Colloidal tubular microrobots for cargo transport and compression.

Microrobot swarms have seen increased interest in recent years due to their potentials for in vivo delivery and imaging with cooperative propulsion modes and enhanced imaging signals. Yet most swarms developed so far are limited to dense particle aggregates, far simpler than complicated three-dimensional assemblies of anisotropic particles. Here, we show via assembly path design that complex hollow tubular structures can be assembled from simple isotropic colloidal spheres and those complicated, metastable, microtubes can be formed from simple, energetically favorable colloidal membranes. The assembled microtubes can remain intact and roll under a precessing magnetic field, with propulsion directions and velocities precisely controlled by field components. The hollow spaces inside enable these tubular microrobots to grab, transport, and release cargos on command. We also demonstrate unique compressing and uncompressing capabilities with our tubular microrobots, making them effective microtweezers. Our work shows that complicated microrobots can be transformed from simple assemblies, providing an insight on building micromachines.

Photocontrollable Elongation Actuation of Liquid Crystal Elastomer Films with Well-Defined Crease Structures.

Although liquid crystal elastomers (LCEs) have demonstrated various applications in artificial muscles and soft robotics, their inherent flexibility and orientation-dependent forces limit their functions. For instance, LCEs can sustain a high actuation force when they contract but cannot elongate to drive loads with large displacements. In this study, it is demonstrated that photocontrollable elongation actuation with a large strain can be achieved in polydomain LCEs by programming the crease structures in a well-defined order to couple the actuation forces. Efficient photoactuation without overheating-induced damage to the materials is favored, based on the well-designed photosensitive molecular switch crosslinker via the synergy of photochemical and photothermal effects. The LCE actuator can jack up heavy loads, elongate freely, and contract back to manipulate distant objects. Theoretical analysis based on a finite element simulation of the deformation energy during the actuation process reveals a trade-off between the abilities of jacking-up and withstanding load. More importantly, this study simplifies the design of a single material with functions inherent only in other soft robotic devices based on the assembly of multiple modules, thus providing a design strategy for surpassing instinctive properties of conventional soft materials to expand the functions of soft robotics.

Multifunctional Ionic Conductive Anisotropic Elastomers with Self-Wrinkling Microstructures by In Situ Phase Separation.

Multifunctional flexible sensors are the development trend of wearable electronic devices in the future. As the core of flexible sensors, the key is to construct a stable multifunctional integrated conductive elastomer. Here, ionic conductive elastomers (ICEs) with self-wrinkling microstructures are designed and prepared by in situ phase separation induced by a one-step polymerization reaction. The ICEs are composed of ionic liquids as ionic conductors doped into liquid crystal elastomers. The doped ionic liquids cluster into small droplets and in situ induce the formation of wrinkle structures on the upper surface of the films. The prepared ICEs exhibit mechanochromism, conductivity, large tensile strain, low hysteresis, high cycle stability, and sensitivity during the tension-release process, which achieve dual-mode outputs of optical and electrical signals for information transmission and sensors.

Photo-triggered full-color circularly polarized luminescence based on photonic capsules for multilevel information encryption.

Materials with phototunable full-color circularly polarized luminescence (CPL) have a large storage density, high-security level, and enormous prospects in the field of information encryption and decryption. In this work, device-friendly solid films with color tunability are prepared by constructing Förster resonance energy transfer (FRET) platforms with chiral donors and achiral molecular switches in liquid crystal photonic capsules (LCPCs). These LCPCs exhibit photoswitchable CPL from initial blue emission to RGB trichromatic signals under UV irradiation due to the synergistic effect of energy and chirality transfer and show strong time dependence because of the different FRET efficiencies at each time node. Based on these phototunable CPL and time response characteristics, the concept of multilevel data encryption by using LCPC films is demonstrated.

Pyroptosis-Mediated Synergistic Photodynamic and Photothermal Immunotherapy Enabled by a Tumor-Membrane-Targeted Photosensitive Dimer.

Overcoming the resistance to apoptosis and immunosuppression of tumor cells is a significant challenge in augmenting the effect of cancer immunotherapy. Pyroptosis, a lytic programmed cell-death pathway unlike apoptosis, is considered a type of immunogenic cell death (ICD) that can intensify the ICD process in tumor cells, releasing dramatically increased tumor-associated antigens and damage-associated molecular patterns to promote cancer immunotherapy. Herein, a tumor cell membrane-targeted aggregation-induced emission photosensitive dimer is found to be able to achieve highly efficient ICD under the synergistic effect of photodynamic and photothermal therapy. The photosensitive dimer can efficiently produce type-I reactive oxygen species (ROS) by photodynamic therapy in hypoxic tumor tissue, leading to pyroptosis by direct cell membrane damage, which is further reinforced by its photothermal effect. Furthermore, the enhanced ICD effect based on the dimer can completely eliminate the primary tumor on the seventh day of treatment and can also boost systemic antitumor immunity by generating immune memory, which is demonstrated by the superior antitumor therapeutic effects on both solid tumors and metastatic tumors when healing 4T1 tumor mouse models with poor immunogenicity.

Light-Driven Aqueous Dissipative Pseudorotaxanes with Tunable Fluorescence Enabling Deformable Nano-Assemblies.

Developing an artificial dynamic nanoscale molecular machine that dissipatively self-assembles far from equilibrium is fundamentally important but is significantly challenging. Herein, we report dissipatively self-assembling light-activated convertible pseudorotaxanes (PRs) that show tunable fluorescence and enable deformable nano-assemblies. A pyridinium-conjugated sulfonato-merocyanine derivative (EPMEH) and cucurbit[8]uril (CB[8]) form the 2EPMEH ⊂ CB[8] [3]PR in a 2:1 stoichiometry, which phototransforms into a transient spiropyran containing 1:1 EPSP ⊂ CB[8] [2]PR when exposed to light. The transient [2]PR thermally relaxes (reversibly) to the [3]PR in the dark accompanied by periodic fluorescence changes that include near-infrared emission. Moreover, octahedral and spherical nanoparticles are formed through the dissipative self-assembly of the two PRs, and the Golgi apparatus is dynamically imaged using fluorescent dissipative nano-assemblies.

Rheological Tunable Magnetic Fluids with Long-Term Stability.

Magnetic fluids have advantages such as flow ability and solid-like property in strong magnetic fields, but have to suffer from the tradeoff between suspension stability and flow resistance. In this work, a thermal/photo/magnetorheological water-based magnetic fluid is fabricated by using oleic acid-coated Fe3 O4 (Fe3 O4 @OA) nanoparticles as the magnetic particles and the amphiphilic penta block copolymer (PTMC-F127-PTMC)-based aqueous solution as the carrier fluid. Due to the hydrophobic self-assembly between Fe3 O4 @OA and PTMC-F127-PTMC, the Newtonian-like magnetic fluid has outstanding long-term stability and reversible rheological changes between the low-viscosity flow state and the 3D gel structure. In the linear viscoelastic region, the viscosity exhibits an abrupt increase from below 0.10 Pa s at 20 °C to ≈1.3 × 104  Pa s at 40 °C. Benefitting from the photothermal and magnetocaloric effects of the Fe3 O4 @OA nanoparticles, the rheological change process also can be controlled by near infrared light and alternating magnetic field, which endows the magnetic fluid with the applications in the fields of mobile valves, moveable switches, buffer or damping materials in sealed devices, etc.

Hypoxia-Responsive Photosensitizer Targeting Dual Organelles for Photodynamic Therapy of Tumors.

Developing safe and precise image-guided photodynamic therapy is a challenge. In this study, the hypoxic properties of solid tumors are exploited to construct a hypoxia-responsive photosensitizer, TPA-Azo. Introducing the azo group into the photosensitizer TPA-BN with aggregation-induced emission quenches its fluorescence. When the nonfluorescent TPA-Azo enters hypoxic tumors, it is reduced by the overexpressed azoreductase to generate a fluorescent photosensitizer TPA-BN with an amino group that exhibits fluorescence-activatable image-guided photodynamic therapy with dual-organelle (lipid droplets and lysosomes) targeting. This design strategy provides a basis for the development of fluorescence-activatable photosensitizers.

Bioinspired MXene-Based Soft Actuators Exhibiting Angle-Independent Structural Color.

In nature, many living organisms exhibiting unique structural coloration and soft-bodied actuation have inspired scientists to develop advanced structural colored soft actuators toward biomimetic soft robots. However, it is challenging to simultaneously biomimic the angle-independent structural color and shape-morphing capabilities found in the plum-throated cotinga flying bird. Herein, we report biomimetic MXene-based soft actuators with angle-independent structural color that are fabricated through controlled self-assembly of colloidal SiO2 nanoparticles onto highly aligned MXene films followed by vacuum-assisted infiltration of polyvinylidene fluoride into the interstices. The resulting soft actuators are found to exhibit brilliant, angle-independent structural color, as well as ultrafast actuation and recovery speeds (a maximum curvature of 0.52 mm-1 can be achieved within 1.16 s, and a recovery time of ~ 0.24 s) in response to acetone vapor. As proof-of-concept illustrations, structural colored soft actuators are applied to demonstrate a blue gripper-like bird's claw that can capture the target, artificial green tendrils that can twine around tree branches, and an artificial multicolored butterfly that can flutter its wings upon cyclic exposure to acetone vapor. The strategy is expected to offer new insights into the development of biomimetic multifunctional soft actuators for somatosensory soft robotics and next-generation intelligent machines.

Stretchable and self-healable spoof plasmonic meta-waveguide for wearable wireless communication system.

Microwave transmission lines in wearable systems are easily damaged after frequent mechanical deformation, posing a severe threat to wireless communication. Here, we report a new strategy to achieve stretchable microwave transmission lines with superior reliability and durability by integrating a self-healable elastomer with serpentine-geometry plasmonic meta-waveguide to support the spoof surface plasmon polariton (SSPP). After mechanical damage, the self-healable elastomer can autonomously repair itself to maintain the electromagnetic performance and mechanical strength. Meanwhile, the specially designed SSPP structure exhibits excellent stability and damage resistance. Even if the self-healing process has not been completed or the eventual repair effect is not ideal, the spoof plasmonic meta-waveguide can still maintain reliable performance. Self-healing material enhances strength and durability, while the SSPP improves stability and gives more tolerance to the self-healing process. Our design coordinates the structural design with material synthesis to maximize the advantages of the SSPP and self-healing material, significantly improving the reliability and durability of stretchable microwave transmission lines. We also perform communication quality experiments to demonstrate the potential of the proposed meta-waveguide as interconnects in future body area network systems.

Amphiphilicity-Controlled Polychromatic Emissive Supramolecular Self-Assemblies for Highly Sensitive and Efficient Artificial Light-Harvesting Systems.

Dynamic sequential control of photoluminescence by supramolecular approaches has become a great issue in supramolecular chemistry. However, developing a systematic strategy to construct polychromatic photoluminescent supramolecular self-assemblies for improving the efficiency and sensitivity of artificial light-harvesting systems still remains a challenge. Here, a series of amphiphilicity-controlled supramolecular self-assemblies with polychromatic fluorescence based on lower-rim hexyl-modified sulfonatocalix[4]arene (SC4A6) and N-alkyl-modified p-phenylene divinylpyridiniums (PVPn, n = 2-7) as efficient light-harvesting platforms is reported. PVPn shows wide ranges of polychromatic fluorescence by co-assembling with SC4A6, whose emission trends significantly depend on the modified alkyl-chains of PVPn. The formed PVPn-SC4A6 co-assemblies as light-harvesting platforms are extremely sensitive for transferring the energy to two near-infrared emissive acceptors, Nile blue (NiB) and Rhodamine 800. After optimizing the amphiphilicity of PVPn-SC4A6 systems, the PVPn-SC4A6-NiB light-harvesting systems achieve an ultrasensitive working concentration for NiB (2 nm) and an ultrahigh antenna effect up to 91.0. Furthermore, the two different kinds of light-harvesting nanoparticles exhibit good performance on near-infrared imaging in the Golgi apparatus and mitochondria, respectively.

A high mobility air-stable n-type organic small molecule semiconductor with high UV-visible-to-NIR photoresponse.

An organic semiconductor with high carrier mobility and efficient light absorption over a wide spectral range is of the most important yet challenging material for constructing a broadband responsive organic photodetector. However, the development of such organic semiconductors, especially for air-stable n-type organic small molecule semiconductors, is still at an early stage. Here we report the fabrication of high-performance n-type semiconducting crystalline nanosheets and the development of air-stable field-effect transistors, phototransistors, with high response over a broad spectrum. The n-type small molecule semiconductor is assembled into a crystalline nanosheet based on the solvent-phase interfacial self-assembly method. N-type field-effect transistors with high electron mobility are fabricated and their electrical performances exhibit excellent air stability. Impressively, the demonstrated phototransistors exhibit an ultrahigh responsivity over a wide spectral range from 365 to 940 nm, with a maximum photoresponsivity of 9.2 × 105 A W-1 and specific detectivity of 5.26 × 1013 Jones, which is the best performance among the reported n-type organic small molecule-based phototransistors.

Light-activated photodeformable supramolecular dissipative self-assemblies.

Dissipative self-assembly, one of fundamentally important out-of-equilibrium self-assembly systems, can serve as a controllable platform to exhibit temporal processes for various non-stimulus responsive properties. However, construction of light-fueled dissipative self-assembly structures with transformable morphology to modulate non-photoresponsive properties remains a great challenge. Here, we report a light-activated photodeformable dissipative self-assembly system in aqueous solution as metastable fluorescent palette. Zwitterionic sulfonato-merocyanine is employed as a light-induced amphiphile to co-assemble with polyethyleneimine after light irradiation. The formed spherical nanoparticles spontaneously transform into cuboid ones in the dark with simultaneous variation of the particle sizes. Then the two kinds of nanoparticles can reversibly interconvert to each other by periodical light irradiation and thermal relaxation. Furthermore, after loading different fluorophores exhibiting red, green, blue emissions and their mixtures, all these fluorescent dissipative deformable nanoparticles display time-dependent fluorescence variation with wide range of colors. Owing to the excellent performance of photodeformable dissipative assembly platform, the light-controlled fluorescence has achieved a 358-fold enhancement. Therefore, exposing the nanoparticles loaded with fluorophores to light in a spatially controlled manner allows us to draw multicolored fluorescent images that spontaneously disappeared after a specific period of time.

Synchronous Imaging in Golgi Apparatus and Lysosome Enabled by Amphiphilic Calixarene-Based Artificial Light-Harvesting Systems.

Artificial supramolecular light-harvesting systems have expanded various properties on photoluminescence, enabling promising applications on cell imaging, especially for imaging in organelles. Supramolecular light-harvesting systems have been used for imaging in some organelles such as lysosome, Golgi apparatus, and mitochondrion, but developing a supramolecular light-harvesting platform for imaging two organelles synchronously still remains a great challenge. Here, we report a series of lower-rim dodecyl-modified sulfonato-calix[4]arene-mediated supramolecular light-harvesting platforms for efficient light-harvesting from three naphthalene diphenylvinylpyridiniums containing acceptors, Nile Red, and Nile Blue. All of the constructed supramolecular light-harvesting systems possess high light-harvesting efficiency. Furthermore, when the two acceptors are loaded simultaneously in a single light-harvesting donor system for imaging in human prostate cancer cells, organelle imaging in lysosome and Golgi apparatus can be realized at the same time with distinctive wavelength emission. Nile Red receives the light-harvesting energy from the donors, reaching orange emissions (625 nm) in lysosome while Nile Blue shows a near-infrared light-harvesting emission at 675 nm in Golgi apparatus in the same cells. Thus, the light harvesting system provides a pathway for synchronously efficient cell imaging in two distinct organelles with a single type of photoluminescent supramolecular nanoparticles.

An Artificial Light-Harvesting System with Controllable Efficiency Enabled by an Annulene-Based Anisotropic Fluid.

The development of controllable artificial light-harvesting systems based on liquid crystal (LC) materials, i.e., anisotropic fluids, remains a challenge. Herein, an annulene-based discotic LC compound 6 with a saddle-shaped cyclooctatetrathiophene core has been synthesized to construct a tunable light-harvesting platform. The LC material shows a typical aggregation-induced emission, which can act as a suitable light-harvesting donor. By loading Nile red (NiR) as an acceptor, an artificial light-harvesting system is achieved. Relying on the thermal-responsive self-assembling ability of 6 with variable molecular order, the efficiency of such 6-NiR system can be controlled by temperature. This light-harvesting system works sensitively at a high donor/acceptor ratio as 1000 : 1, and exhibits a high antenna effect (39.1) at a 100 : 1 donor/acceptor ratio. This thermochromic artificial light-harvesting LC system could find potential applications in smart devices employing soft materials.

Thermo- and Mechanochromic Camouflage and Self-Healing in Biomimetic Soft Actuators Based on Liquid Crystal Elastomers.

In nature, many mysterious creatures capable of deformation camouflage, color camouflage, and self-healing have inspired scientists to develop various biomimetic soft robots. However, the systematic integration of all the above functionalities into a single soft actuator system still remains a challenge. Here we chemically introduce a multi-stimuli-responsive tetraarylsuccinonitrile (TASN) chromophore into a liquid crystal elastomer (LCE) network through a facile thiol-ene photoaddition method. The obtained TASN-LCE soft actuators not only exhibit reversible shape-morphing and reversible color-changing behavior in response to heat and mechanical compression, but also show excellent self-healing, reprogramming and recycling characteristics. We hope that such a TASN-LCE actuator system endowed with dynamic distortion, thermo- and mechano-chromic camouflage, and self-healing functionalities would pave the way for further development of multifunctional biomimetic soft robotic devices.

Liquid Crystals: Versatile Self-Organized Smart Soft Materials.

Smart soft materials are envisioned to be the building blocks of the next generation of advanced devices and digitally augmented technologies. In this context, liquid crystals (LCs) owing to their responsive and adaptive attributes could serve as promising smart soft materials. LCs played a critical role in revolutionizing the information display industry in the 20th century. However, in the turn of the 21st century, numerous beyond-display applications of LCs have been demonstrated, which elegantly exploit their controllable stimuli-responsive and adaptive characteristics. For these applications, new LC materials have been rationally designed and developed. In this Review, we present the recent developments in light driven chiral LCs, i.e., cholesteric and blue phases, LC based smart windows that control the entrance of heat and light from outdoor to the interior of buildings and built environments depending on the weather conditions, LC elastomers for bioinspired, biological, and actuator applications, LC based biosensors for detection of proteins, nucleic acids, and viruses, LC based porous membranes for the separation of ions, molecules, and microbes, living LCs, and LCs under macro- and nanoscopic confinement. The Review concludes with a summary and perspectives on the challenges and opportunities for LCs as smart soft materials. This Review is anticipated to stimulate eclectic ideas toward the implementation of the nature's delicate phase of matter in future generations of smart and augmented devices and beyond.

Visible Light-Driven Molecular Switches and Motors: Recent Developments and Applications.

Inspired by human vision, a diverse range of light-driven molecular switches and motors have been developed for fundamental understanding and application in material science and biology. Recently, the design and synthesis of visible light-driven molecular switches and motors have been actively pursued. This emerging trend is partly motivated to avoid the harmful effects of ultraviolet light, which was necessary to drive the classical molecular switches and motors at least in one direction, impeding their employment in biomedical and photopharmacology applications. Moreover, visible light-driven molecular switches and motors are demonstrated to enable benign optical materials for advanced photonic devices. Therefore, during the past several years, visible light-driven molecular switches based on azobenzene derivatives, diarylethenes, 1,2-dicyanodithienylethenes, hemithioindigo derivatives, iminothioindoxyls, donor-acceptor Stenhouse adducts, and overcrowded alkene based molecular motors have been judiciously designed, synthesized, and used in the development of functional materials and systems for a wide range of applications. In this Review, we present the recent developments toward the design of visible light-driven molecular switches and motors, with their applications in the fabrication of functional materials and systems in material science, bioscience, pharmacology, etc. The visible light-driven molecular switches and motors realized so far undoubtedly widen the scope of these interesting compounds for technological and biological applications. We hope this Review article could provide additional impetus and inspire further research interests for future exploration of visible light-driven advanced materials, systems, and devices.

Stimulus-driven liquid metal and liquid crystal network actuators for programmable soft robotics.

Sophisticated soft matter engineering has been endorsed as an emerging paradigm for developing untethered soft robots with built-in electronic functions and biomimetic adaptation capacities. However, the integration of flexible electronic components into soft robotic actuators is challenging due to strain mismatch and material incompatibilities. Herein, we report a general strategy to integrate electrically conductive liquid metals (LMs) and shape-morphing liquid crystal networks (LCNs) towards multifunctional and programmable soft robotics. A unique colloidal LM ink with superior adhesion and photothermal conversion efficiency was judiciously designed and fabricated by ultrasonicating LMs and miniature carboxylated gold nanorods (MiniGNR-COOH) in an aqueous suspension of biological bacterial cellulose. The designed nanocellulose-based colloidal LM ink is used for shape-deformable and electrically conductive LM-LCN soft robots that can be electro- and photo-thermally actuated. As proof-of-concept demonstrations, we present a light-fueled soft oscillator, an inchworm-inspired soft crawler and programmable robotic Shadow Play exhibiting multifunctional controllability. The strategy disclosed here could open up a new technological arena for advanced multifunctional soft materials with potential utility in bioinspired soft machines, integrated soft electronics, human-computer interaction and beyond.

Combined electric and photocontrol of selective light reflection at an oblique helicoidal cholesteric liquid crystal doped with azoxybenzene derivative.

An oblique helicoidal cholesteric liquid crystal Ch_{OH} represents a unique optical material with a single-harmonic periodic modulation of the refractive index and a pitch that can be tuned by an electric or magnetic field in a broad range from submicrometers to micrometers. In this work, we demonstrate that the oblique helicoidal cholesteric doped with azoxybenzene molecules can be tuned by both the electric field and light irradiation. The tuning mechanism is explained by the kinetics of trans-cis photoisomerization of the azoxybenzene molecules. At a fixed voltage, UV irradiation causes a redshift of the reflection peak by more than 200 nm. The effect is caused by an increase of the bend elastic constant of Ch_{OH} under irradiation. The demonstrated principle has the potential for applications such as smart windows, sensors, tunable lasers, and filters.