Vacuum Thermoforming of Optically Switchable Liquid Crystalline Elastomer Spherical Actuators.

Liquid crystal elastomer (LCE) actuators are generally limited in shape, size, and quantity by the need for aligning via stretching and fixing via photopolymerizing. A thermoplastic LCE is presented that may be vacuum thermoformed into centimeter-sized hemispheres. The scalable industrial process induces LCE alignment without requiring postfixing. The hemispheres display remarkable properties, actuating with strains around 20% and transitioning from opaque and scattering to highly translucent upon heating: both the physical and optical effects are fully reversible. Simulations reveal the LCE experiences biaxial strains during processing, the magnitude varying as a function of location on the hemisphere: the resulting alignment describing the hemisphere actuation well. The thermoplastic LCE hemispheres may be combined to form complete spheres by simply heating the joint. The hemisphere can also be physically deformed into a ball which can then unfold back into the hemisphere again. By doping the hemispheres with photoswitches, fluorescent or photothermal dyes, devices are formed for light collection and redistribution, addressable water containers that may pour at will, and light-responsive surfing devices. This is the first example of an LCE amenable to high-volume industrial vacuum thermoforming which may lead to intricate 3D-shaped actuators with new functional properties.

Dual-Wavelength Volumetric Microlithography for Rapid Production of 4D Microstructures.

4D microstructured actuators are micro-objects made of stimuli-responsive materials capable of induced shape deformations, with applications ranging from microrobotics to smart micropatterned haptic surfaces. The novel technology dual-wavelength volumetric microlithography (DWVML) realizes rapid printing of high-resolution 3D microstructures and so has the potential to pave the way to feasible manufacturing of 4D microdevices. In this work, DWVML is applied for the first time to printing stimuli-responsive materials, namely, liquid crystal networks (LCNs). An LCN photoresist is developed and characterized, and large arrays of up to 5625 LCN micropillars with programmable shape changes are produced by means of DWVML in the time span of seconds, over areas as large as ∼5.4 mm2. The production rate of 0.24 mm3 h-1 is achieved, exceeding speeds previously reported for additive manufacturing of LCNs by 2 orders of magnitude. Finally, a membrane with tunable, micrometer-sized pores is fabricated to illustrate the potential DWVML holds for real-world applications.

Sticky Multicolor Mechanochromic Labels.

Sticky-colored labels are an efficient way to communicate visual information. However, most labels are static. Here, we propose a new category of dynamic sticky labels that change structural colors when stretched. The sticky mechanochromic labels can be pasted on flexible surfaces such as fabric and rubber or even on brittle materials. To enhance their applicability, we demonstrate a simple method for imprinting structural color patterns that are either always visible or reversibly revealed or concealed upon mechanical deformation. The mechanochromic patterns are imprinted with a photomask during the ultraviolet (UV) cross-linking of acrylate-terminated cholesteric liquid crystal oligomers in a single step at room temperature. The photomask locally controls the cross-linking degree and volumetric response of the cholesteric liquid crystal elastomers (CLCEs). A nonuniform thickness change induced by the Poisson's ratio contrast between the pattern and the surrounding background might lead to a color-separation effect. Our sticky multicolor mechanochromic labels may be utilized in stress-strain sensing, building environments, smart clothing, security labels, and decoration.

Impact of Endcap Molecules on Temperature-Responsive Cholesteric Liquid Crystal Oligomers in Structural Color Stability and Hypsochromic Shift.

Cholesteric liquid crystal oligomers are an interesting class of temperature responsive structurally colored materials. However, the role of endcap molecules in these oligomers is rather unexplored. In this work, we demonstrate the role of endcap molecules on structural color stability and hypsochromic shift in temperature-responsive cholesteric liquid crystal oligomers. First, new liquid crystal monoacrylate endcap molecules are synthesized, which are then used to synthesize various cholesteric liquid crystal oligomers. In addition, cholesteric oligomers using commercial monoacrylate endcap molecules are also prepared. It is found that the molecular weight and the polydispersity of the oligomers can be tuned by the endcapping molecules. The oligomers are used to produce reflective, structurally colored coatings. It was found that the coatings using the commercial monoacrylate lose their color and crystallize over time, most likely due to the presence of crystalline dimers. The coatings containing the newly synthesized monoacrylate endcap molecules did not exhibit this crystallization, resulting in structurally colored coatings that remained stable over time. These latter coatings possessed temperature responsive hypochromic behavior, which makes them interesting for advanced optical applications.

Shape-Morphing Photoresponsive Hydrogels Reveal Dynamic Topographical Conditioning of Fibroblasts.

The extracellular environment defines a physical boundary condition with which cells interact. However, to date, cell response to geometrical environmental cues is largely studied in static settings, which fails to capture the spatiotemporally varying cues cells receive in native tissues. Here, a photoresponsive spiropyran-based hydrogel is presented as a dynamic, cell-compatible, and reconfigurable substrate. Local stimulation with blue light (455 nm) alters hydrogel swelling, resulting in on-demand reversible micrometer-scale changes in surface topography within 15 min, allowing investigation into cell response to controlled geometry actuations. At short term (1 h after actuation), fibroblasts respond to multiple rounds of recurring topographical changes by reorganizing their nucleus and focal adhesions (FA). FAs form primarily at the dynamic regions of the hydrogel; however, this propensity is abolished when the topography is reconfigured from grooves to pits, demonstrating that topographical changes dynamically condition fibroblasts. Further, this dynamic conditioning is found to be associated with long-term (72 h) maintenance of focal adhesions and epigenetic modifications. Overall, this study offers a new approach to dissect the dynamic interplay between cells and their microenvironment and shines a new light on the cell's ability to adapt to topographical changes through FA-based mechanotransduction.

Fully (Re)configurable Interactive Material through a Switchable Photothermal Charge Transfer Complex Gated by a Supramolecular Liquid Crystal Elastomer Actuator.

Charge transfer complexes (CTCs) based on self-assembled donor and acceptor molecules allow light absorption of significantly redshifted wavelengths to either the donor or acceptor. In this work, we demonstrate a CTC embedded in a hydrogen-bonded liquid crystal elastomer (LCE), which in itself is fully reformable and reprocessable. The LCE host acts as a gate, directing the self-assembly of the CTC. When hydrogen bonding is present, the CTC behaves as a near-infrared (NIR) dye allowing photothermal actuation of the LCE. The CTC can be disassembled in specific regions of the LCE film by disrupting the hydrogen bond interactions, allowing selective NIR heating and localized actuation of the films. The metastable non-CTC state may persist for weeks or can be recovered on demand by heat treatment. Besides the CTC variability, the capability of completely reforming the shape, color, and actuation mode of the LCE provides an interactive material with unprecedented application versatility.

Switching between 3D Surface Topographies in Liquid Crystal Elastomer Coatings Using Two-Step Imprint Lithography.

While dynamic surface topographies are fabricated using liquid crystal (LC) polymers, switching between two distinct 3D topographies remains challenging. In this work, two switchable 3D surface topographies are created in LC elastomer (LCE) coatings using a two-step imprint lithography process. A first imprinting creates a surface microstructure on the LCE coating which is polymerized by a base catalyzed partial thiol-acrylate crosslinking step. The structured coating is then imprinted with a second mold to program the second topography, which is subsequently fully polymerized by light. The resulting LCE coatings display reversible surface switching between the two programmed 3D states. By varying the molds used during the two imprinting steps, diverse dynamic topographies can be achieved. For example, by using grating and rough molds sequentially, switchable surface topographies between a random scatterer and an ordered diffractor are achieved. Additionally, by using negative and positive triangular prism molds consecutively, dynamic surface topographies switching between two 3D structural states are achieved, driven by differential order/disorder transitions in the different areas of the film. It is anticipated that this platform of dynamic 3D topological switching can be used for many applications, including antifouling and biomedical surfaces, switchable friction elements, tunable optics, and beyond.

A Degradable Sustained-Release Drug Delivery System for Bleb-Forming Glaucoma Surgery.

Fibrosis of the filtering bleb is one of the main causes of failure after bleb-forming glaucoma surgery. Intraoperative application of mitomycin C (MMC) is the current gold standard to reduce the fibrotic response. However, MMC is cytotoxic and one-time application is often insufficient. A sustained-release drug delivery system (DDS), loaded with MMC, may be less cytotoxic and equally or more effective. Two degradable (polycaprolactone (PCL) and polylactic-co-glycolic acid (PLGA)) MMC-loaded DDSs are developed. Release kinetics are first assessed in vitro followed by rabbit implants in conjunction with the PRESERFLO MicroShunt. As a control, the MicroShunt is implanted with adjunctive use of a MMC solution. Rabbits are euthanized at postoperative day (POD) 28 and 90. The PLGA and PCL DDSs release (on average) 99% and 75% of MMC, respectively. All groups show functioning blebs until POD 90. Rabbits implanted with a DDS show more inflammation with avascular thin-walled blebs when compared to the control. However, collagen is more loosely arranged. The PLGA DDS shows less inflammation, less foreign body response (FBR), and more complete degradation at POD 90 when compared to the PCL DDS. Further optimization with regard to dosage is required to reduce side effects to the conjunctiva.

Photomechanical response under physiological conditions of azobenzene-containing 4D-printed liquid crystal elastomer actuators.

Soft and mechanically responsive actuators hold the promise to revolutionize the design and manufacturing of devices in the areas of microfluidics, soft robotics and biomedical engineering. In many of these applications, the actuators need to operate in a wet environment that can strongly affect their performance. In this paper, we report on the photomechanical response in a biological buffer of azobenzene-containing liquid crystal elastomer (LCE)-based actuators, prepared by four-dimensional (4D) printing. Although the photothermal contribution to the photoresponse is largely cancelled by the heat withdrawing capacity of the employed buffer, a significant photoinduced reversible contraction, in the range of 7% of its initial length, has been achieved under load, taking just a few seconds to reach half of the maximum contraction. Effective photomechanical work performance under physiological conditions has, therefore, been demonstrated in the 4D-printed actuators. Advantageously, the photomechanical response is not sensitive to salts present in the buffer differently to hydrogels with responses highly dependent on the fluid composition. Our work highlights the capabilities of photomechanical actuators, created using 4D printing, when operating under physiological conditions, thus showing their potential for application in the microfluidics and biomedical fields.

The Interplay between Different Stimuli in a 4D Printed Photo-, Thermal-, and Water-Responsive Liquid Crystal Elastomer Actuator.

Multi-stimuli responsivity in 3D-printed objects is receiving much attention. However, the simultaneous interplay between different environmental stimuli is largely unexplored. In this work, we demonstrate direct ink writing of an oligomeric ink containing an azobenzene photo-switch with an accessible hydrogen bond allowing triple responsivity to light, heat, and water. The resulting printed liquid crystal elastomer performs multiple actuations, the specific response depending on the environmental conditions. Bilayer films formed by printing on a static substrate can rapidly change shape, bending almost 80 degrees if irradiated in air or undergoing a shrinkage of about 50 % of its length when heated. The bilayer film assumes dramatically different shapes in water depending on combined environmental temperature and lighting conditions.

Uni- and Bidirectional Rotation and Speed Control in Chiral Photonic Micromotors Powered by Light.

Liquid crystalline polymers are attractive materials for untethered miniature soft robots. When they contain azo dyes, they acquire light-responsive actuation properties. However, the manipulation of such photoresponsive polymers at the micrometer scale remains largely unexplored. Here, uni- and bidirectional rotation and speed control of polymerized azo-containing chiral liquid crystalline photonic microparticles powered by light is reported. The rotation of these polymer particles is first studied in an optical trap experimentally and theoretically. The micro-sized polymer particles respond to the handedness of a circularly polarized trapping laser due to their chirality and exhibit uni- and bidirectional rotation depending on their alignment within the optical tweezers. The attained optical torque causes the particles to spin with a rotation rate of several hertz. The angular speed can be controlled by small structural changes, induced by ultraviolet (UV) light absorption. After switching off the UV illumination, the particle recovers its rotation speed. The results provide evidence of uni- and bidirectional motion and speed control in light-responsive polymer particles and offer a new way to devise light-controlled rotary microengines at the micrometer scale.

Programming Thermochromic Liquid Crystal Hetero-Oligomers for Near-Infrared Reflectors: Unequal Incorporation of Similar Reactive Mesogens in Thiol-ene Oligomers.

Cholesteric liquid crystal oligomers are widely researched for their interesting thermochromic properties. However, structure-property relationships to program the thermochromic properties of these oligomers have been rarely reported. In this work, we use the versatile thiol-ene click reaction to synthesize a series of hetero-oligomers and study the impact of different compositions on the thermochromic behavior of the resulting material. Characterization of the oligomers shows significantly different rates of reaction for the monomers despite their very similar structures, which leads to oligomer compositions that do not match the original reaction feed. The oligomers are then used to produce thin near-infrared reflecting coatings. The best-performing thermochromic reflector has a room-temperature reflection band that shifts a total of 510 nanometers upon heating to 120 °C. The shift is repeatable for up to 10 times with no appreciable degradation. The room temperature reflection of the coatings is shown to be tunable not only by adjusting the chiral dopant concentration but also by the ratio of the monomers. Finally, we show that the oligomers can be chemically modified by making their reactive end groups undergo a reaction with monothiol compounds. These modifications allow for further fine-tuning of liquid crystal oligomers for heat-regulating window films, for example.

A multifunctional structural coloured electronic skin monitoring body motion and temperature.

Multifunctional e-skins provide information on physiological and environmental parameters. However, the development and fabrication of such devices is challenging. Here, structural coloured electronic skins are presented, which are prepared via scalable methods that can simultaneously monitor the skin temperature and body motion when patched onto the human skin.

Understanding and Improving the Oil and Water Barrier Performance of a Waterborne Coating on Paperboard.

Using paperboard as packaging material is more sustainable than using plastic. To be a viable replacement, however, the barrier properties of paperboard need to be improved. Applying a waterborne barrier coating for both oil and water is an attractive method to improve the barrier performance of paperboard food packaging. However, not much is known about the oil and water barrier properties and penetration pathways of such coatings. Here, an alkali-soluble resin (ASR)-stabilized waterborne emulsion polymer was prepared and applied on untreated paperboard. Its performance as oil and water barrier coating was investigated, and the penetration pathways for both oil and water through the coating are discussed. The presence of surface defects in the coating applied on the paperboard strongly affects both the oil and water barrier properties, but the coating's morphology and chemical nature only play a major role in the water barrier performance. The optimal barrier performance for oil and water was achieved when adding 5 wt % isopropanol (IPA) to the dispersion and applying two coating layers on paperboard. The IPA improves film formation and reduces the number of surface defects, which is explained by a more favorable spreading coefficient of the coating over the paperboard substrate. These insights will help to improve the oil and water barrier properties of polymer-coated paperboard for more sustainable packaging applications.

Liquid crystal-based structural color actuators.

Animals can modify their body shape and/or color for protection, camouflage and communication. This adaptability has inspired fabrication of actuators with structural color changes to endow soft robots with additional functionalities. Using liquid crystal-based materials for actuators with structural color changes is a promising approach. In this review, we discuss the current state of liquid crystal-based actuators with structural color changes and the potential applications of these structural color actuators in soft robotic devices.

Tuning the Gas Separation Performances of Smectic Liquid Crystalline Polymer Membranes by Molecular Engineering.

The effect of layer spacing and halogenation on the gas separation performances of free-standing smectic LC polymer membranes is being investigated by molecular engineering. LC membranes with various layer spacings and halogenated LCs were fabricated while having a planar aligned smectic morphology. Single permeation and sorption data show a correlation between gas diffusion and layer spacing, which results in increasing gas permeabilities with increasing layer spacing while the ideal gas selectivity of He over CO2 or He over N2 decreases. The calculated diffusion coefficients show a 6-fold increase when going from membranes with a layer spacing of 31.9 Å to membranes with a layer spacing of 45.2 Å, demonstrating that the layer spacing in smectic LC membranes mainly affects the diffusion of gasses rather than their solubility. A comparison of gas sorption and permeation performances of smectic LC membranes with and without halogenated LCs shows only a limited effect of LC halogenation by a slight increase in both solubility and diffusion coefficients for the membranes with halogenated LCs, resulting in a slightly higher gas permeation and increased ideal gas selectivities towards CO2. These results show that layer spacing plays an important role in the gas separation performances of smectic LC polymer membranes.

Ink-Deposited Transparent Electrochromic Structural Colored Foils.

Despite progress in the field of electrochromic devices, developing structural color-tunable photonic systems having both high transparency and flexibility remains challenging. Here, an ink-deposited transparent electrochromic structural colored foil displaying reflective colors, tuned by an integrated heater, is prepared in a single-substrate method. Efficient and homogeneous heating is induced by a gravure printed silver nanowire-based substrate, delivering an electrothermal response upon applying an electrical potential. On top of this flexible, transparent heater, a cholesteric liquid crystal ink is bar-coated and subsequently photopolymerized, yielding a structural colored film that exhibits temperature-responsive color changes. The transparent electrochromic foils appear colorless at room temperature but demonstrate structural color tuning with high optical quality when modifying the electrical potential. Both optical and electrothermal performances were preserved when deforming the foils. Applying the conductive and structural colored inks via the easy processable, continuous methods of gravure printing and bar-coating highlights the potential for scaling up to large-scale stimuli-responsive, transparent optical foils. These transparent structural colored foils can be potentially used for a wide range of photonic devices including smart windows, displays, and sensors and can be directly installed on top of curved, flexible surfaces.

Direct Ink Writing of Recyclable Supramolecular Soft Actuators.

Direct ink writing (DIW) of liquid crystal elastomers (LCEs) has rapidly paved its way into the field of soft actuators and other stimuli-responsive devices. However, currently used LCE systems for DIW require postprinting (photo)polymerization, thereby forming a covalent network, making the process time-consuming and the material nonrecyclable. In this work, a DIW approach is developed for printing a supramolecular poly(thio)urethane LCE to overcome these drawbacks of permanent cross-linking. The thermo-reversible nature of the supramolecular cross-links enables the interplay between melt-processable behavior required for extrusion and formation of the network to fix the alignment. After printing, the actuators demonstrated a reversible contraction of 12.7% or bending and curling motions when printed on a passive substrate. The thermoplastic ink enables recyclability, as shown by cutting and printing the actuators five times. However, the actuation performance diminishes. This work highlights the potential of supramolecular LCE inks for DIW soft circular actuators and other devices.

Pigmented Structural Color Actuators Fueled by Near-Infrared Light.

Cuttlefish can modify their body shape and both their pigmentary and structural colors for protection. This adaptability has inspired the development of appearance-changing polymers such as structural color actuators, although in most cases, the original shape has been confined to being flat, and pigmented structural color actuators have not yet been reported. Here, we have successfully created a pigmented structural color actuator using a cholesteric liquid crystal elastomer with a lower actuation temperature where both actuation and coloration (structural and pigmental) are tunable with temperature and NIR light. The shape, structural color, and absorption of the NIR-absorbing dye pigment of the actuator all change with temperature. Light can be used to trigger local in-plane bending actuation in flat films and local shape changes in a variety of 3D-shaped objects. A cuttlefish mimic that can sense light and respond by locally changing its appearance was also made to demonstrate the potential of pigmented structural color actuators for signaling and camouflage in soft robotics.