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.

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.

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.

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.

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.

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.

Degradation-Induced Actuation in Oxidation-Responsive Liquid Crystal Elastomers.

Stimuli-responsive materials that exhibit a mechanical response to specific biological conditions are of considerable interest for responsive, implantable medical devices. Herein, we report the synthesis, processing and characterization of oxidation-responsive liquid crystal elastomers that demonstrate programmable shape changes in response to reactive oxygen species. Direct ink writing (DIW) is used to fabricate Liquid Crystal Elastomers (LCEs) with programmed molecular orientation and anisotropic mechanical properties. LCE structures were immersed in different media (oxidative, basic and saline) at body temperature to measure in vitro degradation. Oxidation-sensitive hydrophobic thioether linkages transition to hydrophilic sulfoxide and sulfone groups. The introduction of these polar moieties brings about anisotropic swelling of the polymer network in an aqueous environment, inducing complex shape changes. 3D-printed uniaxial strips exhibit 8% contraction along the nematic director and 16% orthogonal expansion in oxidative media, while printed LCEs azimuthally deform into cones 19 times their original thickness. Ultimately, these LCEs degrade completely. In contrast, LCEs subjected to basic and saline solutions showed no apparent response. These oxidation-responsive LCEs with programmable shape changes may enable a wide range of applications in target specific drug delivery systems and other diagnostic and therapeutic tools.

Liquid crystal elastomers as substrates for 3D, robust, implantable electronics.

New device architectures favorable for interaction with the soft and dynamic biological tissue are critical for the design of indwelling biosensors and neural interfaces. For the long-term use of such devices within the body, it is also critical that the component materials resist the physiological harsh mechanical and chemical conditions. Here, we describe the design and fabrication of mechanically and chemically robust 3D implantable electronics. This is achieved by using traditional photolithography to pattern electronics on liquid crystal elastomers (LCEs), a class of shape programmable materials. The chemical durability of LCE is evaluated under accelerated in vitro conditions simulating the physiological environment; for example, LCE exhibits less than 1% mass change under a hydrolytic medium simulating >1 year in vivo. By employing twisted nematic LCEs as dynamic substrates, we demonstrate electronics that are fabricated on planar substrates but upon release morph into programmed 3D shapes. These shapes are designed to enable intrinsically low failure strain materials to be extrinsically stretchable. For example, helical multichannel cables for electrode arrays withstand cyclic stretching and buckling over 10 000 cycles at 60% strain while being soaked in phosphate-buffered saline. We envision that these LCE-based electronics can be used for applications in implantable neural interfaces and biosensors.