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Hydrogels are often synthesized through photoinitiated step-, chain-, and mixed-mode polymerizations, generating diverse network topologies and resultant material properties that depend on the underlying network connectivity. While many photocrosslinking reactions are available, few afford controllable connectivity of the hydrogel network. Herein, a versatile photochemical strategy is introduced for tuning the structure of poly(ethylene glycol) (PEG) hydrogels using macromolecular monomers functionalized with maleimide and styrene moieties. Hydrogels are prepared along a gradient of topologies by varying the ratio of step-growth (maleimide dimerization) to chain-growth (maleimide-styrene alternating copolymerization) network-forming reactions. The initial PEG content and final network physical properties (e.g., modulus, swelling, diffusivity) are tailored in an independent manner, highlighting configurable gel mechanics and reactivity. These photochemical reactions allow high-fidelity photopatterning and 3D printing and are compatible with 2D and 3D cell culture. Ultimately, this photopolymer chemistry allows facile control over network connectivity to achieve adjustable material properties for broad applications., (© 2024 Wiley‐VCH GmbH.)

Liquid crystalline elastomers (LCEs) are anisotropic soft materials capable of large dimensional changes when subjected to a stimulus. The magnitude and directionality of the stimuli-induced thermomechanical response is associated with the alignment of the LCE. Recent reports detail the preparation of LCEs by additive manufacturing (AM) techniques, predominately using direct ink write printing. Another AM technique, digital light process (DLP) 3D printing, has generated significant interest as it affords LCE free-forms with high fidelity and resolution. However, one challenge of printing LCEs using vat polymerization methods such as DLP is enforcing alignment. Here, we document the preparation of aligned, main-chain LCEs via DLP 3D printing using a 100 mT magnetic field. Systematic examination isolates the contribution of magnetic field strength, alignment time, and build layer thickness on the degree of orientation in 3D printed LCEs. Informed by this fundamental understanding, DLP is used to print complex LCE free-forms with through-thickness variation in both spatial orientations. The hierarchical variation in spatial orientation within LCE free-forms is used to produce objects that exhibit mechanical instabilities upon heating. DLP printing of aligned LCEs opens new opportunities to fabricate stimuli-responsive materials in form factors optimized for functional use in soft robotics and energy absorption., (© 2024 Wiley‐VCH GmbH.)

Granular biomaterials have found widespread applications in tissue engineering, in part because of their inherent porosity, tunable properties, injectability, and 3D printability. However, the assembly of granular hydrogels typically relies on spherical microparticles and more complex particle geometries have been limited in scope, often requiring templating of individual microgels by microfluidics or in-mold polymerization. Here, we use dithiolane-functionalized synthetic macromolecules to fabricate photopolymerized microgels via batch emulsion, and then harness the dynamic disulfide crosslinks to rearrange the network. Through unconfined compression between parallel plates in the presence of photoinitiated radicals, we transform the isotropic microgels are transformed into disks. Characterizing this process, we find that the areas of the microgel surface in contact with the compressive plates are flattened while the curvature of the uncompressed microgel boundaries increases. When cultured with C2C12 myoblasts, cells localize to regions of higher curvature on the disk-shaped microgel surfaces. This altered localization affects cell-driven construction of large supraparticle scaffold assemblies, with spherical particles assembling without specific junction structure while disk microgels assemble preferentially on their curved surfaces. These results represent a unique spatiotemporal process for rapid reprocessing of microgels into anisotropic shapes, providing new opportunities to study shape-driven mechanobiological cues during and after granular hydrogel assembly., (© 2023 Wiley‐VCH GmbH.)

Covalent adaptable crosslinks, such as the alkyl-hydrazone, endow hydrogels with unique viscoelastic properties applicable to cell delivery and bioink systems. However, the alkyl-hydrazone crosslink lacks stability in biologically relevant environments. Furthermore, when formed with biopolymers such as hyaluronic acid (HA), low molecular weight polymers (<60 kDa), or low polymer content (<2 wt%) hydrogels are typically employed as entanglements reduce injectability. Here, a high molecular weight (>60 kDa) HA alkyl-hydrazone crosslinked hydrogel is modified with benzaldehyde-poly(ethylene glycol) 3 -azide to incorporate azide functional groups. By reacting azide-modified HA with a multi-arm poly(ethylene glycol) (PEG) functionalized with bicyclononyne, stabilizing triazole bonds are formed through strain-promoted azide-alkyne cycloaddition (SPAAC). Increasing the fraction of triazole bonds within the hydrogel network from 0% to 12% SPAAC substantially increases stability. The slow gelation kinetics of the SPAAC reaction in the 12% SPAAC hydrogel enables transient self-healing properties and a similar extrusion force as the 0% SPAAC hydrogel. Methyl-PEG 4 -hydrazide is then introduced to further slowdown network evolution, which temporarily lowers the extrusion force, improves printability, and increases post-extrusion mesenchymal stem cell viability and function in the 12% SPAAC hydrogel. This work demonstrates improved stability and temporal injectability of high molecular weight HA-PEG hydrogels for extrusion-based printing and cell delivery., (© 2024 Wiley‐VCH GmbH.)

Liquid crystalline elastomers (LCEs) are soft materials that associate order and deformation. Upon deformation, mechanically induced changes order affect entropy and can produce a caloric output (elastocaloric). Elastocaloric effects in materials continue to be considered for functional use as solid state refrigerants. Prior elastocaloric investigations of LCEs and related materials have measured ≈2 °C temperature changes upon deformation (100% strain). Here, the elastocaloric response of LCEs is explored that are prepared with a subambient nematic to isotropic transition temperature. These materials are referred as "isotropic" liquid crystalline elastomers. The LCEs are prepared by a two-step thiol-Michael/thiol-ene reaction. This polymer network chemistry enhances elastic recovery and reduces hysteresis compared to acrylate-based chemistries. The LCEs exhibit appreciable elastocaloric temperature changes upon deformation and recovery (> ± 3 °C, total ΔT of 6 °C) to deformation driven by minimal force (<< 1 MPa). Notably, the strong association of deformation and order and the resulting temperature change attained at low force achieves a responsivity of 14 °C MPa -1 which is seven times greater than natural rubber., (© 2024 Wiley‐VCH GmbH.)

Liquid crystalline elastomers (LCEs) are stimuli-responsive materials that transduce an input energy into a mechanical response. LCE composites prepared with photothermal agents, such as nanoinclusions, are a means to realize wireless, remote, and local control of deformation with light. Amongst photothermal agents, gold nanorods (AuNRs) are highly efficient converters when the irradiation wavelength matches the longitudinal surface plasmon resonance (LSPR) of the AuNRs. However, AuNR aggregation broadens the LSPR which also reduces photothermal efficiency. Here, the surface chemistry of AuNRs is engineered via a well-controlled two-step ligand exchange with a monofunctional poly(ethylene glycol) (PEG) thiol that greatly improves the dispersion of AuNRs in LCEs. Accordingly, LCE-AuNR nanocomposites with very low PEG-AuNR content (0.01 wt%) prepared by 3D printing are shown to be highly efficient photothermal actuators with rapid response (>60% strain s -1 ) upon irradiation with near-infrared (NIR; 808 nm) light. Because of the excellent dispersion of PEG-AuNR within the LCE, unabsorbed NIR light transmits through the nanocomposites and can actuate a series of samples. Further, the dispersion also allows for the optical deformation of millimeter-thick 3D printed structures without sacrificing actuation speed. The realization of well-dispersed nanoinclusions to maximize the stimulus-response of LCEs can benefit functional implementation in soft robotics or medical devices., (© 2024 Wiley‐VCH GmbH.)

The performance of robotic systems can benefit from low-density material actuators that emulate muscle typology (e.g., fast and slow twitch) of natural systems. Recent reports detail the thermomechanical, chemical, electrical, and pneumatic response of twisted and coiled fibers. The geometrical constraints imparted on typically commodity materials realize distinguished stimuli-induced actuation including low density, high force, and moderate stroke. Here, actuators are prepared by twisting fibers composed of liquid crystal elastomers (LCEs). The actuators combine the inherent stimuli-response of LCEs with the geometrical constraints of twisted fiber actuators to dramatically increase the deformation rate, specific work, and achievable force output. In some geometries, the thermomechanical response of the LCE exhibits a pseudo-first-order transition., (© 2024 Wiley‐VCH GmbH.)

The ability of cells to organize into tissues with proper structure and function requires the effective coordination of proliferation, migration, polarization, and differentiation across length scales. Skeletal muscle is innately anisotropic; however, few biomaterials can emulate mechanical anisotropy to determine its influence on tissue patterning without introducing confounding topography. Here, we demonstrate that substrate stiffness anisotropy coordinates contractility-driven collective cellular dynamics resulting in C2C12 myotube alignment over millimeter-scale distances. When cultured on mechanically anisotropic liquid crystalline polymer networks (LCNs) lacking topography, C2C12 myoblasts collectively polarize in the stiffest direction. Cellular coordination is amplified through reciprocal cell-ECM dynamics that emerge during fusion, driving global myotube-ECM ordering. Conversely, myotube alignment was restricted to small local domains with no directional preference on mechanically isotropic LCNs of the same chemical formulation. These findings provide valuable insights for designing biomaterials that mimic anisotropic microenvironments and underscore the importance of stiffness anisotropy in orchestrating tissue morphogenesis.

Thermochromic materials have found widespread commercial use in packaging as temperature indicators. Often, these products utilize leuco dyes that are mixed into conventional polymeric resins to prepare coatings or films that exhibit temperature-dependent color change. Here, we consider a distinctive approach to thermochromism via the selective reflection of liquid crystalline elastomers that retain the helicoidal structure of the cholesteric phase (CLCEs). Upon heating, the order of the CLCEs reduces and approaches zero, resulting in a change in birefringence as well as material thickness, both of which manifest as changes in the selective reflection to heating. This examination systematically prepares CLCEs capable of reversible thermochromic response as a function of cross-link density and liquid crystalline composition. A particular focus of this examination is the preparation of CLCEs composed of chiral and achiral liquid crystalline monomers that reduce the strength of the mesogen-mesogen interaction and accordingly reduce the nematic-isotropic transition temperature. The low birefringence of some of the CLCE compositions facilitates thermochromic reflection tuning, followed by switching.

Polymer stabilized cholesteric liquid crystals (PSCLCs) are electrically reconfigurable reflective elements. Prior studies have hypothesized and indirectly confirmed that the electro-optic response of these composites is associated with the electrically mediated distortion of the stabilizing polymer network. The proposed mechanism is based on the retention of structural chirality in the polymer stabilizing network, which upon deformation is spatially distorted, which accordingly affects the pitch of the surrounding low molar-mass liquid crystal host. Here, we utilize fluorescent confocal polarized microscopy to directly assess the electro-optic response of PSCLCs. By utilizing dual fluorescent probes, sequential imaging experiments confirm that the periodicity of the polymer stabilizing network matches that of the low molar-mass liquid crystal host. Further, we isolate distinct ion-polymer interactions that manifest in certain photopolymerization conditions.

Pressure-sensitive adhesives (PSAs) are widely employed in consumer goods, health care, and commercial industry. Anisotropic adhesion of PSAs is often desirable to enable high force capacity coupled with facile release and has typically been realized through the introduction of complex surface and/or bulk microstructures while also maintaining high surface conformability. Although effective, microstructure fabrication can add cost and complexity to adhesive fabrication. Here, we explore aligned liquid crystalline elastomers (LCEs) as directional adhesives. Aligned LCEs exhibit direction-dependent stiffness, dissipation, and nonlinear deformation under load. By varying the cross-link content, we study how the bulk mechanical properties of LCEs correlate to their peel strength and peel anisotropy. We demonstrate up to a 9-fold difference in peel force measured when the LCE is peeled parallel vs perpendicular to the alignment axis. Opportunities to spatially localize adhesion are presented in a monolithic LCE patterned with different director orientations.

Oligomers prepared by chain extension of liquid crystalline monomers are thermotropic. The alignment of liquid crystalline oligomers to shear flow via direct ink write printing is an increasingly popular approach to prepare aligned and 3-D printed liquid crystalline elastomers (LCEs). Here, we are concerned with the contribution of order and thermal history on the rheological properties of liquid crystalline. When the oligomers begin in a polydomain nematic state, the transition to an aligned nematic state occurs gradually over a wide range of shear rates. Conversely, when the oligomers begin in an isotropic state they behave as a Newtonian fluid until a critical shear rate is reached, at which point they align in a critical manner. It is shown that by either decreasing liquid crystalline content or increasing temperature, the viscosity of the oligomer melt decreases while this critical shear rate increases. In addition, the normal stress of oligomers is positive over all shear rates but decreases significantly in magnitude with increasing temperature. By combining the analysis of both temperature and liquid crystalline content, it is demonstrated that the temperature relative to the nematic-isotropic transition temperature is key to the oligomers' unique flow behaviors.

Liquid crystal elastomer films that morph into cones are strikingly capable lifters. Thus motivated, we combine theory, numerics, and experiments to reexamine the load-bearing capacity of conical shells. We show that a cone squashed between frictionless surfaces buckles at a smaller load, even in scaling, than the classical Seide-Koiter result. Such buckling begins in a region of greatly amplified azimuthal compression generated in an outer boundary layer with oscillatory bend. Experimentally and numerically, buckling then grows subcritically over the full cone. We derive a new thin-limit formula for the critical load, ∝t^{5/2}, and validate it numerically. We also investigate deep postbuckling, finding further instabilities producing intricate states with multiple Pogorelov-type curved ridges arranged in concentric circles or Archimedean spirals. Finally, we investigate the forces exerted by such states, which limit lifting performance in active cones.

Electrocatalytic synthesis under mild conditions has become increasingly important as one of the practical alternatives for industrial applications, especially for the green ammonia (NH 3 ) industry. A properly engineered electrocatalyst plays a vital role in the realization of superior catalytic performance. Among various types of promising nanomaterials, metal-organic frameworks (MOFs) are competitive candidates for developing efficient electrocatalytic NH 3 synthesis from simple nitrogen-containing molecules or ions, such as N 2 and NO 3 - . In this review, recent advances in the development of electrocatalysts derived from MOFs for the electrosynthesis of NH 3 are collected, categorized, and discussed, including their application in the N 2 reduction reaction (NRR) and the NO 3 - reduction reaction (NO 3 RR). Firstly, the fundamental principles are illustrated, such as plausible mechanisms of NH 3 generation from N 2 and NO 3 - , the apparatus of corresponding electrocatalysis, parameters for evaluation of reaction efficiency, and detection methods of yielding NH 3 . Then, the electrocatalysts for NRR processes are discussed in detail, including pristine MOFs, MOF-hybrids, MOF-derived N-doped porous carbons, single atomic catalysts from pyrolysis of MOFs, and other MOF-related materials. Subsequently, MOF-related NO 3 RR processes are also listed and discussed. Finally, the existing challenges and prospects for the rational design and fabrication of electrocatalysts from MOFs for electrochemical NH 3 synthesis are presented, such as the evolution of investigation methods with artificial intelligence, innovation in synthetic methods of MOF-related catalysts, advancement of characterization techniques, and extended electrocatalytic reactions., (© 2023. Shanghai Jiao Tong University.)

Polymer stabilization of cholesteric liquid crystals can enable dynamic reconfiguration of the selective reflection of the CLC phase. Here, we explore how the contribution of the elasticity of the polymer stabilizing network affects the ion-mediated, electromechanical deformation and associated electro-optic response in PSCLCs. We utilize a free-radical chain transfer reaction between acrylate and thiol monomers that has been used to prepare elastomeric networks. This work maps the compositional contributions of total concentration and crosslink density to tuning and recovery.

Liquid crystalline elastomers (LCEs) are shape-changing materials that exhibit large deformations in response to applied stimuli. Local control of the orientation of LCEs spatially directs the deformation of these materials to realize a spontaneous shape change in response to stimuli. Prior approaches to shape programming in LCEs utilize patterning techniques that involve the detailed inscription of spatially varying nematic fields to produce sheets. These patterned sheets deform into elaborate geometries with complex Gaussian curvatures. Here, we present an alternative approach to realize shape-morphing in LCEs where spatial patterning of the crosslink density locally regulates the material deformation magnitude on either side of a prescribed interface curve. We also present a simple mathematical model describing the behavior of these materials. Further experiments coupled with the mathematical model demonstrate the control of the sign of Gaussian curvature, which is used in combination with heat transfer effects to design LCEs that self-clean as a result of temperature-dependent actuation properties.

The anisotropy of liquid crystalline elastomers (LCEs) is derived from the interaction-facilitated orientation of the molecular constituents. Here, we correlate the thermomechanical response of a series of LCEs subjected to mechanical alignment to measurements of the Hermans orientation parameter. The LCEs were systematically prepared with varying concentrations of liquid crystalline mesogens, which affects the relative degree of achievable order. These compositions were subject to varying degrees of mechanical alignment to prepare LCEs with orientations that span a wide range of orientation parameters. The stimuli-response of the LCEs indicates that the liquid crystalline content defines the temperature of actuation, whereas the orientation parameter of the LCE is intricately correlated to both the total actuation strain of the LCE as well as the rate of thermomechanical response.

The large, directional stimuli-response of aligned liquid crystalline elastomers (LCEs) could enable functional utility in robotics, medicine, consumer goods, and photonics. The alignment of LCEs has historically been realized via mechanical alignment of a two-stage reaction. Recent reports widely utilize chain extension reactions of liquid crystal monomers (LCM) to form LCEs that are subject to either surface-enforced or mechanical alignment. Here, we prepare LCEs that contain intra-mesogenic supramolecular bonds synthesized via direct free-radical chain transfer photopolymerization processible by a distinctive mechanical alignment mechanism. The LCEs were prepared by the polymerization of a benzoic acid monomer (11OBA), which dimerized to form a liquid crystal monomer, with a diacrylate LCM (C6M). The incorporation of the intra-mesogenic hydrogen bonds increases the achievable nematic order from mechanical programming. Accordingly, LCEs prepared with larger 11OBA concentration exhibit higher magnitude thermomechanical strain values when compared to a LCE containing only covalent bonds. These LCEs can be reprogrammed with heat to return the aligned film to the polydomain state. The LCE can then be subsequently programmed to orient in a different direction. The facile preparation of (re)programmable LCEs with supramolecular bonds opens new avenues for the implementation of these materials as shape deployable elements.

Snap-through mechanisms are pervasive in everyday life in biological systems, engineered devices, and consumer products. Snap-through transitions can be realized in responsive materials via stimuli-induced mechanical instability. Here, we demonstrate a rapid and powerful snap-through response in liquid crystalline elastomers (LCEs). While LCEs have been extensively examined as material actuators, their deformation rate is limited by the second-order character of their phase transition. In this work, we locally pattern the director orientation of LCEs and fabricate mechanical elements with through-thickness (functionally graded) modulus gradients to realize stimuli-induced responses as fast as 6 ms. The rapid acceleration and associated force output of the LCE elements cause the elements to leap to heights over 200 times the material thickness. The experimental examination in functionally graded LCE elements is complemented with computational evaluation of the underlying mechanics. The experimentally validated model is then exercised as a design tool to guide functional implementation, visualized as directional leaping.

Perovskite-related materials show very promising properties in many fields. Pb-free perovskites are particularly interesting, because of the toxicity of Pb. In this study, hybrid double perovskite MA 2 KBiCl 6 (MA = methylammonium cation) was found to have interesting variable temperature behaviours. Both variable temperature single crystal X-ray diffraction, synchrotron powder diffraction, and Raman spectroscopy were conducted to reveal a rhombohedral to cubic phase transition at around 330 K and an order to disorder transition for inorganic cage below 210 K.

Liquid crystalline elastomers (LCEs) are stimuli-responsive materials capable of undergoing large deformations. The thermomechanical response of LCEs is attributable to the coupling of polymer network properties and disruption of order between liquid crystalline mesogens. Complex deformations have been realized in LCEs by either programming the nematic director via surface-enforced alignment or localized mechanical deformation in materials incorporating dynamic covalent chemistries. Here, the preparation of LCEs via thiol-Michael addition reaction is reported that are amenable to surface-enforced alignment. Afforded by the thiol-Michael addition reaction, dynamic covalent bonds are uniquely incorporated in chemistries subject to surface-enforce alignment. Accordingly, LCEs prepared with complex director profiles are able to be programmed and reprogrammed by (re)activating the dynamic covalent chemistry to realize distinctive shape transformations., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Granular synthetic hydrogels are useful bioinks for their compatibility with a variety of chemistries, affording printable, stimuli-responsive scaffolds with programmable structure and function. Additive manufacturing of microscale hydrogels, or microgels, allows for the fabrication of large cellularized constructs with percolating interstitial space, providing a platform for tissue engineering at length scales that are inaccessible by bulk encapsulation where transport of media and other biological factors are limited by scaffold density. Herein, synthetic microgels with varying degrees of degradability are prepared with diameters on the order of hundreds of microns by submerged electrospray and UV photopolymerization. Porous microgel scaffolds are assembled by particle jamming and extrusion printing, and semi-orthogonal chemical cues are utilized to tune the void fraction in printed scaffolds in a logic-gated manner. Scaffolds with different void fractions are easily cellularized post printing and microgels can be directly annealed into cell-laden structures. Finally, high-throughput direct encapsulation of cells within printable microgels is demonstrated, enabling large-scale 3D culture in a macroporous biomaterial. This approach provides unprecedented spatiotemporal control over the properties of printed microporous annealed particle scaffolds for 2.5D and 3D tissue culture., (© 2022 Wiley-VCH GmbH.)

Liquid crystal elastomers (LCE) are an emerging class of material actuators. LCE undergo macroscopic dimensional changes when subjected to a stimulus. The large stimuli-response of LCE is associated with thermotropic disruption of order. Historically, comparatively high temperatures are required to disrupt orientation in LCE to achieve meaningful work output. Here, we introduce an approach to prepare LCE via thiol-Michael/thiol-ene reactions that actuate at or below ambient temperature. Alignment was imparted to the LCE by mechanical alignment and 3D printing. The LCE materials detailed here achieve strains of 40 % with a maximum deformation rate of 6.5 % °C -1 . The functional utility of the tunability of the thermotropic response of these materials is illustrated in reconfiguration triggered via body heat and sequential actuation of a multi-material element., (© 2022 Wiley-VCH GmbH.)

Liquid crystal elastomers (LCEs) are stimuli-responsive materials that undergo large shape transformations after undergoing an order-disorder transition. While shape reconfigurations in LCEs are predominantly triggered by heat, there is a considerable interest in developing highly specific triggers that work at room temperature. Herein, we report the fabrication of biocatalytic LCEs that respond to the presence of urea by covalently immobilizing urease within chemically responsive LCE networks. The hydrogen-bonded LCEs developed in this work exhibited contractile strains of up to 36% upon exposure to a base. Notably, the generation of ammonia by immobilized urease triggered a disruption in the supramolecular network and a large reduction of liquid crystalline order in the films when the LCEs were exposed to urea. This reduction in order was macroscopically translated into a strain response that could be modulated by changing the concentration of urea or exposure time to the substrate. Local control of the mechanical response of the LCE was realized by spatially patterning the enzyme on the surface of the films. Subsequent exposure of enzymatically patterned LCE to urea-triggered 3D shape transformations into a curl, arch, or accordion-like structure, depending on the motif patterned on the film surface. Furthermore, we showed that the presence of salt was critical to prevent bridging of the network by the presence of ammonium ions, thereby enabling such macroscopic 3D shape changes. The large actuation potential of LCEs and the ability to translate the biocatalytic activity of enzymes to macroscopic 3D shape transformations could enable use in applications ranging from cell culture, medicine, or antifouling.

Liquid crystalline monomers can be oligomerized and subsequently 3-D printed to prepare liquid crystalline elastomers (LCEs) with spatial variation of the nematic director to create soft materials that undergo complex shape change when subject to stimulus. Here, we detail the correlation of alignment in 3-D printed LCE on the shear history of the oligomeric ink. This coupling is evident both in the polymerization of sheared LCE samples as well as steady-state rheological experiments that quantify the time-dependent flow behaviors of these complex fluids. Under a steady shear flow, oligomeric LC inks transition from a nematic state with unaligned (polydomain) orientation to a uniaxially aligned (monodomain) nematic phase over a large range of applied strain. After cessation of shear flow, the oligomeric LC inks return the polydomain orientation over approximately 30 minutes. The alignment of liquid crystalline segments in the LCE (and the associated stimuli-response of the materials) is ultimately correlated to the degree of strain applied to the ink.

Extensive prior research has explored the stabilization of the CLC phase with polymer networks. These prior efforts have demonstrated both tunable and switchable electro-optic reconfiguration of the selective reflection of the CLC phase. Recently, we and other groups have detailed that polymer stabilization of the CLC phase with liquid crystalline monomers retains "structural" chirality ( e.g. , the chiral phase templates the morphology of the achiral polymer network). Here, we demonstrate that structural chirality can be retained in aliphatic, non-liquid crystalline monomers. PSCLCs prepared by photoinitiated polymerization of aliphatic polymer networks exhibit reversible electro-optic responses. Facilitated by the retention of structural chirality in aliphatic stabilizing polymer networks, we explore the role of surface affinity and crosslink density in the transfer of structural chirality to the liquid crystal media.

Diarylethene-functionalized liquid-crystalline elastomers (DAE-LCEs) containing thiol-anhydride bonds were prepared and shown to undergo reversible, reprogrammable photoinduced actuation. Upon exposure to UV light, a monodomain DAE-LCE generated 5.5 % strain. This photogenerated strain was demonstrated to be optically reversible over five cycles of alternating UV/Visible light exposure with minimal photochrome fatigue. The incorporation of thiol-anhydride dynamic bonds allowed for retention of actuated states. Further, re-programming of the nematic director was achieved by heating above the temperature for bond exchange to occur (70 °C) yet below the nematic-to-isotropic transition temperature (100 °C) such that order was maintained between mesogens. The observed thermal stability of each of the diarylethene isomers of over 72 h allowed for decoupling of photo-induced processes and polymer network effects, showing that both polymer relaxation and back-isomerization of the diarylethene contributed to LCE relaxation over a period of 12 hours after actuation unless bond exchange occurred., (© 2022 Wiley-VCH GmbH.)

Liquid crystal polymer networks (LCNs) are stimuli-responsive materials that can be programmed to realize spatial variation in mechanical response and undergo shape transformation. Herein, we report a process to introduce chemical specificity to the stimuli response of LCNs by integrating enzymes as molecular triggers. Specifically, the enzyme urease was immobilized in LCN films via acyl fluoride conjugation chemistry. Activity assays and confocal fluorescence imaging confirmed retention of urease activity after immobilization as well as widespread distribution of enzyme on the film. The addition of urea triggered a response in the LCN whereby newly generated ammonia reacted with free acyl fluorides to form benzamide moieties. These moieties were capable of dimerizing through the formation of supramolecular hydrogen bonds, which was reflected in a 4-fold increase in Young's modulus. Through dynamic mechanical analysis and calorimetry, we further confirmed that the degree of hydrogen bonding in the LCNs could be judiciously designed to fine-tune the mechanical properties and glass transition temperature. These findings demonstrate the untapped potential of biochemical mechanisms as molecular triggers in LCNs and open the door to the use of nucleophilic chemistries in modulating the mechanical properties of LCNs.

The integration of soft, stimuli-responsive materials in robotic systems is a promising approach to introduce dexterous and delicate manipulation of objects. Electrical control of mechanical response offers many benefits in robotic systems including the availability of this energy input, the associated response time, magnitude of actuation, and opportunity for self-regulation. Here, a materials chemistry is detailed to prepare liquid crystal elastomers (LCEs) with a 14:1 modulus contrast and increase in dielectric constant to enhance electromechanical deformation. The inherent modulus contrast of these LCEs (when coated with compliant electrodes) directly convert an electric field to a directional expansion of 20%. The electromechanical response of LCE actuators is observed upon application of voltage ranging from 0.5 to 6 kV. The deformation of these materials is rapid, reaching strain rates of 18% s -1 . Upon removal of the electric field, little hysteresis is observed. Patterning the spatial orientation of the nematic director of the LCEs results in a 2D-3D shape transformation to a cone 8 mm in height. Individual and sequential addressing of an array of LCE actuators is demonstrated as a haptic surface., (© 2021 Wiley-VCH GmbH.)

The blue phases are observed in highly chiral liquid crystalline compositions that nascently organize into a three-dimensional, crystalline nanostructure. The periodicity of the unit cell lattice spacing is on the order of the wavelength of visible light and accordingly, the blue phases exhibit a selective reflection as a photonic crystal. Here, we detail the synthesis of liquid crystalline elastomers that retain blue phase I, blue phase II, and blue phase III. The mechanical properties and optical reconfiguration via deformation of retained blue phases are contrasted to the cholesteric phase in fully solid elastomers with glass transition temperatures below room temperature. Mechanical deformation and chemical swelling of the lightly crosslinked polymer networks induces lattice asymmetry in the blue phase evident in the tuning of the selective reflection. The lattice periodicity of the blue phase elastomer is minimally affected by temperature. The oblique lattice planes of the blue phase tilt and red-shift in response to mechanical deformation. The retention of the blue phases in fully solid, elastomeric films could enable functional implementations in photonics, sensing, and energy applications., (© 2021. The Author(s).)

Machines are systems that harness input power to extend or advance function. Fundamentally, machines are based on the integration of materials with mechanisms to accomplish tasks-such as generating motion or lifting an object. An emerging research paradigm is the design, synthesis, and integration of responsive materials within or as machines. Herein, a particular focus is the integration of responsive materials to enable robotic (machine) functions such as gripping, lifting, or motility (walking, crawling, swimming, and flying). Key functional considerations of responsive materials in machine implementations are response time, cyclability (frequency and ruggedness), sizing, payload capacity, amenability to mechanical programming, performance in extreme environments, and autonomy. This review summarizes the material transformation mechanisms, mechanical design, and robotic integration of responsive materials including shape memory alloys (SMAs), piezoelectrics, dielectric elastomer actuators (DEAs), ionic electroactive polymers (IEAPs), pneumatics and hydraulics systems, shape memory polymers (SMPs), hydrogels, and liquid crystalline elastomers (LCEs) and networks (LCNs). Structural and geometrical fabrication of these materials as wires, coils, films, tubes, cones, unimorphs, bimorphs, and printed elements enables differentiated mechanical responses and consistently enables and extends functional use., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

It has previously been shown that for polymer-stabilized cholesteric liquid crystals (PSCLCs) with negative dielectric anisotropy, the position and bandwidth of the selective reflection notch can be controlled by a direct-current (DC) electric field. The field-induced deformation of the polymer network that stabilizes the devices is mediated by ionic charges trapped in or near the polymer. A unique and reversible electro-optic response is reported here for relatively thin films (≤5 μm). Increasing the DC field strength redshifts the reflection notch to longer wavelength until the reflection disappears at high DC fields. The extent of the tuning range is dependent on the cell thickness. The transition from the reflective to the clear state is due to the electrically controlled, chirped pitch across the small cell gap and not to the field-induced reorientation of the liquid crystal molecules themselves. The transition is reversible. By adjusting the DC field strength, various reflection wavelengths can be addressed from either a different reflective (colored) state at 0 V or a transparent state at a high DC field. Relatively fast responses (~50 ms rise times and ~200 ms fall times) are observed for these thin PSCLCs.

Programming the local orientation of liquid crystal elastomers (LCEs) is a differentiated approach to prepare monolithic material compositions with localized deformation. Our prior efforts prepared LCEs with surface-enforced spatial variations in orientation to localize deformation when the LCEs were subjected to directional load. However, because these surface alignment methods included regions of planar orientation, the deformation of these programmed LCEs is inherently directional. The absence of macroscopic orientation in polydomain LCEs results in uniform, nonlinear deformation in all axes (omnidirectional soft elasticity). Here, we exploit the distinct mechanical response of polydomain LCEs prepared with isotropic or nematic genesis. By localizing the polydomain genesis via masked photopolymerizations conducted at different temperatures, we detail the preparation of main-chain, polydomain LCEs that are homogeneous in composition but exhibit spatially localized programmability in their mechanical response that is uniform in all directions.

Vanadium dioxide, a well-known phase transition material with abrupt resistance change during its transition temperature, is herein used to fabricate the transparent mesh film onto a glass slide through self-assembly mesh printing. A record high ON/OFF ratio up to 10 4 is achieved together with high visible transmittance of 86% compared to the normal glass slide with visible transmittance at 88%. The high transparent properties make the resistive switches applicable for next-generation electronics, such as see-through computing device and beyond. A simple and scalable mesh printing approach-integrated phase change material may provide a promising way to fabricate transparent resistance switches for next-generation electronics., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

Liquid crystal elastomers (LCEs) are anisotropic polymeric materials. When subjected to an applied stress, liquid crystalline (LC) mesogens within the elastomeric polymer network (re)orient to the loading direction. The (re)orientation during deformation results in nonlinear stress-strain dependence (referred to as soft elasticity). Here, we uniquely explore mechanotropic phase transitions in elastomers with appreciable mesogenic content and compare these responses to LCEs in the polydomain orientation. The isotropic (amorphous) elastomers undergo significant directional orientation upon loading, evident in strong birefringence and x-ray diffraction. Functionally, the mechanotropic displacement of the elastomers to load is also nonlinear. However, unlike the analogous polydomain LCE compositions examined here, the isotropic elastomers rapidly recover after deformation. The mechanotropic orientation of the mesogens in these materials increase the toughness of these thiol-ene photopolymers by nearly 1300 % relative to a chemically similar elastomer prepared from wholly isotropic precursors., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The hybrid nature and soft lattice of organolead halide perovskites render their structural changes and optical properties susceptible to external driving forces such as temperature and pressure, remarkably different from conventional semiconductors. Here, we investigate the pressure-induced optical response of a typical two-dimensional perovskite crystal, phenylethylamine lead iodide. At a moderate pressure within 3.5 GPa, its photoluminescence red-shifts continuously, exhibiting an ultrabroad energy tunability range up to 320 meV in the visible spectrum, with quantum yield remaining nearly constant. First-principles calculations suggest that an out-of-plane quasi-uniaxial compression occurs under a hydrostatic pressure, while the energy is absorbed by the reversible and elastic tilting of the benzene rings within the long-chain ligands. This anisotropic structural deformation effectively modulates the quantum confinement effect by 250 meV via barrier height lowering. The broad tunability within a relatively low pressure range will expand optoelectronic applications to a new paradigm with pressure as a tuning knob.

Copper-doped hydroxyapatite (HA) of nominal composition Ca 10 (PO 4 ) 6 [Cu x (OH) 2-2x O x ] (0.0 ≤ x ≤ 0.8) was prepared by solid-state and wet chemical processing to explore the impact of the synthesis route and mode of crystal chemical incorporation of copper on the antibacterial efficacy against Escherichia coli ( E. coli ) and Staphylococcus aureus ( S. aureus ) strains. Apatites prepared by solid-state reaction showed unit cell volume dilation from 527.17 Å 3 for copper-free HA to 533.31 Å 3 for material of the putative composition Ca 10 (PO 4 ) 6 [Cu 0.8 (OH) 0.4 O 0.8 ] consistent with Cu + insertion into the [001] hydroxyapatite channel. This was less pronounced (528.30 Å 3 to 529.3 Å 3 ) in the corresponding wet chemical synthesised products, suggesting less complete Cu tunnel incorporation and partial tenancy of Cu in place of calcium. X-ray absorption spectroscopy suggests fast quenching is necessary to prevent oxidation of Cu + to Cu 2+ . Raman spectroscopy revealed an absorption band at 630 cm -1 characteristic of symmetric O-Cu + -O units tenanted in the apatite channel while solid-state 31 P magic-angle-spinning nuclear magnetic resonance (MAS NMR) supported a vacancy-Cu + substitution model within the apatite channel. The copper doping strategy increases antibacterial efficiency by 25% to 55% compared to undoped HA, with the finer particle sizes and greater specific surface areas of the wet chemical material demonstrating superior efficacy.

Materials that can be switched between low and high thermal conductivity states would advance the control and conversion of thermal energy. Employing in situ time-domain thermoreflectance (TDTR) and in situ synchrotron X-ray scattering, we report a reversible, light-responsive azobenzene polymer that switches between high (0.35 W m -1 K -1 ) and low thermal conductivity (0.10 W m -1 K -1 ) states. This threefold change in the thermal conductivity is achieved by modulation of chain alignment resulted from the conformational transition between planar ( trans ) and nonplanar ( cis ) azobenzene groups under UV and green light illumination. This conformational transition leads to changes in the π-π stacking geometry and drives the crystal-to-liquid transition, which is fully reversible and occurs on a time scale of tens of seconds at room temperature. This result demonstrates an effective control of the thermophysical properties of polymers by modulating interchain π-π networks by light., Competing Interests: The authors declare no conflict of interest.

Resolving the structure-property relationships of two-dimensional (2D) organic-inorganic hybrid perovskites is essential for the development of photovoltaic and photoelectronic devices. Here, pressure (0-10 GPa) was applied to 2D hybrid perovskite flakes mechanically exfoliated from butylammonium lead halide single crystals, (C 4 H 9 NH 3 ) 2 PbI 4 , from which we observed a series of changes of the strong excitonic emissions in the photoluminescence spectra. By correlating with in situ high-pressure X-ray diffraction results, we examine successfully the relationship between structural modifications in the inorganic PbI 4 2- layer and their excitonic properties. During the transition between Pbca (1b) phase and Pbca (1a) phase at around 0.1 GPa, the decrease in ⟨Pb-I-Pb⟩ bond angle and increase in Pb-I bond length lead to an abrupt blue shift of the excitonic bandgap. The presence of the P2 1 /a phase above 1.4 GPa increases the ⟨Pb-I-Pb⟩ bond angle and decreases the Pb-I bond length, leading to a deep red shift of the excitonic bandgap. The total band gap narrowing of ∼350 meV to 2.03 eV at 5.3 GPa before amorphization, facilitates (C 4 H 9 NH 3 ) 2 PbI 4 as a much better solar absorber. Moreover, phase transitions inevitably modify the carrier lifetime of (C 4 H 9 NH 3 ) 2 PbI 4 , where an initial 150 ps at ambient phase is prolongated to 190 ps in the Pbca (1a) phase along with enhanced photoluminescence (PL), originating from pressure-induced strong radiative recombination of trapped excitons.The onset of P2 1 /a phase shortens significantly the carrier lifetime to 53 ps along with a weak PL emission due to pressure-induced severe lattice distortion and amorphization. High-pressure study on (C 4 H 9 NH 3 ) 2 PbI 4 nm-thin flakes may provide insights into the mechanisms for synthetically designing novel 2D hybrid perovskite based photoelectronic devices and solar cells.

Photoresponsive liquid crystal elastomers (LCEs) are a unique class of anisotropic materials capable of undergoing large-scale, macroscopic deformations when exposed to light. Here, surface-aligned, azobenzene-functionalized LCEs are prepared via a radical-mediated, thiol-acrylate chain transfer reaction. A long-lived, macroscopic shape deformation is realized in an LCE composed with an o-fluorinated azobenzene (oF-azo) monomer. Under UV irradiation, the oF-azo LCE exhibits a persistent shape deformation for >72 h. By contrasting the photomechanical response of the oF-azo LCE to analogs prepared from classical and m-fluorinated azobenzene derivatives, the origin of the persistent deformation is clearly attributed to the underlying influence of positional functionalization on the kinetics of cis→trans isomerization. Informed by these studies and enabled by the salient features of light-induced deformations, oF-azo LCEs are demonstrated to undergo all-optical control of shape deformation and shape restoration., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Electrical control of the pitch has been reported in a variant of the cholesteric liquid crystal phase composed of chiral dopants and liquid crystal dimers with a bent conformation, such as CB7CB. For a finite range of applied electric field, the dimeric mesogens assume an oblique helicoidal structure, in which the helical axis is aligned along the electric field and the local director is tilted towards the helical axis (rather than being perpendicular to it). An electric field can directly regulate the periodicity (pitch), allowing reconfiguration of the optical response from a scattering or transparent state to a reflective state. Here, we employ po stabilization to retain the oblique helicoidal state absent an applied field. The polymer stabilized oblique helicoidal structures were investigated under various conditions and material compositions. With polymer stabilization, the magnitude of the selective reflection is found to be dependent on the strength of the applied field. Comparison of the electro-optical response of samples with and without a polymer network elucidates the relative role of boundary conditions, anchoring strength, and elastic energy on the stability of the oblique helicoidal state.

The pressure-induced structural evolution of formamidinium-based perovskite FAPbI 3 was investigated using in situ synchrotron X-ray diffraction and laser-excited photoluminescence methods. Cubic α-FAPbI 3 ( Pm3̅ m) partially and irreversibly transformed to hexagonal δ-FAPbI 3 ( P6 3 mc) at a pressure less than 0.1 GPa. Structural transitions of α-FAPbI 3 followed the sequence of Pm3̅ m → P4/ mbm → Im3̅ → partial amorphous during compression to 6.59 GPa, whereas the δ-phase converted to an orthorhombic Cmc2 1 structure between 1.26 and 1.73 GPa. During decompression, FAPbI 3 recovered the P6 3 mc structure of the δ-phase as a minor component (∼18 wt %) from 2.41-1.40 GPa and the Pm3̅ m structure of the α-phase becomes dominant (∼82 wt %) at 0.10 GPa but with an increased fraction of δ-FAPbI 3 . The photoluminescence behaviors from both the α- and δ-forms were likely controlled by radiative recombination at the defect levels rather than band-edge emission during pressure cycling. FAPbI 3 polymorphism is exquisitely sensitive to pressure. While modest pressures can engineer FAPbI 3 -based photovoltaic devices, irreversible δ-phase crystallization may be a limiting factor and should be taken into account.

The reversible, ultrafast, and multistimuli responsive phase transition of vanadium dioxide (VO 2 ) makes it an intriguing "smart" material. Its crystallographic transition from the monoclinic to tetragonal phases can be triggered by diverse stimuli including optical, thermal, electrical, electrochemical, mechanical, or magnetic perturbations. Consequently, the development of high-performance smart devices based on VO 2 grows rapidly. This review systematically summarizes VO 2 -based emerging technologies by classifying different stimuli (inputs) with their corresponding responses (outputs) including consideration of the mechanisms at play. The potential applications of such devices are vast and include switches, memories, photodetectors, actuators, smart windows, camouflages, passive radiators, resonators, sensors, field effect transistors, magnetic refrigeration, and oscillators. Finally, the challenges of integrating VO 2 into smart devices are discussed and future developments in this area are considered., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Liquid crystalline elastomers (LCEs) are widely recognized for their exceptional promise as actuating materials. Here, the comparatively less celebrated but also compelling nonlinear response of these materials to mechanical load is examined. Prior examinations of planarly aligned LCEs exhibit unidirectional nonlinear deformation to mechanical loads. A methodology is presented to realize surface-templated homeotropic orientation in LCEs and omnidirectional nonlinearity in mechanical deformation. Inkjet printing of the homeotropic alignment surface localizes regions of homeotropic and planar orientation within a monolithic LCE element. The local control of the self-assembly and orientation of the LCE, when subject to rational design, yield functional materials continuous in composition with discontinuous mechanical deformation. The variation in mechanical deformation in the film can enable the realization of nontrivial performance. For example, a patterned LCE is prepared and shown to exhibit a near-zero Poisson's ratio. Further, it is demonstrated that the local control of deformation can enable the fabrication of rugged, flexible electronic devices. An additively manufactured device withstands complex mechanical deformations that would normally cause catastrophic failure., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Liquid crystalline elastomers (LCEs) are soft, anisotropic materials that exhibit large shape transformations when subjected to various stimuli. Here we demonstrate a facile approach to enhance the out-of-plane work capacity of these materials by an order of magnitude, to nearly 20 J/kg. The enhancement in force output is enabled by the development of a room temperature polymerizable composition used both to prepare individual films, organized via directed self-assembly to retain arrays of topological defect profiles, as well as act as an adhesive to combine the LCE layers. The material actuator is shown to displace a load >2500× heavier than its own weight nearly 0.5 mm.

Nematic elastomers dramatically change their shape in response to diverse stimuli including light and heat. In this paper, we provide a systematic framework for the design of complex three dimensional shapes through the actuation of heterogeneously patterned nematic elastomer sheets. These sheets are composed of nonisometric origami building blocks which, when appropriately linked together, can actuate into a diverse array of three dimensional faceted shapes. We demonstrate both theoretically and experimentally that the nonisometric origami building blocks actuate in the predicted manner, and that the integration of multiple building blocks leads to complex, yet predictable and robust, shapes. We then show that this experimentally realized functionality enables a rich design landscape for actuation using nematic elastomers. We highlight this landscape through examples, which utilize large arrays of these building blocks to realize a desired three dimensional origami shape. In combination, these results amount to an engineering design principle, which provides a template for the programming of arbitrarily complex three dimensional shapes on demand.

Reconfigurable optical materials are critical to realizing light control in eyewear or architectural windows. Here, we report on the electrical reconfiguration of the selective reflection of cholesteric liquid crystals (LCs). The distinctive responses detailed here are enabled by the preparation of a structurally chiral polymer stabilizing network that enforces anchoring of a low-molar-mass liquid crystalline media with positive dielectric anisotropy. The pitch of the reflective optical elements is directly regulated by a dc field, resulting in red or blue reflection wavelength tuning or broadening. The use of the positive dielectric LC host in concert with optimization of the material preparation conditions allows for reorientation of the LC molecules to achieve an optically clear state (homeotropic orientation) by the application of an ac field. In this way, the selective reflection of the optical elements can be moved, widened, and turned on and off. The electro-optic characteristics of these materials are another step forward to enabling the use of these materials in optics and photonics., Competing Interests: The authors declare no competing financial interest.

Liquid crystal elastomers (LCEs) are soft materials capable of large, reversible shape changes, which may find potential application as artificial muscles, soft robots, and dynamic functional architectures. Here, the design and additive manufacturing of LCE actuators (LCEAs) with spatially programed nematic order that exhibit large, reversible, and repeatable contraction with high specific work capacity are reported. First, a photopolymerizable, solvent-free, main-chain LCE ink is created via aza-Michael addition with the appropriate viscoelastic properties for 3D printing. Next, high operating temperature direct ink writing of LCE inks is used to align their mesogen domains along the direction of the print path. To demonstrate the power of this additive manufacturing approach, shape-morphing LCEA architectures are fabricated, which undergo reversible planar-to-3D and 3D-to-3D' transformations on demand, that can lift significantly more weight than other LCEAs reported to date., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)