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.

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.

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.

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.

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.

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.

Processing advances in liquid crystal elastomers provide a path to biomedical applications.

Liquid crystal elastomers (LCEs) are a class of stimuli-responsive polymers that undergo reversible shape-change in response to environmental changes. The shape change of LCEs can be programmed during processing by orienting the liquid crystal phase prior to crosslinking. The suite of processing techniques that has been developed has resulted in a myriad of LCEs with different shape-changing behavior and mechanical properties. Aligning LCEs via mechanical straining yields large uniaxial actuators capable of a moderate force output. Magnetic fields are utilized to control the alignment within LCE microstructures. The generation of out-of-plane deformations such as bending, twisting, and coning is enabled by surface alignment techniques within thin films. 4D printing processes have emerged that enable the fabrication of centimeter-scale, 3D LCE structures with a complex alignment. The processing technique also determines, to a large extent, the potential applications of the LCE. For example, 4D printing enables the fabrication of LCE actuators capable of replicating the forces generated by human muscles. Employing surface alignment techniques, LCE films can be designed for use as coatings or as substrates for stretchable electronics. The growth of new processes and strategies opens and strengthens the path for LCEs to be applicable within biomedical device designs.

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.