Sustainable manufacturing of sensors onto soft systems using self-coagulating conductive Pickering emulsions.

Compliant sensors based on composite materials are necessary components for geometrically complex systems such as wearable devices or soft robots. Composite materials consisting of polymer matrices and conductive fillers have facilitated the manufacture of compliant sensors due to their potential to be scaled in printing processes. Printing composite materials generally entails the use of solvents, such as toluene or cyclohexane, to dissolve the polymer resin and thin down the material to a printable viscosity. However, such solvents cause swelling and decomposition of most polymer substrates, limiting the utility of the composite materials. Moreover, many such conventional solvents are toxic or otherwise present health hazards. Here, sustainable manufacturing of sensors is reported, which uses an ethanol-based Pickering emulsion that spontaneously coagulates and forms a conductive composite. The Pickering emulsion consists of emulsified polymer precursors stabilized by conductive nanoparticles in an ethanol carrier. Upon evaporation of the ethanol, the precursors are released, which then coalesce amid nanoparticle networks and spontaneously polymerize in contact with the atmospheric moisture. We printed the self-coagulating conductive Pickering emulsion onto a variety of soft polymeric systems, including all-soft actuators and conventional textiles, to sensitize these systems. The resulting compliant sensors exhibit high strain sensitivity with negligible hysteresis, making them suitable for wearable and robotic applications.

Precise nanofiltration in a fouling-resistant self-assembled membrane with water-continuous transport pathways.

Self-assembled materials are attractive for next-generation membranes. However, the need to align self-assembled nanostructures (e.g. cylinders, lamellae) and the narrow stability windows for ordered bicontinuous systems present serious challenges. We propose and demonstrate a novel approach that circumvents these challenges by exploiting size-selective transport in the water-continuous medium of a nanostructured polymer templated from a self-assembled lyotropic H1 mesophase. Optimization of the mesophase composition enables high-fidelity retention of the H1 structure on photoinduced cross-linking. The resulting material is a mechanically robust nanostructured polymer possessing internally and externally cross-linked nanofibrils surrounded by a continuous aqueous medium. Fabricated membranes show size selectivity at the 1- to 2-nm length scale and water permeabilities of ~10 liters m-2 hour-1 bar-1 µm. Moreover, the membranes display excellent antimicrobial properties due to the quaternary ammonium groups on the nanofibril surfaces. These results represent a breakthrough for the potential use of polymerized lyotropic mesophase membranes in practical water purification applications.

Flat Drops, Elastic Sheets, and Microcapsules by Interfacial Assembly of a Bacterial Biofilm Protein, BslA.

Protein adsorption and assembly at interfaces provide a potentially versatile route to create useful constructs for fluid compartmentalization. In this context, we consider the interfacial assembly of a bacterial biofilm protein, BslA, at air-water and oil-water interfaces. Densely packed, high modulus monolayers form at air-water interfaces, leading to the formation of flattened sessile water drops. BslA forms elastic sheets at oil-water interfaces, leading to the production of stable monodisperse oil-in-water microcapsules. By contrast, water-in-oil microcapsules are unstable but display arrested rather than full coalescence on contact. The disparity in stability likely originates from a low areal density of BslA hydrophobic caps on the exterior surface of water-in-oil microcapsules, relative to the inverse case. In direct analogy with small molecule surfactants, the lack of stability of individual water-in-oil microcapsules is consistent with the large value of the hydrophilic-lipophilic balance (HLB number) calculated based on the BslA crystal structure. The occurrence of arrested coalescence indicates that the surface activity of BslA is similar to that of colloidal particles that produce Pickering emulsions, with the stability of partially coalesced structures ensured by interfacial jamming. Micropipette aspiration and flow in tapered capillaries experiments reveal intriguing reversible and nonreversible modes of mechanical deformation, respectively. The mechanical robustness of the microcapsules and the ability to engineer their shape and to design highly specific binding responses through protein engineering suggest that these microcapsules may be useful for biomedical applications.

Photoresponsive and Magnetoresponsive Graphene Oxide Microcapsules Fabricated by Droplet Microfluidics.

Fluid compartmentalization by microencapsulation is important in scenarios where protection or controlled release of encapsulated species, or isolation of chemical transformations is the central concern. Realizing responsive encapsulation systems by incorporating functional nanomaterials is of particular interest. We report here on the development of graphene oxide microcapsules enabled by a single-step microfluidic process. Interfacial reaction of epoxide-bearing graphene oxide sheets and an amine-functionalized macromolecular silicone fluid creates a chemically cross-linked film with micronscale thickness at the surface of water-in-oil droplets generated by microfluidic devices. The resulting microcapsules are monodisperse, mechanically resilient, and shape-tunable constructs. Ferrite nanoparticles are incorporated via the aqueous phase and enable microcapsule positioning by a magnetic field. We exploit the photothermal response of graphene oxide to realize microcapsules with photoresponsive release characteristics and show that the microcapsule permeability is significantly enhanced by near-IR illumination. The dual magnetic and photoresponsive characteristics, combined with the use of a single-step process employing biocompatible fluids, represent highly compelling aspects for practical applications.

Controlling orientational order in block copolymers using low-intensity magnetic fields.

The interaction of fields with condensed matter during phase transitions produces a rich variety of physical phenomena. Self-assembly of liquid crystalline block copolymers (LC BCPs) in the presence of a magnetic field, for example, can result in highly oriented microstructures due to the LC BCP's anisotropic magnetic susceptibility. We show that such oriented mesophases can be produced using low-intensity fields (<0.5 T) that are accessible using permanent magnets, in contrast to the high fields (>4 T) and superconducting magnets required to date. Low-intensity field alignment is enabled by the addition of labile mesogens that coassemble with the system's nematic and smectic A mesophases. The alignment saturation field strength and alignment kinetics have pronounced dependences on the free mesogen concentration. Highly aligned states with orientation distribution coefficients close to unity were obtained at fields as small as 0.2 T. This remarkable field response originates in an enhancement of alignment kinetics due to a reduction in viscosity, and increased magnetostatic energy due to increases in grain size, in the presence of labile mesogens. These developments provide routes for controlling structural order in BCPs, including the possibility of producing nontrivial textures and patterns of alignment by locally screening fields using magnetic nanoparticles.

Highly stiff yet elastic microcapsules incorporating cellulose nanofibrils.

Microcapsules with high mechanical stability and elasticity are desirable in a variety of contexts. We report a single-step method to fabricate such microcapsules by microfluidic interfacial complexation between high stiffness cellulose nanofibrils (CNF) and an oil-soluble cationic random copolymer. Single-capsule compression measurements reveal an elastic modulus of 53 MPa for the CNF-based capsule shell with complete recovery of deformation from strains as large as 19%. We demonstrate the ability to manipulate the shell modulus by the use of polyacrylic acid (PAA) as a binder material, and observe a direct relationship between the shell modulus and the PAA concentration, with moduli as large as 0.5 GPa attained. These results demonstrate that CNF incorporation provides a facile route for producing strong yet flexible microcapsule shells.

Highly Selective Vertically Aligned Nanopores in Sustainably Derived Polymer Membranes by Molecular Templating.

We describe a combination of molecular templating and directed self-assembly to realize highly selective vertically aligned nanopores in polymer membranes using sustainably derived materials. The approach exploits a structure-directing molecule to template the assembly of plant-derived fatty acids into highly ordered columnar mesophases. Directed self-assembly using physical confinement and magnetic fields provides vertical alignment of the columnar nanostructures in large area (several cm2) thin films. Chemically cross-linking the mesophase with added conventional vinyl comonomers and removing the molecular template results in a mechanically robust polymer film with vertically aligned 1.2-1.5 nm diameter nanopores with a large specific surface area of ∼670 m2/g. The nanoporous polymer films display exceptional size and charge selectivity as demonstrated by adsorption experiments using model penetrant molecules. These materials have significant potential to function as high-performance nanofiltration membranes and as nanoporous thin films for high-density lithographic pattern transfer. The scalability of the fabrication process suggests that practical applications can be reasonably anticipated.

Soft microcapsules with highly plastic shells formed by interfacial polyelectrolyte-nanoparticle complexation.

Composite microcapsules have been aggressively pursued as designed chemical entities for biomedical and other applications. Common preparations rely on multi-step, time consuming processes. Here, we present a single-step approach to fabricate such microcapsules with shells composed of nanoparticle-polyelectrolyte and protein-polyelectrolyte complexes, and demonstrate control of the mechanical and release properties of these constructs. Interfacial polyelectrolyte-nanoparticle and polyelectrolyte-protein complexation across a water-oil droplet interface results in the formation of capsules with shell thicknesses of a few µm. Silica shell microcapsules exhibited a significant plastic response at small deformations, whereas lysozyme incorporated shells displayed a more elastic response. We exploit the plasticity of nanoparticle incorporated shells to produce microcapsules with high aspect ratio protrusions by micropipette aspiration.

Single-step microfluidic fabrication of soft monodisperse polyelectrolyte microcapsules by interfacial complexation.

Common methods for fabrication of polyelectrolyte microcapsules rely on a multi-step process. We propose a single-step approach to generate polyelectrolyte microcapsules with 1-2 µm shells based on polyelectrolyte complexation across a water/oil droplet interface and study the effect of parameters controlling the polyelectrolyte complexation on shell thickness.