Photo- and Stress-Induced Bending of (E)-1,2-Bis(pyridinium-4-yl)ethene Dinitrate Crystals.

We report on the elastic and photodynamic properties of (E)-1,2-bis(pyridinium-4-yl)ethene dinitrate [H2Ebpe](NO3)2, whose needle-like crystals can be reversibly deformed by applying external mechanical stress. The macro-scale mechanical properties of [H2Ebpe](NO3)2 crystals were quantified by a three-point bending test, which gave a stress-strain curve with an elastic modulus of 1.18 GPa, and its values are lower than those of other flexible elastic organic crystals. It can also be reversibly bent through the [2+2] cycloaddition reaction of the olefin moiety, depending on the direction of UV irradiation.

Fast Light-Driven Motion of Polydopamine Nanomembranes.

The actuation of micro- and nanostructures controlled by external stimuli remains one of the exciting challenges in nanotechnology due to the wealth of fundamental questions and potential applications in energy harvesting, robotics, sensing, biomedicine, and tunable metamaterials. Photoactuation utilizes the conversion of light into motion through reversible chemical and physical processes and enables remote and spatiotemporal control of the actuation. Here, we report a fast light-to-motion conversion in few-nanometer thick bare polydopamine (PDA) membranes stimulated by visible light. Light-induced heating of PDA leads to desorption of water molecules and contraction of membranes in less than 140 µs. Switching off the light leads to a spontaneous expansion in less than 20 ms due to heat dissipation and water adsorption. Our findings demonstrate that pristine PDA membranes are multiresponsive materials that can be harnessed as robust building blocks for soft, micro-, and nanoscale actuators stimulated by light, temperature, and moisture level.

Localized Photoactuation of Polymer Pens for Nanolithography.

Localized actuation is an important goal of nanotechnology broadly impacting applications such as programmable materials, soft robotics, and nanolithography. Despite significant recent advances, actuation with high temporal and spatial resolution remains challenging to achieve. Herein, we demonstrate strongly localized photoactuation of polymer pens made of polydimethylsiloxane (PDMS) and surface-functionalized short carbon nanotubes based on a fundamental understanding of the nanocomposite chemistry and device innovations in directing intense light with digital micromirrors to microscale domains. We show that local illumination can drive a small group of pens (3 × 3 over 170 µm × 170 µm) within a massively two-dimensional array to attain an out-of-plane motion by more than 7 µm for active molecular printing. The observed effect marks a striking three-order-of-magnitude improvement over the state of the art and suggests new opportunities for active actuation.

Springtail-inspired Light-driven Soft Jumping Robots Based on Liquid Crystal Elastomers with Monolithic Three-leaf Panel Fold Structure.

Jump is an important form of motion that enables animals to escape from predators, increase their range of activities, and better adapt to the environment. Inspired by springtails, we describe a light-driven soft jumping robot based on a double-folded liquid crystal elastomer (LCE) ribbon actuator with a monolithic three-leaf panel fold structure. This robot can achieve remarkable jumping height, jumping distance, and maximum take-off velocity, of up to 87 body length (BL), 65 BL, and 930 BL s-1 , respectively, under near-infrared light irradiation. Further, it is possible to control the height, distance, and direction of jump by changing the size and crease angle of the double-folded LCE ribbon actuators. These robots can efficiently jump over obstacles and can jump continuously, even in complex environments. Our simple design strategy improves the performance of jumping actuators and we expect it to have a wide-ranging impact on the strength, continuity, and adaptability of future soft robots.

Controlling Long-Distance Photoactuation with Protein Additives.

Long-distance wireless actuation indicates precise remote control over materials, sensors, and devices that are widely utilized in biomedical, defence, disaster relief, deep ocean, and outer space applications to replace human work. Unlike radio frequency (RF) control, which has low tolerance toward electromagnetic interference (EMI), light control represents a promising method to overcome EMI. Nonetheless, long-distance light-controlled wireless actuation able to compete with RF control has not been achieved until now due to the lack of highly light-sensitive actuator designs. Here, it is demonstrate that amyloid-like protein aggregates can organize photomodule single-layer reduced graphene oxide (rGO) into a well-defined multilayer stack to display long-distance photoactuation. The amyloid-like proteinaceous component docks the rGO layers together to form a hybrid film, which can reliably adhere onto various material surfaces with robust interfacial adhesion. The sensitive photothermal effect and a fast bending in 1 s to switch a circuit are achieved after forming the film on a plastic substrate and irradiating the bilayer film with a blue laser from 100 m away. A photoactuation distance of 50 km can be further extrapolated based on a commercial high-power laser. This study reveals the great potential of amyloid-like aggregates in remote light control of robots and devices.

A Millimeter-Scale Snail Robot Based on a Light-Powered Liquid Crystal Elastomer Continuous Actuator.

Crawling by means of the traveling deformation of a soft body is a widespread mode of locomotion in nature-animals across scales, from microscopic nematodes to earthworms to gastropods, use it to move around challenging terrestrial environments. Snails, in particular, use mucus-a slippery, aqueous secretion-to enhance the interaction between their ventral foot and the contact surface. In this study, a millimeter-scale soft crawling robot is demonstrated that uses a similar mechanism to move efficiently in a variety of configurations: on horizontal, vertical, as well as upside-down surfaces; on smooth and rough surfaces; and through obstacles comparable in size to its dimensions. The traveling deformation of the robot soft body is generated via a local light-induced phase transition in a liquid crystal elastomer and resembles the pedal waves of terrestrial gastropods. This work offers a new approach to micro-engineering with smart materials as well as a tool to better understand this mode of locomotion in nature.

Light-Driven, Caterpillar-Inspired Miniature Inching Robot.

Liquid crystal elastomers are among the best candidates for artificial muscles, and the materials of choice when constructing microscale robotic systems. Recently, significant efforts are dedicated to designing stimuli-responsive actuators that can reproduce the shape-change of soft bodies of animals by means of proper external energy source. However, transferring material deformation efficiently into autonomous robotic locomotion remains a challenge. This paper reports on a miniature inching robot fabricated from a monolithic liquid crystal elastomer film, which upon visible-light excitation is capable of mimicking caterpillar locomotion on different substrates like a blazed grating and a paper surface. The motion is driven by spatially uniform visible light with relatively low intensity, rendering the robot "human-friendly," i.e., operational also on human skin. The design paves the way toward light-driven, soft, mobile microdevices capable of operating in various environments, including the close proximity of humans.

Light-Driven Transport of a Liquid Marble with and against Surface Flows.

Liquid marbles, that is, liquid drops coated by a hydrophobic powder, do not wet any solid or liquid substrate, making their transport and manipulation both highly desirable and challenging. Herein, we describe the light-driven transport of floating liquid marbles and emphasize a surprising motion behavior. Liquid marbles are deposited on a water solution containing photosensitive surfactants. Irradiation of the solution generates photoreversible Marangoni flows that transport the liquid marbles toward UV light and away from blue light when the thickness of the liquid substrate is large enough (Marangoni regime). Below a critical thickness, the liquid marbles move in the opposite direction to that of the surface flow at a speed increasing with decreasing liquid thickness (anti-Marangoni). We demonstrate that the anti-Marangoni motion is driven by the free surface deformation, which propels the non-wetting marble against the surface flow. We call this behavior "slide effect".

Fast Photoactuation and Environmental Response of Humidity-Sensitive pDAP-Silicon Nanocantilevers.

Multi-responsive nanomembranes are a new class of advanced materials that can be harnessed in complex architectures for micro and nano-manipulators, artificial muscles, energy harvesting, soft robotics, and sensors. The design and fabrication of responsive membranes must meet such challenges as trade-offs between responsiveness and mechanical durability, volumetric low-cost production ensuring low environmental impact, and compatibility with standard technologies or biological systems This work demonstrates the fabrication of multi-responsive, mechanically robust poly(1,3-diaminopropane) (pDAP) nanomembranes and their application in fast photoactuators. The pDAP films are developed using a plasma-assisted polymerization technique that offers large-scale production and versatility of potential industrial relevance. The pDAP layers exhibit high elasticity with the Young's modulus of ≈7 GPa and remarkable mechanical durability across 20-80 °C temperatures. Notably, pDAP membranes reveal immediate and reversible contraction triggered by light, rising temperature, or reducing relative humidity underpinned by a reversible water sorption mechanism. These features enable the fabrication of photoactuators composed of pDAP-coated Si nanocantilevers, demonstrating ms timescale response to light, tens of µm deflections, and robust performance up to kHz frequencies. These results advance fundamental research on multi-responsive nanomembranes and hold the potential to boost versatile applications in light-to-motion conversion and sensing toward the industrial level.

Rational Structural Design of Polymer Pens for Energy-Efficient Photoactuation.

Photoactuated pens have emerged as promising tools for expedient, mask-free, and versatile nanomanufacturing. However, the challenge of effectively controlling individual pens in large arrays for high-throughput patterning has been a significant hurdle. In this study, we introduce novel generations of photoactuated pens and explore the impact of pen architecture on photoactuation efficiency and crosstalk through simulations and experiments. By introducing a thermal insulating layer and incorporating an air ap in the architecture design, we have achieved the separation of pens into independent units. This new design allowed for improved control over the actuation behavior of individual pens, markedly reducing the influence of neighboring pens. The results of our research suggest novel applications of photoactive composite films as advanced actuators across diverse fields, including lithography, adaptive optics, and soft robotics.

Photomotion of Hydrogels with Covalently Attached Azo Dye Moieties-Thermoresponsive and Non-Thermoresponsive Gels.

The unique photomotion of azo materials under irradiation has been in the focus of research for decades and has been expanded to different classes of solids such as polymeric glasses, liquid crystalline materials, and elastomers. In this communication, azo dye-containing gels are obtained by photocrosslinking of non-thermoresponsive and lower critical solution temperature type thermoresponsive copolymers. These are analysed with light microscopy regarding their actuation behaviour under laser irradiation. The influences of the cloud-point temperature and of the laser power are investigated in a series of comparative experiments. The thermoresponsive hydrogels show more intense photoactuation when the cloud-point temperature of the non-crosslinked polymer is above, but closer to, room temperature, while higher laser powers lead to stronger motion, indicating a photothermal mechanism. In non-thermoresponsive gels, considerably weaker photoactuation occurs, signifying a secondary mechanism that is a direct consequence of the optical field-azo dye interaction.

Light-Fueled Polymer Film Capable of Directional Crawling, Friction-Controlled Climbing, and Self-Sustained Motion on a Human Hair.

Recent efforts in stimuli-responsive soft materials have enabled wirelessly controlled actuation with increasing degrees of freedom, yielding miniature robots capable of various locomotion in open environments such as on a plane or inside fluids. However, grand challenges remain in harnessing photomechanical deformation to induce locomotion and control of friction during the movement, especially for robotic actuations within constrained spaces. Here, the authors report a centimeter-long polymer strip made of a liquid crystal network that is capable of versatile light-fueled motions along a human hair. The soft polymer robot can translocate directionally upon temporally modulated excitation and climb vertically through friction control with light. A self-oscillating strip is demonstrated to continuously translocate along the hair upon a constant light stimulus, and its gaiting is associated to the smoothness of the hair surface. The results offer new insights to small-scale photo-actuator, mechanical control, and automation in soft micro robotics.

Conjugated Organic Photothermal Films for Spatiotemporal Thermal Engineering.

With the growth of photoenergy harvesting and thermal engineering, photothermal materials (PTMs) have attracted substantial interest due to their unique functions such as localized heat generation, spatiotemporal thermal controllability, invisibility, and light harvesting capabilities. In particular, π-conjugated organic PTMs show advantages over inorganic or metallic PTMs in thin film applications due to their large light absorptivity, ease of synthesis and tunability of molecular structures for realizing high NIR absorption, flexibility, and solution processability. This review is intended to provide an overview of organic PTMs, including both molecular and polymeric PTMs. A description of the photothermal (PT) effect and conversion efficiency (ηPT ) for organic films is provided. After that, the chemical structure and optical properties of organic PTMs are discussed. Finally, emerging applications of organic PT films from the perspective of spatiotemporal thermal engineering principles are illustrated.

Tunable Photomechanics in Diarylethene-Driven Liquid Crystal Network Actuators.

The response of soft actuators made of stimuli-responsive materials can be phenomenologically described by a stimulus-deformation curve, depicting the controllability and sensitivity of the actuator system. Manipulating such stimulus-deformation curve allows fabricating soft microrobots with reconfigurable actuation behavior, which is not easily achievable using conventional materials. Here, we report a light-driven actuator based on a liquid crystal polymer network containing diarylethene (DAE) photoswitches as cross-links, in which the stimulus-deformation curve under visible-light illumination is tuned with UV light. The tuning is brought about by the reversible electrocyclization of the DAE units. Because of the excellent thermal stability of the visible-absorbing closed-form DAEs, the absorbance of the actuator can be optically fixed to a desired value, which in turn dictates the efficiency of photothermally induced deformation. We employ the controllability in devising a logical AND gate with macroscopic output, i.e., an actuator that bends negligibly under UV or visible light irradiation, but with profound shape change when addressed to both simultaneously. The results provide design tools for reconfigurable microrobotics and polymer-based logic gating.

Photo-Actuation of Liquid Crystalline Elastomer Materials Doped with Visible Absorber Dyes under Quasi-Daylight.

We studied the effect of visible absorber dyes on the photo-actuation performances of liquid crystalline elastomer (LCE) materials under quasi-daylight irradiation. The dye-doped LCE materials were prepared through infiltrating visible absorber dyes into a polysiloxane-based LCE matrix based on its solvent-swollen characteristic. They demonstrated well absorption properties in visible spectrum range and performed strong actuation upon the irradiation from quasi-daylight source, thus indicating that the presence of visible absorber dyes effectively sensitized the LCE materials to light irradiation since the light energy was absorbed by the dyes and then converted into heat to trigger the phase change of LCE matrix. The photo-actuation properties of dye-doped LCE materials with different visible absorber dyes, varied dye contents, and irradiation intensities were investigated. It was shown that the visible absorber dyes with different absorption bands created different photo-actuation performances of LCE materials, the one whose absorption band is near the intensity peak position of quasi-daylight spectrum created the optimum photo-actuation performance. The result disclosed a valuable light utilization way for photo-controlled LCE materials since it revealed that a light-absorbing dye, whose absorption band is in the high intensity region of light spectrum, is capable of effectively utilizing light energy to drive the actuation of LCE materials.

Three-Dimensional Microstructured Azobenzene-Containing Gelatin as a Photoactuable Cell Confining System.

In materials science, there is a considerable interest in the fabrication of highly engineered biomaterials that can interact with cells and control their shape. In particular, from the literature, the role played by physical cell confinement in cellular structural organization and thus in the regulation of its functions has been well-established. In this context, the addition of a dynamic feature to physically confining platforms aiming at reproducing in vitro the well-known dynamic interaction between the cells and their microenvironment would be highly desirable. To this aim, we have developed an advanced gelatin-based hydrogel that can be finely micropatterned by two-photon polymerization and stimulated in a controlled way by light irradiation thanks to the presence of an azobenzene cross-linker. Light-triggered expansion of gelatin microstructures induced an in-plane nuclear deformation of physically confined NIH-3T3 cells. The microfabricated photoactuable gelatin shown in this work paves the way to new "dynamic" caging culture systems that can find applications, for example, as "engineered stem cell niches".

Nanostructured Composites Based on Liquid-Crystalline Elastomers.

Liquid-crystalline elastomers (LCEs) are the object of many research investigations due to their reversible and controllable shape deformations, and their high potential for use in the field of soft robots and artificial muscles. This review focuses on recent studies about polymer composites based on LCEs and nanomaterials having different chemistry and morphology, with the aim of instilling new physical properties into LCEs. The synthesis, physico-chemical characterization, actuation properties, and applications of LCE-based composites reported in the literature are reviewed. Several cases are discussed: (1) the addition of various carbon nanomaterials to LCEs, from carbon black to carbon nanotubes, to the recent attempts to include graphene layers to enhance the thermo-mechanic properties of LCEs; (2) the use of various types of nanoparticles, such as ferroelectric ceramics, gold nanoparticles, conductive molybdenum-oxide nanowires, and magnetic iron-oxide nanoparticles, to induce electro-actuation, magnetic-actuation, or photo-actuation into the LCE-based composites; (3) the deposition on LCE surfaces of thin layers of conductive materials (i.e., conductive polymers and gold nanolayers) to produce bending actuation by applying on/off voltage cycles or surface-wrinkling phenomena in view of tunable optical applications. Some future perspectives of this field of soft materials conclude the review.

Self-Regulating Iris Based on Light-Actuated Liquid Crystal Elastomer.

The iris, found in many animal species, is a biological tissue that can change the aperture (pupil) size to regulate light transmission into the eye in response to varying illumination conditions. The self-regulation of the eye lies behind its autofocusing ability and large dynamic range, rendering it the ultimate "imaging device" and a continuous source of inspiration in science. In optical imaging devices, adjustable apertures play a vital role as they control the light exposure, the depth of field, and optical aberrations of the systems. Tunable irises demonstrated to date require external control through mechanical actuation, and are not capable of autonomous action in response to changing light intensity without control circuitry. A self-regulating artificial iris would offer new opportunities for device automation and stabilization. Here, this paper reports the first iris-like, liquid crystal elastomer device that can perform automatic shape-adjustment by reacting to the incident light power density. Similar to natural iris, the device closes under increasing light intensity, and upon reaching the minimum pupil size, reduces the light transmission by a factor of seven. The light-responsive materials design, together with photoalignment-based control over the molecular orientation, provides a new approach to automatic, self-regulating optical systems based on soft smart materials.

Influence of a Crosslinker Containing an Azo Group on the Actuation Properties of a Photoactuating LCE System.

Photoactuating liquid crystalline elastomers (LCE) are promising candidates for an application as artificial muscles in microdevices. In this work, we demonstrate that by optimizing (1) the illumination conditions and (2) the mixture of azo monomer and azo crosslinker, thick films of an all-azo LCE can be prepared, which show a strong length change without bending during photoactuation. This becomes possible by working with white light (about 440 nm), whose absorption is low, leading to a large penetration depth. By adding an azo crosslinker to a previously prepared system, several improvements of the actuation properties-like a stronger photoactuation at lower operational temperatures-could be achieved. In addition, films of different crosslinker concentrations and thicknesses were produced by photopolymerization at varying temperatures within a magnetic field, and their thermo- and photoresponsive behavior was investigated. An extraordinarily strong maximal thermal actuation of 46% and-by exposure to white light at 70 °C-a photoresponsive change in length of up to 40% in just about 13 s could be obtained. Even densely crosslinked samples were still able to photoactuate remarkably. Isothermal back-deformation could either be achieved by irradiation with red light (7 min) or by keeping the film in the dark (13 min).

Photo-chemopropulsion--light-stimulated movement of microdroplets.

The controlled movement of a chemical container by the light-activated expulsion of a chemical fuel, named here "photo-chemopropulsion", is an exciting new development in the array of mechanisms employed for controlling the movement of microvehicles, herein represented by lipid-based microdroplets. This "chemopropulsion" effect can be switched on and off, and is fully reversible.