Material assembly from collective action of shape-changing polymers.

Some animals form transient, responsive and solid-like ensembles through dynamic structural interactions. These ensembles demonstrate emergent responses such as spontaneous self-assembly, which are difficult to achieve in synthetic soft matter. Here we use shape-morphing units comprising responsive polymers to create solids that self-assemble, modulate their volume and disassemble on demand. The ensemble is composed of a responsive hydrogel, liquid crystal elastomer or semicrystalline polymer ribbons that reversibly bend or twist. The dispersions of these ribbons mechanically interlock, inducing reversible aggregation. The aggregated liquid crystal elastomer ribbons have a 12-fold increase in the yield stress compared with cooled dispersion and contract by 34% on heating. Ribbon type, concentration and shape dictate the aggregation and govern the global mechanical properties of the solid that forms. Coating liquid crystal elastomer ribbons with a liquid metal begets photoresponsive and electrically conductive aggregates, whereas seeding cells on hydrogel ribbons enables self-assembling three-dimensional scaffolds, providing a versatile platform for the design of dynamic materials.

Competitive fitness of asymptomatic bacteriuria E. coli strain 83972 against uropathogens in human urine.

Urinary tract infection (UTI) is one of the most common bacterial infections worldwide. The main causative agent of UTI is uropathogenic Escherichia coli (UPEC). There is an immediate need for novel prophylactic and treatment strategies against UTI because of the increasing incidence of antimicrobial resistance among uropathogens. ABU 83972, an asymptomatic bacteriuria-causing E. coli strain, prevents UTI by suppressing the colonization of UPEC. However, the nature of competition and growth repression of UPEC by ABU 83972 is unclear and is the subject of our investigation. Here, we characterized the growth kinetics of ABU 83972 and uropathogens in human urine and laboratory media. Next, we performed a series of competitive co-culture experiments where ABU 83972 and uropathogens were inoculated at a 1:1 ratio in human urine and in various media, and their relative abundance was determined. In human urine, ABU 83972 outcompeted UPEC and additional uropathogens, reaching up to 90% of the total population after 24 hours of incubation. In contrast, UPEC outcompeted ABU 83972 in LB and M9 minimal media and exhibited superior colonization than ABU 83972 in the mouse urinary bladder. Since engineered living materials (ELMs) can be used to retain an organism of interest in a particular location, we developed ABU 83972-containing ELMs that effectively outcompeted UPEC in human urine. In summary, our work establishes that ABU 83972 outcompetes UPEC in a milieu- and cell-density-dependent manner, highlighting the importance of the metabolites and nutrients found in the human urine as determinants of the competitive fitness of ABU 83972.

Three-dimensional blueprinting of molecular patterns in liquid crystalline polymers.

Exploiting the interplay of anisotropic diamagnetic susceptibility of liquid crystalline monomers and site selective photopolymerization enables the fabrication of 3D freeforms with highly refined microstructures. Utilizing chain transfer agents in the mesogenic inks presents a pathway for broadly tuning the mechanical properties of liquid crystalline polymers and their response to stimuli. In particular, the combination of 1,4-benzenedimethanethiol and tetrabromomethane is shown to enable voxelated blueprinting of molecular order, while allowing for a modulation of the crosslink density and the mechanical properties. The formulation of these monomers allows for the resolution of the voxels to approach the limits set by the coherence lengths defined by the anchoring from surfaces. These compositions demonstrate the expected thermotropic responses while allowing for their functionalization with photochromic switches to elicit photomechanical responses. Actuation strains are shown to outstrip that accomplished with prior systems that did not access chain transfer agents to modulate the structure of the macromolecular network. Test cases of this system are shown to create freeform actuators that exploit the refined director patterns during high-resolution printing. These include topological defects, hierarchically-structured light responsive grippers, and biomimetic flyers whose flight dynamics can be actively modulated via irradiation with light.

Self-Assembled Microactuators Using Chiral Liquid Crystal Elastomers.

Materials that undergo reversible changes in form typically require top-down processing to program the microstructure of the material. As a result, it is difficult to program microscale, 3D shape-morphing materials that undergo non-uniaxial deformations. Here, a simple bottom-up fabrication approach to prepare bending microactuators is described. Spontaneous self-assembly of liquid crystal (LC) monomers with controlled chirality within 3D micromold results in a change in molecular orientation across thickness of the microstructure. As a result, heating induces bending in these microactuators. The concentration of chiral dopant is varied to adjust the chirality of the monomer mixture. Liquid crystal elastomer (LCE) microactuators doped with 0.05 wt% of chiral dopant produce needle-shaped actuators that bend from flat to an angle of 27.2 ± 11.3° at 180 °C. Higher concentrations of chiral dopant lead to actuators with reduced bending, and lower concentrations of chiral dopant lead to actuators with poorly controlled bending. Asymmetric molecular alignment inside 3D structure is confirmed by sectioning actuators. Arrays of microactuators that all bend in the same direction can be fabricated if symmetry of geometry of the microstructure is broken. It is envisioned that the new platform to synthesize microstructures can further be applied in soft robotics and biomedical devices.

A multifunctional shape-morphing elastomer with liquid metal inclusions.

Natural soft tissue achieves a rich variety of functionality through a hierarchy of molecular, microscale, and mesoscale structures and ordering. Inspired by such architectures, we introduce a soft, multifunctional composite capable of a unique combination of sensing, mechanically robust electronic connectivity, and active shape morphing. The material is composed of a compliant and deformable liquid crystal elastomer (LCE) matrix that can achieve macroscopic shape change through a liquid crystal phase transition. The matrix is dispersed with liquid metal (LM) microparticles that are used to tailor the thermal and electrical conductivity of the LCE without detrimentally altering its mechanical or shape-morphing properties. Demonstrations of this composite for sensing, actuation, circuitry, and soft robot locomotion suggest the potential for versatile, tissue-like multifunctionality.

Liquid Crystalline Polymers: Opportunities to Shape Neural Interfaces.

OBJECTIVES: Polymers have emerged as constituent materials for the creation of microscale neural interfaces; however, limitations regarding water permeability, delamination, and material degradation impact polymeric device robustness. Liquid crystal polymers (LCPs) have molecular order like a solid but with the fluidity of a liquid, resulting in a unique material, with properties including low water permeability, chemical inertness, and mechanical toughness. The objective of this article is to review the state-of-the-art regarding the use of LCPs in neural interface applications and discuss challenges and opportunities where this class of materials can advance the field of neural interfaces. MATERIALS AND METHODS: This review article focuses on studies that leverage LCP materials to interface with the nervous system in vivo. A comprehensive literature search was performed using PubMed, Web of Science (Clarivate Analytics), and Google Scholar. RESULTS: There have been recent efforts to create neural interfaces that leverage the material advantages of LCPs. The literature offers examples of LCP as a basis for implantable medical devices and neural interfaces in the form of planar electrode arrays for retinal prosthetic, electrocorticography applications, and cuff-like structures for interfacing the peripheral nerve. In addition, there have been efforts to create penetrating intracortical devices capable of microstimulation and resolution of biopotentials. Recent work with a subclass of LCPs, namely liquid crystal elastomers, demonstrates that it is possible to create devices with features that deploy away from a central implantation site to interface with a volume of tissue while offering the possibility of minimizing tissue damage. CONCLUSION: We envision the creation of novel microscale neural interfaces that leverage the physical properties of LCPs and have the capability of deploying within neural tissue for enhanced integration and performance.

Stimuli-responsive engineered living materials.

Stimuli-responsive materials are able to undergo controllable changes in materials properties in response to external cues. Increasing efforts have been directed towards building materials that mimic the responsive nature of biological systems. Nevertheless, limitations remain surrounding the way these synthetic materials interact and respond to their environment. In particular, it is difficult to synthesize synthetic materials that respond with specificity to poorly differentiated (bio)chemical and weak physical stimuli. The emerging area of engineered living materials (ELMs) includes composites that combine living cells and synthetic materials. ELMs have yielded promising advances in the creation of stimuli-responsive materials that respond with diverse outputs in response to a broad array of biochemical and physical stimuli. This review describes advances made in the genetic engineering of the living component and the processing-property relationships of stimuli-responsive ELMs. Finally, the implementation of stimuli-responsive ELMs as environmental sensors, biomedical sensors, drug delivery vehicles, and soft robots is discussed.

4D-Printing of Photoswitchable Actuators.

Shape-switching behavior, where a transient stimulus induces an indefinitely stable deformation that can be recovered on exposure to another transient stimulus, is critical to building smart structures from responsive polymers as continue power is not needed to maintain deformations. Herein, we 4D-print shape-switching liquid crystalline elastomers (LCEs) functionalized with supramolecular crosslinks, dynamic covalent crosslinks, and azobenzene. The salient property of shape-switching LCEs is that light induces long-lived, deformation that can be recovered on-demand by heating. UV-light isomerizes azobenzene from trans to cis, and temporarily breaks the supramolecular crosslinks, resulting in a programmed deformation. After UV, the shape-switching LCEs fix more than 90 % of the deformation over 3 days by the reformed supramolecular crosslinks. Using the shape-switching properties, we print Braille-like actuators that can be photoswitched to display different letters. This new class of photoswitchable actuators may impact applications such as deployable devices where continuous application of power is impractical.

Size of liquid metal particles influences actuation properties of a liquid crystal elastomer composite.

Composites of liquid crystal elastomer (LCE) that are electrically conductive have the potential to function as soft "artificial muscle" actuators that can be reversibly stimulated with electrical Joule-heating. Conductivity can be achieved by embedding the LCE with droplets of an alloy of gallium and indium that is liquid at room temperature. These soft artificial muscles are capable of >50% reversible actuation with an applied load. The key to actuation at high loadings of liquid metal (LM) is that the droplets deform with the surrounding matrix. By controlling the size of LM droplets through simple processing techniques, we show that the actuator properties of the LM-LCE muscle can be tuned. For example, composites with smaller liquid metal particles (ca. 10 µm or less) are stiffer than those with larger liquid metal particles (ca. >100 µm) and are capable of greater force output. However, smaller particles reduce actuation strain and composites with large particles exhibit significantly greater stroke length. Such tunability in actuation properties permits the fabrication of specialized soft artificial muscles, where processing of the composite controls actuation strain and actuation force.

Molecularly-ordered hydrogels with controllable, anisotropic stimulus response.

Hydrogels which morph between programmed shapes in response to aqueous stimuli are of significant interest for biosensors and artificial muscles, among other applications. However, programming hydrogel shape change at small size scales is a significant challenge. Here we use the inherent ordering capabilities of liquid crystals to create a mechanically anisotropic hydrogel; when coupled with responsive comonomers, the mechanical anisotropy in the network guides shape change in response to the desired aqueous condition. Our synthetic strategy hinges on the use of a methacrylic chromonic liquid crystal monomer which can be combined with a non-polymerizable chromonic of similar structure to vary the magnitude of shape change while retaining liquid crystalline order. This shape change is directional due to the mechanical anisotropy of the gel, which is up to 50% stiffer along the chromonic stack direction than perpendicular. Additionally, we show that the type of stimulus to which these anisotropic gels respond can be switched by incorporating responsive, hydrophilic comonomers without destroying the nematic phase or alignment. The utility of these properties is demonstrated in polymerized microstructures which exhibit Gaussian curvature in response to high pH due to emergent ordering in a micron-sized capillary.

Topology optimization for the design of folding liquid crystal elastomer actuators.

Aligned liquid crystal elastomers (LCEs) are capable of undergoing large reversible shape change in response to thermal stimuli and may act as actuators for many potential applications such as self-assembly and deployment of micro devices. Recent advances in LCE patterning tools have demonstrated sub-millimetre control of director orientation, enabling the preparation of materials with arbitrarily complex director fields. However, without design tools to connect the 2D director pattern with the activated 3D shape, LCE design relies on intuition and trial and error. Here we present a design methodology to generate reliable folding in monolithic LCEs designed with topology optimization. The distributions of order/disorder and director orientations are optimized so that the remotely actuated deformation closely matches a target deformation for origami folding. The optimal design exhibits a strategy to counteract the mechanical frustration that may lead to an undesirable deformation, such as anti-clastic bending. Multi-hinge networks were developed using insights from the optimal hinge designs and were demonstrated through the fabrication and reversible actuation of a self-folding box. Topology optimization provides an important step towards leveraging the opportunities afforded by LCE patterning into functional designs.

Reconfigurable Growth of Engineered Living Materials.

The growth of multicellular organisms is a process akin to additive manufacturing where cellular proliferation and mechanical boundary conditions, among other factors, drive morphogenesis. Engineers have limited ability to engineer morphogenesis to manufacture goods or to reconfigure materials comprised of biomass. Herein, a method that uses biological processes to grow and regrow magnetic engineered living materials (mELMs) into desired geometries is reported. These composites contain Saccharomyces cerevisiae and magnetic particles within a hydrogel matrix. The reconfigurable manufacturing process relies on the growth of living cells, magnetic forces, and elastic recovery of the hydrogel. The mELM then adopts a form in an external magnetic field. Yeast within the material proliferates, resulting in 259 ± 14% volume expansion. Yeast proliferation fixes the magnetic deformation, even when the magnetic field is removed. The shape fixity can be up to 99.3 ± 0.3%. The grown mELM can recover up to 73.9 ± 1.9% of the original form by removing yeast cell walls. The directed growth and recovery process can be repeated at least five times. This work enables ELMs to be processed and reprocessed into user-defined geometries without external material deposition.

Evaluation of Low-Loss Polymer Switches for Multinuclear MRI/S.

Implementation of multinuclear MRI/S as a diagnostic tool in clinical settings faces many challenges. One of those challenges is the development of highly sensitive multinuclear RF coils. Current multi-tuning techniques incorporate lossy components that impact the highest achievable SNR for at least one of the coil frequencies. As a result, optimization of multinuclear coil designs continues to be a priority for RF hardware engineers. To address this challenge, a new frequency switching technology that incorporates stimuli-responsive polymer materials was explored. Q measurements were used as a comparison metric between single-tuned, a standard switching network, and the proposed switching technology. The Q losses measured in the new switching method remained below 38% when compared to single-tuned coils. These results are consistent with low loss values reported using traditional switching networks. Furthermore, preliminary testing indicates that there is potential for improvement. These results establish the new technology as a promising alternative to traditional switching techniques.Clinical Relevance- A low loss multi-tuning technique for MRI radiofrequency coils has the potential of improving the study and diagnosis of disease.

Liquid crystal elastomer based dynamic device for urethral support: Potential treatment for stress urinary incontinence.

Stress urinary incontinence (SUI) is characterized by the involuntary loss of urine due to increased intra-abdominal pressure during coughing, sneezing, or exercising. SUI affects 20-40% of the female population and is exacerbated by aging. Severe SUI is commonly treated with surgical implantation of an autologous or a synthetic sling underneath the urethra for support. These slings, however, are static, and their tension cannot be non-invasively adjusted, if needed, after implantation. This study reports the fabrication of a novel device based on liquid crystal elastomers (LCEs) capable of changing shape in response to temperature increase induced by transcutaneous IR light. The shape change of the LCE-based device was characterized in a scar tissue phantom model. An in vitro urinary tract model was designed to study the efficacy of the LCE-based device to support continence and adjust sling tension with IR illumination. Finally, the device was acutely implanted and tested for induced tension changes in female multiparous New Zealand white rabbits. The LCE device achieved 5.6% ± 1.1% actuation when embedded in an agar gel with an elastic modulus of 100 kPa. The corresponding device temperature was 44.9 °C ± 0.4 °C, and the surrounding agar temperature stayed at 42.1 °C ± 0.4 °C. Leaking time in the in vitro urinary tract model significantly decreased (p < 0.0001) when an LCE-based cuff was sutured around the model urethra from 5.2min ± 1min to 2min ±0.5min when the cuff was illuminated with IR light. Normalized leak point force (LPF) increased significantly (p = 0.01) with the implantation of an LCE-CB cuff around the bladder neck of multiparous rabbits. It decreased significantly (p = 0.023) when the device was actuated via IR light illumination. These results demonstrate that LCE material could be used to fabricate a dynamic device for treating SUI in women.

Digitally Programmable Manufacturing of Living Materials Grown from Biowaste.

Material manufacturing strategies that use little energy, valorize waste, and result in degradable products are urgently needed. Strategies that transform abundant biomass into functional materials form one approach to these emerging manufacturing techniques. From a biological standpoint, morphogenesis of biological tissues is a "manufacturing" mode without energy-intensive processes, large carbon footprints, and toxic wastes. Inspired by biological morphogenesis, we propose a manufacturing strategy by embedding living Saccharomyces cerevisiae (Baker's yeast) within a synthetic acrylic hydrogel matrix. By culturing the living materials in media derived from bread waste, encapsulated yeast cells can proliferate, resulting in a dramatic dry mass and volume increase of the whole living material. After growth, the final material is up to 96 wt % biomass and 590% larger in volume than the initial object. By digitally programming the cell viability through UV irradiation or photodynamic inactivation, the living materials can form complex user-defined relief surfaces or 3D objects during growth. Ultimately, the grown structures can also be designed to be degradable. The proposed living material manufacturing strategy cultured from biowaste may pave the way for future ecologically friendly manufacturing of materials.

Programmable Shape Change in Semicrystalline Liquid Crystal Elastomers.

Liquid crystal elastomers (LCEs) are stimuli-responsive materials capable of reversible and programmable shape change in response to an environmental stimulus. Despite the highly responsive nature of these materials, the modest elastic modulus and blocking stress exhibited by these actuating materials can be limiting in some engineering applications. Here, we engineer a semicrystalline LCE, where the incorporation of semicrystallinity in a lightly cross-linked liquid crystalline network yields tough and highly responsive materials. Directed self-assembly can be employed to program director profiles through the thickness of the semicrystalline LCE. In short, we use the alignment of a liquid crystal monomer phase to pattern the anisotropy of a semicrystalline polymer network. Both the semicrystalline-liquid crystalline and liquid crystalline-isotropic phase transition temperatures provide controllable shape transformations. A planarly aligned sample's normalized dimension parallel to the nematic director decreases from 1 at room temperature to 0.42 at 250 °C. The introduction of the semicrystalline nature also enhances the mechanical properties exhibited by the semicrystalline LCE. Semicrystalline LCEs have a storage modulus of 390 MPa at room temperature, and monodomain samples are capable of generating a contractile stress of 2.7 MPa on heating from 25 to 50 °C, far below the nematic to isotropic transition temperature. The robust mechanical properties of this material combined with the high actuation strain can be leveraged for applications such as soft robotics and actuators capable of doing significant work.

Controlling shape morphing and cell release in engineered living materials.

Engineered living materials (ELMs) derive functionality from both a polymer matrix and the behavior of living cells within the material. The long-term goal of this work is to enable a system of ELM-based medical devices with both mechanical and bioactive functionality. Here, we fabricate multifunctional, stimuli-responsive ELMs comprised of acrylic hydrogel matrix and Escherichia coli. These ELMs undergo controlled changes in form and have a controlled release of bacteria from the composite. We hypothesize that the mechanical forces associated with cell proliferation within a covalently-crosslinked, non-degradable hydrogel are responsible for both phenomena. At constant cell loading, increased hydrogel elastic modulus significantly reduces both cell delivery and volume change associated with cell proliferation. ELMs that change volume over 100 % also result in ~106 colony forming units/mL in the growth medium over 2 h after 1 day of growth. At constant monomer feed ratios, increased cell loading leads to significantly increased cell delivery. Finally, these prokaryotic ELMs were investigated for their potential to deliver a probiotic that can reduce the proliferation of a uropathogen in vitro. Controlling the long-term delivery of bacteria could potentially be used in biomedical applications to modulate microbial communities within the human body.

Photopatterning Crystal Orientation in Shape-Morphing Polymers.

Shape-morphing polymers have gained particular attention due to their unique capability of shape transformation under numerous external stimuli such as light, pH, and temperature. Their shape-morphing properties can be used in various applications such as robotics, artificial muscles, and biomedical devices. To take advantage of the stimuli-responsive properties of the smart polymers in such applications, programming shape change precisely through a facile synthetic procedure is essential. Programmable shape-morphing is readily obtained in hydrogels and liquid crystal polymer networks, but shape programming of semicrystalline polymers usually relies on low-resolution mechanical deformation. In this paper, a semicrystalline shape-morphing polymer with a controlled shape programmability was developed via photopatterning crystal orientation using a spatially controlled photopolymerization technique. The semicrystalline polymer network forms aligned crystallites at the boundaries between dark and bright regions during photopolymerization using a projector, which introduces an anisotropic stimulus response in the films. The semicrystalline polymer films with photoaligned crystallites expand 9-15% in the direction perpendicular to the patterned lines when heated above the melting temperature. Furthermore, spatially patterning the crystal orientation enables the formation of various complex 3D structures including a helical coil, a coil with a handedness inversion, a cone, a saddle, and a twisting flower. Finally, the magnitude of the shape transformation was controlled by varying the polymerization temperatures, and the actuation temperature was tuned by changing the amount of crystallinity in the polymer films. The simplicity and ease of control of our approach to program complex 3D structures from 2D semicrystalline polymer films make it a promising system for the aforementioned applications.

4D-Printable Liquid Metal-Liquid Crystal Elastomer Composites.

Soft actuators that undergo programmable shape change in response to a stimulus are enabling components of future soft robots and other soft machines. Strategies to power these actuators often require the incorporation of rigid, electrically conductive materials into the soft actuator, thus limiting the compliance and shape change of the material. In this study, we develop a 4D-printable composite composed of liquid crystal elastomer (LCE) matrix with dispersed droplets of eutectic gallium indium alloy (EGaIn). Using deformable EGaIn droplets in place of rigid conductive fillers preserves the compliance and shape-morphing properties of the LCE. The process enables 4D-printed LCE actuators capable of photothermal and electrothermal actuation. At low liquid metal (LM) concentrations (71 wt %), the composite actuator exhibits a photothermal response upon irradiation of near-IR light. Printed actuators with a twisted nematic configuration are capable of bending angles of 150° at 800 mW cm-2. At higher LM concentrations (88 wt %), the embedded LM droplets can form percolating networks that conduct electricity and enable electrical Joule heating of the LCE. Actuation strain ranging from 5 to 12% is controlled by the amount of electrical power that is delivered to the composite. We also introduce a method for multimaterial printing of monolithic structures where the LM filler loading is spatially varied. These multifunctional materials exhibit innate responsivity where the actuator behaves as an electrical switch and can report one of two states (on/off). These multiresponsive, 4D-printable composites enable multifunctional, mechanically active structures that can be powered with IR light or low DC voltages.

From Chaos to Control: Programmable Crack Patterning with Molecular Order in Polymer Substrates.

Cracks are typically associated with the failure of materials. However, cracks can also be used to create periodic patterns on the surfaces of materials, as observed in the skin of crocodiles and elephants. In synthetic materials, surface patterns are critical to micro- and nanoscale fabrication processes. Here, a strategy is presented that enables freely programmable patterns of cracks on the surface of a polymer and then uses these cracks to pattern other materials. Cracks form during deposition of a thin film metal on a liquid crystal polymer network (LCN) and follow the spatially patterned molecular order of the polymer. These patterned sub-micrometer scale cracks have an order parameter of 0.98 ± 0.02 and form readily over centimeter-scale areas on the flexible substrates. The patterning of the LCN enables cracks that turn corners, spiral azimuthally, or radiate from a point. Conductive inks can be filled into these oriented cracks, resulting in flexible, anisotropic, and transparent conductors. This materials-based processing approach to patterning cracks enables unprecedented control of the orientation, length, width, and depth of the cracks without costly lithography methods. This approach promises new architectures of electronics, sensors, fluidics, optics, and other devices with micro- and nanoscale features.