Reconfiguration, Welding, Reprogramming, and Complex Shape Transformation of An Optical Shape Memory Polymer Network Enabled by Patterned Secondary Crosslinking.

Stimuli-triggered generation of complicated 3D shapes from 2D strips or plates without using sophisticated molds is desirable and achieving such 2D-to-3D shape transformation in combination with shape reconfiguration, welding, and reprogramming on a single material is very challenging. Here, a convenient and facile strategy using the solution of a disulfide-containing diamine for patterned secondary crosslinking of an optical shape-memory polymer network is developed to integrate the above performances. The dangling thiolectones attached to the backbones react with the diamine in the solution-deposited region so that the secondary crosslinking may not only weld individual strips into assembled 3D shapes but also suppress the relaxation of the deformed polymer chains to different extents for shape reconfiguration or heating-induced complex 3D deformations. In addition, as the dynamic disulfide bonds can be thermally activated to erase the initial programming information and the excessive thiolectones are available for subsequent patterned crosslinking, the material also allows shape reprogramming. Combining welding with patterning treatment, it is further demonstrated that a gripper can be assembled and photothermally controlled to readily grasp an object.

Effect of Crystal Transformation on the Intrinsic Defects and the Microwave Absorption Performance of Mo2 TiC2 Tx /RGO Microspheres.

The nitrides and carbides of transition metals are highly favored due to their excellent physical and chemical properties, among which MXene is a hot research topic for microwave absorption. Herein, the controlled preparation of 3D Mo2 TiC2 Tx -based microspheres toward microwave absorption is reported for the first time. With the merits of the performances of both reduced graphite oxide (RGO) and MXene sufficiently considered, the influence of carbonization temperature on the internal crystal structure and the effective microwave-material interaction surface of the prepared Mo2 TiC2 Tx /RGO is systematically investigated. The structure-activity relationships relating the apparent morphology and crystal structure to the microwave absorption performance are deeply explored, and the wave absorption mechanism is put forward as well. The results show that the Mo2 TiC2 Tx /RGO-700 product obtained after heating treatment at 700 °C exhibits excellent microwave absorption performance, with the RLmin being up to -55.1 dB@2.1 mm@13.8 GHz, and the corresponding effective absorption bandwidth covering 5.7 GHz. The outstanding microwave absorption characteristics are attributed to the appropriate impedance matching, high specific surface area, rich intrinsic defects, desirable conductivity, and strong multipolarization capabilities. This work enriches the types of MXene-based composite absorbers and provides a new strategy for controlled preparation of high-performance 3D composite absorbers.

Porous Liquid-Crystalline Networks with Hydrogel-Like Actuation and Reconfigurable Function.

A porous liquid-crystalline network (LCN), prepared by using a template method, was found to exhibit peculiar actuation functions. The creation of porosity makes the initially hydrophobic LCN behave like a hydrogel, capable of absorbing a large volume of water (up to ten times the sample size of LCN). When the amount of absorbed water is relatively small (about 100 % swelling ratio), the porous LCN displays anisotropic swelling in water and, in the same time, the retained uniaxial alignment of mesogens ensures a thermally induced shape change associated with a LC-isotropic phase transition. Combining the characteristic actuation mechanisms of LCN (order-disorder transition of mesogens) and hydrogel (water absorption), such porous LCNs can be explored for versatile stimuli-triggered shape transformations. Moreover, the porosity enables loading/removal/reloading of functional fillers such as ionic liquids, photothermal dyes and fluorophores, which imparts the porous LCN actuator with reconfigurable functions such as ionic conductivity, light-driven locomotion, and emissive color.

Liquid Crystalline Hydrogel with Thermally Induced Reversible Shape Change and Water-Triggered Shape Memory.

Liquid crystalline hydrogel (LCH) is synthesized through simultaneous polymerization of hydrophobic and hydrophilic monomers in an oil-in-water emulsion, resulting in phase-separated liquid crystalline network (LCN) embedded in a hydrogel matrix. This material features some properties and functions of both LCN and hydrogel, displaying stable LC phase over repeated hydration and dehydration cycles of the hydrogel matrix. Using mechanically stretched and photocrosslinked LCH, the thermally induced LC-isotropic phase transition in LCN domains can be translated into reversible macroscopic deformation of the LCH. Moreover, the LCH exhibits water absorption-controlled shape memory effect.

A Novel Side-Chain Liquid Crystal Elastomer Exhibiting Anomalous Reversible Shape Change.

Liquid crystalline elastomers (LCEs) have been actively investigated as stimuli-controlled actuators and soft robots. The basis of these applications is the ability of LCEs to undergo a reversible shape change upon a liquid crystalline (LC)-isotropic phase transition. Herein, we report the synthesis of a novel LCE based on a side-chain liquid crystalline polymer (SCLCP). In contrast to known LCEs, this LCE exhibits a striking anomalous shape change. Subjecting a mechanically stretched monodomain strip to LC-disorder phase transition, both the length and width of the strip contract in isotropic phase, and both elongate in LC phase. This thermally induced behaviour is the result of a subtle interplay between the relaxation of polymer main chain oriented along the stretching direction and the disordering of side-group mesogens oriented perpendicularly to the stretching direction. This finding points out potential design of LCEs of this peculiar type and possible applications to exploit.

A Multifunctional Dye-doped Liquid Crystal Polymer Actuator: Light-Guided Transportation, Turning in Locomotion, and Autonomous Motion.

A strip of a liquid crystal elastomer doped with a near-infrared dye with one side crosslinked monodomain and the other crosslinked polydomain along the thickness behaves like a multifunctional photoactuator without the need for a support. A flat strip with two ends fixed on substrate surface forms a moving bump under laser scanning, which can be used as light-fueled conveyor to transport an object. Cutting off and laser scanning the bump with two free ends makes a soft and flexible millimeter-scale crawler that can not only move straight and climb an inclined surface, but also undergo light-guided turning to right or left as a result of combined out-of-plane and in-plane actuation. Based on the self-shadowing mechanism, with one end of the strip fixed on substrate surface, it can execute a variety of autonomous arm-like movements under constant laser illumination, such as bending-unbending and twisting, depending on the laser incident angles with respect to the strip actuator.

An Optical Actuator Based on Gold-Nanoparticle-Containing Temperature-Memory Semicrystalline Polymers.

Photoresponsive actuators based on semicrystalline poly(ethylene-co-vinyl acetate) (EVA) loaded with small amounts of gold nanoparticles (AuNPs) are described. Upon absorption of light (532 nm), the heat released by the AuNPs raises the temperature in the irradiated region to Tlight to melt crystallites with lower melting temperatures (Tm Tlight . Once the light is turned off, the recrystallization of oriented chains in the actuation domains upon cooling gives rise to an expansion force. We show that the photoinduced contraction force, Tlight , and the speed for reaching Tlight can readily be adjusted, which makes EVA/AuNP a robust, fast optical actuation system tunable in both speed and magnitude. The material design can easily be extended to other temperature-memory semicrystalline polymers in combination with various light-absorbing and heat-generating additives.

Nanocomplexes of Photolabile Polyelectrolyte and Upconversion Nanoparticles for Near-Infrared Light-Triggered Payload Release.

A new approach to encapsulating charged cargo molecules into a nanovector and subsequently using near-infrared (NIR) light to trigger the release is demonstrated. NIR light-responsive nanovector was prepared through electrostatic interaction-driven complexation between negatively charged silica-coated upconversion nanoparticles (UCNP@silica, 87 nm hydrodynamic diameter, polydispersity index ∼0.05) and a positively charged UV-labile polyelectrolyte bearing pendants of poly(ethylene glycol) and o-nitrobenzyl side groups; whereas charged fluorescein (FLU) was loaded through a co-complexation process. By controlling the amount of polyelectrolyte, UCNP@silica can be covered by the polymer, whereas remaining dispersed in aqueous solution. Under 980 nm laser excitation, UV light emitted by UCNP is absorbed by photolytic side groups within polyelectrolyte, which results in cleavage of o-nitrobenzyl groups and formation of carboxylic acid groups. Such NIR light-induced partial reversal of positive charge to negative charge on the polyelectrolyte layer disrupts the equilibrium among UCNP@silica, polyelectrolyte, and FLU and, consequently, leads to release of FLU molecules.

A new function for thermal phase transition-based polymer actuators: autonomous motion on a surface of constant temperature.

It is very challenging to make materials capable of autonomous oscillation known in many living systems (such as the heartbeat). Herein, we describe an approach to creating a thermo-mechano-thermal feedback loop for thermal phase transition-based polymer actuators, which leads to hour-long, autonomous motion on a substrate surface of constant temperature. We investigated the variables that determine the amplitude and period of the motion, and demonstrated exemplary physical work powered by direct thermomechanical energy conversion. Such continuous motion of a solid polymer driven by thermal energy without the need for temperature up/down switching is unprecedented, and the validated feedback loop can be implemented into other thermal phase transition-based polymer actuators.

Time-dependent aggregation-induced enhanced emission, absorption spectral broadening, and aggregation morphology of a novel perylene derivative with a large D-π-A structure.

Strong aggregation-caused quenching of perylene diimides (PDI) is changed successfully by simple chemical modification with two quinoline moieties through C=C at the bay positions to obtain aggregation-induced enhanced emission (AIEE) of a perylene derivative (Cya-PDI) with a large π-conjugation system. Cya-PDI is weakly luminescent in the well-dispersed CH(3)CN or THF solutions and exhibits an evident time-dependent AIEE and absorption spectra broadening in the aggregated state. In addition, morphological inspection demonstrates that the morphology of the aggregated form of Cya-PDI molecules changed from plate-shaped to rod-like aggregates under the co-effects of time and water. An edge-to-face arrangement of aggregation was proposed and discussed. The fact that the Cya-PDI aggregates show a broad absorption covering the whole visible-light range and strong intermolecular interaction through π-π stacking in the solid state makes them promising materials for optoelectric applications.