Defected twisted ring topology for autonomous periodic flip-spin-orbit soft robot.

Periodic spin-orbit motion is ubiquitous in nature, observed from electrons orbiting nuclei to spinning planets orbiting the Sun. Achieving autonomous periodic orbiting motions, along circular and noncircular paths, in soft mobile robotics is crucial for adaptive and intelligent exploration of unknown environments-a grand challenge yet to be accomplished. Here, we report leveraging a closed-loop twisted ring topology with a defect for an autonomous soft robot capable of achieving periodic spin-orbiting motions with programmed circular and re-programmed irregular-shaped trajectories. Constructed by bonding a twisted liquid crystal elastomer ribbon into a closed-loop ring topology, the robot exhibits three coupled periodic self-motions in response to constant temperature or constant light sources: inside-out flipping, self-spinning around the ring center, and self-orbiting around a point outside the ring. The coupled spinning and orbiting motions share the same direction and period. The spinning or orbiting direction depends on the twisting chirality, while the orbital radius and period are determined by the twisted ring geometry and thermal actuation. The flip-spin and orbiting motions arise from the twisted ring topology and a bonding site defect that breaks the force symmetry, respectively. By utilizing the twisting-encoded autonomous flip-spin-orbit motions, we showcase the robot's potential for intelligently mapping the geometric boundaries of unknown confined spaces, including convex shapes like circles, squares, triangles, and pentagons and concaves shapes with multi-robots, as well as health monitoring of unknown confined spaces with boundary damages.

Coiled Carbon Nanotube Fibers Sheathed by a Reinforced Liquid Crystal Elastomer for Strong and Programmable Artificial Muscles.

Fibers of liquid crystal elastomers (LCEs) as promising artificial muscle show ultralarge and reversible contractile strokes. However, the contractile force is limited by the poor mechanical properties of the LCE fibers. Herein, we report high-strength LCE fibers by introducing a secondary network into the single-network LCE. The double-network LCE (DNLCE) shows considerable improvements in tensile strength (313.9%) and maximum actuation stress (342.8%) compared to pristine LCE. To facilitate the controllability and application, a coiled artificial muscle fiber consisting of DNLCE-coated carbon nanotube (CNT) fiber is prepared. When electrothermally driven, the artificial muscle fiber outputs a high actuation performance and programmable actuation. Furthermore, by knitting the artificial muscle fibers into origami structures, an intelligent gripper and crawling inchworm robot have been demonstrated. These demonstrations provide promising application scenarios for advanced intelligent systems in the future.

Elastocaloric Response of Isotropic Liquid Crystalline Elastomers.

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.

A Self-Healing Conductive Elastomer Based on a Polymerizable Deep Eutectic Solvent.

Conductive elastomers are extensively used in electronics; however, they are prone to mechanical damage, have shortened service life, and cause environmental pollution and resource waste under the influence of external factors. Therefore, conductive elastomers with rapid self-healing properties are crucial for solving these problems. To that end, a conductive elastomer based on a polymerizable deep eutectic solvent as the matrix is developed in this study. The contents of certain small molecules and conductive particles are adjusted to yield a conductive elastomer with excellent comprehensive performance. The elastomer exhibited noteworthy fracture strength (15.7 MPa), ultrahigh fracture elongation (2400%), excellent light transmittance (95.6%), and remarkable self-healing characteristics, with complete electrical healing achieved within 0.6 s, ≈63% strain, and ≈64% stress recovered within 1 min, and healing efficiency close to 99% realized within 24 h. By leveraging these properties, the elastomer is used to construct a sensor that exhibited a gauge factor of ≈0.574 in the strain range 0-2400% and excellent stability. Moreover, the CCK-8 toxicity test and fluorescence staining experiment have demonstrated that conductive elastomers have excellent cell compatibility and also have excellent potential in the field of biomedicine. In particular, the sensor is effectively applied in human motion detection, health monitoring.

Grafted Alkene Chains: Triggers for Defeating Contact Thermal Resistance in Composite Elastomers.

The pursuit of enhancing the heat transfer performance of composite elastomers as the thermal interface materials (TIMs) is a compelling and timely endeavor, given the formidable challenges posed by interfacial thermal transport in the domains of energy science, electronic technology, etc. Despite the efficacy of phase change materials (PCMs) in enhancing composite elastomers' interfacial compatibility, thereby reducing contact thermal resistance for heat transfer improvement, their leakage post-transition has impeded the widespread adoption of this approach. Herein, a strategy is proposed for developing a solid-solid phase change composite elastomer by grafting alkene chains onto the crosslink network to eliminate the possibility of leakage. A series characterization suggest that the resulting material possesses a self-adjusting interfacial compatibility feature to help reduce contact thermal resistance for heat transfer facilitating. The investigations on adhesion strength and surface energy reveal that the presence of amorphous grafted alkane chains at the interface facilitates easier absorption onto the contacting solid surface, enhancing intermolecular interactions at the interface to promote across-boundary heat transfer. By integrating these findings with the thermal performance evaluation of composite elastomers using a real test vehicle, valuable insights are gained for the design of composite elastomers, establishing their suitability as TIMs in relevant fields.

Electroactive Bi-Functional Liquid Crystal Elastomer Actuators.

Liquid crystal elastomers (LCEs) with promising applications in the field of actuators and soft robotics are reported. However, most of them are activated by external heating or light illumination. The examples of electroactive LCEs are still limited; moreover, they are monofunctional with one type of deformation (bending or contraction). Here, the study reports on trilayer electroactive LCE (eLCE) by intimate combination of LCE and ionic electroactive polymer device (i-EAD). This eLCE is bi-functional and can perform either bending or contractile deformations by the control of the low-voltage stimulation. By applying a voltage of ±2 V at 0.1 Hz, the redox behavior and associated ionic motion provide a bending strain difference of 0.80%. Besides, by applying a voltage of ±6 V at 10 Hz, the ionic current-induced Joule heating triggers the muscle-like linear contraction with 20% strain for eLCE without load. With load, eLCE can lift a weight of 270 times of eLCE-actuator weight, while keeping 20% strain and affording 5.38 kJ·m-3 work capacity. This approach of combining two smart polymer technologies (LCE and i-EAD) in a single device is promising for the development of smart materials with multiple degrees of freedom in soft robotics, electronic devices, and sensors.

Rotini-like MXene@LCE Actuator with Diverse and Programmable Actuation Based on Dual-mode Synergy.

Liquid crystalline elastomer (LCE) exhibits muscle-like actuation upon order-disturbed stimulus, offering ample room for designing soft robotic systems. Multimodal LCE is demonstrated to unleash the potential to perform multitasks. However, each actuation mode is typically isolated. In contrast, coordination between different actuation modes based on an MXene-doped LCE is realized, whose actuation can be triggered either by directly heating/cooling or using near-infrared light due to the photo-thermal effect of MXene. As such, the two activation modes (heat and light) not only can work individually to offer stable actuation under different conditions but also can collaborate synergistically to generate more intelligent motions, such as achieving the brake and turn of an autonomous rolling. The principle therefore can diversify the design principles for multifunctional soft actuators and robotics.

Reversible Sensing Technologies Using Upcycled TPEE: Crafting pH and Light Responsive Materials towards Sustainable Monitoring.

Multiresponsive materials with reversible and durable characteristics are indispensable because of their promising applications in environmental change detections. To fabricate multiresponsive materials in mass production, however, complex reactions and impractical situations are often involved. Herein, a dual responsive (light and pH) spiropyran-based smart sensor fabricated by a simple layer-by-layer (LbL) assembly process from upcycled thermoplastic polyester elastomer (TPEE) materials derived from recycled polyethylene terephthalate (r-PET) is proposed. Positively charged chitosan solutions and negatively charged merocyanine-COOH (MC-COOH) solutions are employed in the LbL assembly technique, forming the chitosan-spiropyran deposited TPEE (TPEE-CH-SP) film. Upon UV irradiation, the spiropyran-COOH (SP-COOH) molecules on the TPEE-CH-SP film undergo the ring-opening isomerization, along with an apparent color change from colorless to purple, to transform into the MC-COOH molecules. By further exposing the TPEE-CH-MC film to hydrogen chloride (HCl) and nitric acid (HNO3) vapors, the MC-COOH molecules can be transformed into protonated merocyanine-COOH (MCH-COOH) with the simultaneous color change from purple to yellow.

Wearable and Recyclable Water-Toleration Sensor Derived from Lipoic Acid.

Flexible wearable sensors recently have made significant progress in human motion detection and health monitoring. However, most sensors still face challenges in terms of single detection targets, single application environments, and non-recyclability. Lipoic acid (LA) shows a great application prospect in soft materials due to its unique properties. Herein, ionic conducting elastomers (ICEs) based on polymerizable deep eutectic solvents consisting of LA and choline chloride are prepared. In addition to the good mechanical strength, high transparency, ionic conductivity, and self-healing efficiency, the ICEs exhibit swelling-strengthening behavior and enhanced adhesion strength in underwater environments due to the moisture-induced association of poly(LA) hydrophobic chains, thus making it possible for underwater sensing applications, such as underwater communication. As a strain sensor, it exhibits highly sensitive strain response with repeatability and durability, enabling the monitoring of both large and fine human motions, including joint movements, facial expressions, and pulse waves. Furthermore, due to the enhancement of ion mobility at higher temperatures, it also possesses excellent temperature-sensing performance. Notably, the ICEs can be fully recycled and reused as a new strain/temperature sensor through heating. This study provides a novel strategy for enhancing the mechanical strength of poly(LA) and the fabrication of multifunctional sensors.

Highly Durable Silicone-Based Elastomers Achieved Through the Synergy of Bi-Incompatible Soft Segments and Multi-Scale Hydrogen Bonds.

Developing a silicone elastomer with high strength, exceptional toughness, good crack tolerance, healability, and recyclability, poses significant challenges due to the inherent trade-offs between these properties. Herein, the design of silicone-based elastomers with a nanoscopic microphase separation structure and comprehensive mechanical properties is achieved by combining bi-incompatible soft segments and multi-scale hydrogen bonds. The formation of multi-scale hydrogen bonds involving urethane, urea, and 2-ureido-4[1H]-pyrimidinone (UPy) facilitates efficient reversible crosslinking of the synthesized polymer containing thermodynamically incompatible poly(dimethylsiloxane) (PDMS) and poly(propylene glycol) (PPG). The dynamic dissociation and recombination of hydrogen bonds, coupled with the forced compatibility and spontaneous separation of bi-incompatible soft segments, can effectively dissipate energy, particularly in the crack region during the stretching process. The obtained silicone-based elastomer exhibits a high break strength of 8.0 MPa, good elongation at break of 1910%, ultrahigh toughness of 67.8 MJ m-3, and unprecedented fracture energy of 31.8 kJ m-2 while maintaining their thermal stability, hydrophobicity, healability, and recyclability. This resilient and long-lasting silicone-based elastomer exhibits significant potential for use in flexible electronic devices.

Programmable, Self-Healable, and Photochromic Liquid Crystal Elastomers Based on Dynamic Hindered Urea Bonds for Biomimetic Flowers.

Recently, researchers have been exploring the use of dynamic covalent bonds (DCBs) in the construction of exchangeable liquid crystal elastomers (LCEs) for biomimetic actuators and devices. However, a significant challenge remains in achieving LCEs with both excellent dynamic properties and superior mechanical strength and stability. In this study, a diacrylate-functionalized monomer containing dynamic hindered urea bonds (DA-HUB) is employed to prepare exchangeable LCEs through a self-catalytic Michael addition reaction. By incorporating DA-HUB, the LCE system benefits from DCBs and hydrogen bonding, leading to materials with high mechanical strength and a range of dynamic properties such as programmability, self-healing, and recyclability. Leveraging these characteristics, bilayer LCE actuators with controlled reversible thermal deformation and outstanding dimensional stability are successfully fabricated using a simple welding method. Moreover, a biomimetic triangular plum, inspired by the blooming of flowers, is created to showcase reversible color and shape changes triggered by light and heat. This innovative approach opens new possibilities for the development of biomimetic and smart actuators and devices with multiple functionalities.

Soft Synthetic Cells with Mobile Membrane Ligands for Ex Vivo Expansion of Therapy-Relevant T Cell Phenotypes.

The expansion of T cells ex vivo is crucial for effective immunotherapy but currently limited by a lack of expansion approaches that closely mimic in vivo T cell activation. Taking inspiration from bottom-up synthetic biology, a new synthetic cell technology is introduced based on dispersed liquid-liquid phase-separated droplet-supported lipid bilayers (dsLBs) with tunable biochemical and biophysical characteristics, as artificial antigen presenting cells (aAPCs) for ex vivo T cell expansion. These findings obtained with the dsLB technology reveal three key insights: first, introducing laterally mobile stimulatory ligands on soft aAPCs promotes expansion of IL-4/IL-10 secreting regulatory CD8+ T cells, with a PD-1 negative phenotype, less prone to immune suppression. Second, it is demonstrated that lateral ligand mobility can mask differential T cell activation observed on substrates of varying stiffness. Third, dsLBs are applied to reveal a mechanosensitive component in bispecific Her2/CD3 T cell engager-mediated T cell activation. Based on these three insights, lateral ligand mobility, alongside receptor- and mechanosignaling, is proposed to be considered as a third crucial dimension for the design of ex vivo T cell expansion technologies.

A Molecular Rheology Dynamics Study on 3D Printing of Liquid Crystal Elastomers.

This work presents a rheological study of a biocompatible and biodegradable liquid crystal elastomer (LCE) ink for three dimensional (3D) printing. These materials have shown that their structural variations have an effect on morphology, mechanical properties, alignment, and their impact on cell response. Within the last decade LCEs are extensively studied as potential printing materials for soft robotics applications, due to the actuation properties that are produced when liquid crystal (LC) moieties are induced through external stimuli. This report utilizes experiments and coarse-grained molecular dynamics to study the macroscopic rheology of LCEs in nonlinear shear flow. Results from the shear flow simulations are in line with the outcomes of these experimental investigations. This work believes the insights from these results can be used to design and print new material with desirable properties necessary for targeted applications.

Highly Stretchable, Transparent, Self-Healing Ion-Conducting Elastomers for Long-Term Reliable Human Motion Detection.

The flexible electronic sensor is a critical component of wearable devices, generally requiring high stretchability, excellent transmittance, conductivity, self-healing capability, and strong adhesion. However, designing ion-conducting elastomers meeting all these requirements simultaneously remains a challenge. In this study, a novel approach is presented to fabricate highly stretchable, transparent, and self-healing ion-conducting elastomers, which are synthesized via photo-polymerization of two polymerizable deep eutectic solvents (PDESs) monomers, i.e., methacrylic acid (MAA)/choline chloride (ChCl) and itaconic acid (IA)/ChCl. The as-prepared ion-conducting elastomers possess outstanding properties, including high transparency, conductivity, and the capability to adhere to various substrates. The elastomers also demonstrate ultra-stretchability (up to 3900%) owing to a combination of covalent cross-linking and noncovalent cross-linking. In addition, the elastomers can recover up to 3250% strain and over 94.5% of their original conductivity after self-healing at room temperature for 5 min, indicating remarkable mechanical and conductive self-healing abilities. When utilized as strain sensors to monitor real-time motion of human fingers, wrist, elbow, and knee joints, the elastomers exhibit stable and strong repetitive electrical signals, demonstrating excellent sensing performance for large-scale movements of the human body. It is anticipated that these ion-conducting elastomers will find promising applications in flexible and wearable electronics.

Fabrication of Soft Transparent Patient-Specific Vascular Models with Stereolithographic 3D printing and Thiol-Based Photopolymerizable Coatings.

An ideal vascular phantom should be anatomically accurate, have mechanical properties as close as possible to the tissue, and be sufficiently transparent for ease of visualization. However, materials that enable the convergence of these characteristics have remained elusive. The fabrication of patient-specific vascular phantoms with high anatomical fidelity, optical transparency, and mechanical properties close to those of vascular tissue is reported. These final properties are achieved by 3D printing patient-specific vascular models with commercial elastomeric acrylic-based resins before coating them with thiol-based photopolymerizable resins. Ternary thiol-ene-acrylate chemistry is found optimal. A PETMP/allyl glycerol ether (AGE)/polyethylene glycol diacrylate (PEGDA) coating with a 30/70% AGE/PEGDA ratio applied on a flexible resin yielded elastic modulus, UTS, and elongation of 3.41 MPa, 1.76 MPa, and 63.2%, respectively, in range with the human aortic wall. The PETMP/AGE/PEGDA coating doubled the optical transmission from 40% to 80%, approaching 88% of the benchmark silicone-based elastomer. Higher transparency correlates with a decrease in surface roughness from 2000 to 90 nm after coating. Coated 3D-printed anatomical replicas are showcased for pre-procedural planning and medical training with good radio-opacity and echogenicity. Thiol-click chemistry coatings, as a surface treatment for elastomeric stereolithographic 3D-printed objects, address inherent limitations of photopolymer-based additive manufacturing.

Flexoelectricity in soft elastomers and the molecular mechanisms underpinning the design and emergence of giant flexoelectricity.

Soft robotics requires materials that are capable of large deformation and amenable to actuation with external stimuli such as electric fields. Energy harvesting, biomedical devices, flexible electronics, and sensors are some other applications enabled by electroactive soft materials. The phenomenon of flexoelectricity is an enticing alternative that refers to the development of electric polarization in dielectrics when subjected to strain gradients. In particular, flexoelectricity offers a direct linear coupling between a highly desirable deformation mode (flexure) and electric stimulus. Unfortunately, barring some exceptions, the flexoelectric effect is quite weak and rather substantial bending curvatures are required for an appreciable electromechanical response. Most experiments in the literature appear to confirm modest flexoelectricity in polymers although perplexingly, a singular work has measured a "giant" effect in elastomers under some specific conditions. Due to the lack of an understanding of the microscopic underpinnings of flexoelectricity in elastomers and a commensurate theory, it is not currently possible to either explain the contradictory experimental results on elastomers or pursue avenues for possible design of large flexoelectricity. In this work, we present a statistical-mechanics theory for the emergent flexoelectricity of elastomers consisting of polar monomers. The theory is shown to be valid in broad generality and leads to key insights regarding both giant flexoelectricity and material design. In particular, the theory shows that, in standard elastomer networks, combining stretching and bending is a mechanism for obtaining giant flexoelectricity, which also explains the aforementioned, surprising experimental discovery.

Synthetic and natural rubber associated chemicals drive functional and structural changes as well as adaptations to antibiotics in in vitro marine microbiomes.

The leaching of additives from plastics and elastomers (rubbers) has raised concerns due to their potential negative impacts on the environment and the development of antibiotic resistance. In this study, we investigated the effects of chemicals extracted from two types of rubber on microbiomes derived from a benthic sea urchin and two pelagic fish species. Additionally, we examined whether bacterial communities preconditioned with rubber-associated chemicals displayed adaptations to antibiotics. At the highest tested concentrations of chemicals, we observed reduced maximum growth rates and yields, prolonged lag phases, and increased alpha diversity. While the effects on alpha and beta diversity were not always conclusive, several bacterial genera were significantly influenced by chemicals from the two rubber sources. Subsequent exposure of sea urchin microbiomes preconditioned with rubber chemicals to the antibiotic ciprofloxacin resulted in decreased maximum growth rates. This indicates a more sensitive microbiome to ciprofloxacin when preconditioned with rubber chemicals. Although no significant interaction effects between rubber chemicals and ciprofloxacin exposure were observed in bacterial alpha and beta diversity, we observed log-fold changes in two bacterial genera in response to ciprofloxacin exposure. These findings highlight the structural and functional alterations in microbiomes originating from various marine species when exposed to rubber-associated chemicals and underscore the potential risks posed to marine life.

Nanomagnetic Elastomers for Realizing Highly Responsive Micro- and Nanosystems.

Evolution has produced natural systems that generate motion and sense external stimuli at the micro- and nanoscales. At extremely small scales, the intricate motions and large deformations shown by these biosystems are due to a tipping balance between their structural compliance and the actuating force generated in them. Artificially mimicking such ingenious systems for scientific and engineering applications has been approached through the development and use of different smart materials mostly limited to microscale dimensions. To push the application range down to the nanoscale, we developed a material preparation process that yields a library of nanomagnetic elastomers with high magnetic particle concentrations. Through this process, we have realized a material with the highest magnetic-to-elastic force ratio, as is shown by an extensive mechanical and magnetic characterization of the materials. Furthermore, we have fabricated and actuated micro- and nanostructures mimicking cilia, demonstrating the extreme compliance and responsiveness of the developed materials.

Dynamic-Bond-Mediated Chain Reptation Enhances Energy Dissipation of Elastomers.

Vibrations with various frequencies in daily life and industry can cause health hazards and fatigue failure of critical structures, which requires the development of elastomers with high energy dissipation at desired frequencies. Current strategies relying on tuning characteristic relaxation time of polymer chains are mostly qualitative empirical methods, and it is difficult to precisely control damping performances. Here, we report a general strategy for constructing dynamic crosslinked polymer fluid gels that provide controllable ultrahigh energy dissipation. This is realized by dynamic-bond-mediated chain reptation of polymer fluids in a crosslinked network, where the characteristic time of chain reptation is dominated by the presence of well-defined dissociation time of dynamic bonds and almost independent of their molar mass. Using prototypical supramolecular polydimethylsiloxane elastomers, we demonstrate that dynamic crosslinked polymer fluid gels exhibit a controllable ultrahigh damping performance at desired frequencies (10-2~102 Hz), exceeding that of typical state-of-the-art silicone damping materials. Their shock absorption is over 300 % higher than that of commercial silicone rubber under the same impact force.

Upcycling of Carbon Fiber/Thermoset Composites into High-Performance Elastomers and Repurposed Carbon Fibers.

Recycling of carbon fiber-reinforced polymer composites (CFRCs) based on thermosetting plastics is difficult. In the present study, high-performance CFRCs are fabricated through complexation of aromatic pinacol-cross-linked polyurethane (PU-AP) thermosets with carbon fiber (CF) cloths. PU-AP thermosets exhibit a breaking strength of 95.5 MPa and toughness of 473.6 MJ m-3 and contain abundant hydrogen-bonding groups, which can have strong adhesion with CFs. Because of the high interfacial adhesion between CF cloths and PU-AP thermosets and high toughness of PU-AP thermosets, CF/PU-AP composites possess a high tensile strength of >870 MPa. Upon heating in N,N-dimethylacetamide (DMAc) at 100 °C, the aromatic pinacols in the CF/PU-AP composites can be cleaved, generating non-destructive CF cloths and linear polymers that can be converted to high-performance elastomers. The elastomers are mechanically robust, healable, reprocessable, and damage-resistant with an extremely high tensile strength of 74.2 MPa and fracture energy of 149.6 kJ m-2. As a result, dissociation of CF/PU-AP composites enables the recovery of reusable CF cloths and high-performance elastomers, thus realizing the upcycling of CF/PU-AP composites.