on metallic lithium, sodium and aluminium electrodes. Solid polymer electrolytes and nanoparticle-polymer composites have shown promise as candidates to suppress lithium dendrite growth, but the challenge of simultaneously maintaining high mechanical strength and high ionic conductivity at room temperature has so far been unmet in these materials. Here we report a facile and scalable method of fabricating tough, freestanding membranes that combine the best attributes of solid polymers, nanocomposites and gel-polymer electrolytes. Hairy nanoparticles are employed as multifunctional nodes for polymer crosslinking, which produces mechanically robust membranes that are exceptionally effective in inhibiting dendrite growth in a lithium metal battery. The membranes are also reported to enable stable cycling of lithium batteries paired with conventional intercalating cathodes. Our findings appear to provide an important step towards room-temperature dendrite-free batteries.

Phase stability and dynamics of entangled polymer-nanoparticle composites.

Nanoparticle-polymer composites, or polymer-nanoparticle composites (PNCs), exhibit unusual mechanical and dynamical features when the particle size approaches the random coil dimensions of the host polymer. Here, we harness favourable enthalpic interactions between particle-tethered and free, host polymer chains to create model PNCs, in which spherical nanoparticles are uniformly dispersed in high molecular weight entangled polymers. Investigation of the mechanical properties of these model PNCs reveals that the nanoparticles have profound effects on the host polymer motions on all timescales. On short timescales, nanoparticles slow-down local dynamics of the host polymer segments and lower the glass transition temperature. On intermediate timescales, where polymer chain motion is typically constrained by entanglements with surrounding molecules, nanoparticles provide additional constraints, which lead to an early onset of entangled polymer dynamics. Finally, on long timescales, nanoparticles produce an apparent speeding up of relaxation of their polymer host.

Hyperdiffusive Dynamics in Newtonian Nanoparticle Fluids.

Hyperdiffusive relaxations in soft glassy materials are typically associated with out-of-equilibrium states, and nonequilibrium physics and aging are often invoked in explaining their origins. Here, we report on hyperdiffusive motion in model soft materials comprised of single-component polymer-tethered nanoparticles, which exhibit a readily accessible Newtonian flow regime. In these materials, polymer-mediated interactions lead to strong nanoparticle correlations, hyperdiffusive relaxations, and unusual variations of properties with temperature. We propose that hyperdiffusive relaxations in such materials can arise naturally from nonequilibrium or non-Brownian volume fluctuations forced by equilibrium thermal rearrangements of the particle pair orientations corresponding to equilibrated shear modes.

Biomimetic wet adhesion of viscoelastic liquid films anchored on micropatterned elastic substrates.

Inspired by the natural adhesives in the toe pads of arthropods and some other animals, we explore the effectiveness and peel failure of a thin viscoelastic liquid film anchored on a micropatterned elastic surface. In particular, we focus on the role of the substrate pattern in adhesion energy of the liquid layer and in allowing its clean separation without cohesive failure. Peel tests on the microfabricated wet adhesives showed two distinct modes of adhesive (interfacial) and cohesive (liquid bulk) failures depending on the pattern dimensions. The adhesion energy of a viscoelastic liquid layer on an optimized micropatterned elastic substrate is ~3.5 times higher than that of a control flat bilayer and ~26 times higher than that of a viscoelastic film on a rigid substrate. Adhesive liquid layers anchored by narrow microchannels undergo clean, reversible adhesive failure rather than the cohesive failure seen on flat substrates. An increase in the channel width engenders cohesive failure in which droplets of the wet adhesive remain on the peeled surface.