Highly Stretchable, Self-Healing, and Sensitive E-Skins at -78 °C for Polar Exploration.

Ultralow temperature-tolerant electronic skins (e-skins) can endow polar robots with tactile feedback for exploring in extremely cold polar environments. However, it remains a challenge to develop e-skins that enable sensitive touch sensation and self-healing at ultralow temperatures. Herein, we describe the development of a sensitive robotic hand e-skin that can stretch, self-heal, and sense at temperatures as low as -78 °C. The elastomeric substrate of this e-skin is based on poly(dimethylsiloxane) supramolecular polymers and multistrength dynamic H-bonds, in particular with quadruple H-bonding motifs (UPy). The structure-performance relationship of the elastomer at ultralow temperatures is investigated. The results show that elastomers with side-chain UPy units exhibit higher stretchability (∼3257%) and self-healing efficiency compared to those with main-chain UPy units. This is attributed to the lower binding energy variation and lower potential well. Based on the elastomer with side-chain UPy and man-made electric ink, a sensitive robotic hand e-skin for usage at -78 °C is constructed to precisely sense the shape of objects and specific symbols, and its sensation can completely self-recover after being damaged. The findings of this study contribute to the concept of using robotic hands with e-skins in polar environments that make human involvement limited, dangerous, or impossible.

Liquid Crystal Networks Meet Water: It's Complicated!

Soft robots are composed of compliant materials that facilitate high degrees of freedom, shape-change adaptability, and safer interaction with humans. An attractive choice of material for soft robotics is crosslinked networks of liquid crystal polymers (LCNs), as they are responsive to a wide variety of external stimuli and capable of undergoing fast, programmable, complex shape morphing, which allows for their use in a wide range of soft robotic applications. However, unlike hydrogels, another popular material in soft robotics, LCNs have limited applicability in flooded or aquatic environments. This can be attributed not only to the poor efficiency of common LCN actuation methods underwater but also to the complicated relationship between LCNs and water. In this review, the relationship between water and LCNs is elaborated and the existing body of literature is surveyed where LCNs, both hygroscopic and non-hygroscopic, are utilized in aquatic soft robotic applications. Then the challenges LCNs face in widespread adaptation to aquatic soft robotic applications are discussed and, finally, possible paths forward for their successful use in aquatic environments are envisaged.

Programmable and Self-Healable Liquid Crystal Elastomer Actuators Based on Halogen Bonding.

Shape-changing polymeric materials have gained significant attention in the field of bioinspired soft robotics. However, challenges remain in versatilizing the shape-morphing process to suit different tasks and environments, and in designing systems that combine reversible actuation and self-healing ability. Here, we report halogen-bonded liquid crystal elastomers (LCEs) that can be arbitrarily shape-programmed and that self-heal under mild thermal or photothermal stimulation. We incorporate halogen-bond-donating diiodotetrafluorobenzene molecules as dynamic supramolecular crosslinks into the LCEs and show that these relatively weak crosslinks are pertinent for their mechanical programming and self-healing. Utilizing the halogen-bonded LCEs, we demonstrate proof-of-concept soft robotic motions such as crawling and rolling with programmed velocities. Our results showcase halogen bonding as a promising, yet unexplored tool for the preparation of smart supramolecular constructs for the development of advanced soft actuators.

Force-induced ion generation in zwitterionic hydrogels for a sensitive silent-speech sensor.

Human-sensitive mechanosensation depends on ionic currents controlled by skin mechanoreceptors. Inspired by the sensory behavior of skin, we investigate zwitterionic hydrogels that generate ions under an applied force in a mobile-ion-free system. Within this system, water dissociates as the distance between zwitterions reduces under an applied pressure. Meanwhile, zwitterionic segments can provide migration channels for the generated ions, significantly facilitating ion transport. These combined effects endow a mobile-ion-free zwitterionic skin sensor with sensitive transduction of pressure into ionic currents, achieving a sensitivity up to five times that of nonionic hydrogels. The signal response time, which relies on the crosslinking degree of the zwitterionic hydrogel, was ~38 ms, comparable to that of natural skin. The skin sensor was incorporated into a universal throat-worn silent-speech recognition system that transforms the tiny signals of laryngeal mechanical vibrations into silent speech.

Halogen-bonded shape memory polymers.

Halogen bonding (XB), a non-covalent interaction between an electron-deficient halogen atom and a Lewis base, is widely adopted in organic synthesis and supramolecular crystal engineering. However, the roadmap towards materials applications is hindered by the challenges in harnessing this relatively weak intermolecular interaction to devise human-commanded stimuli-responsive soft materials. Here, we report a liquid crystalline network comprising permanent covalent crosslinks and dynamic halogen bond crosslinks, which possess reversible thermo-responsive shape memory behaviour. Our findings suggest that I···N halogen bond, a paradigmatic motif in crystal engineering studies, enables temporary shape fixation at room temperature and subsequent shape recovery in response to human body temperature. We demonstrate versatile shape programming of the halogen-bonded polymer networks through human-hand operation and propose a micro-robotic injection model for complex 1D to 3D shape morphing in aqueous media at 37 °C. Through systematic structure-property-performance studies, we show the necessity of the I···N crosslinks in driving the shape memory effect. The halogen-bonded shape memory polymers expand the toolbox for the preparation of smart supramolecular constructs with tailored mechanical properties and thermoresponsive behaviour, for the needs of, e.g., future medical devices.

Feedback-controlled hydrogels with homeostatic oscillations and dissipative signal transduction.

Driving systems out of equilibrium under feedback control is characteristic for living systems, where homeostasis and dissipative signal transduction facilitate complex responses. This feature not only inspires dissipative dynamic functionalities in synthetic systems but also poses great challenges in designing novel pathways. Here we report feedback-controlled systems comprising two coupled hydrogels driven by constant light, where the system can be tuned to undergo stable homeostatic self-oscillations or damped steady states of temperature. We demonstrate that stable temperature oscillations can be utilized for dynamic colours and cargo transport, whereas damped steady states enable signal transduction pathways. Here mechanical triggers cause temperature changes that lead to responses such as bending motions inspired by the single-touch mechanoresponse in Mimosa pudica and the frequency-gated snapping motion inspired by the plant arithmetic in the Venus flytrap. The proposed concepts suggest generalizable feedback pathways for dissipative dynamic materials and interactive soft robotics.

A Degradable-Renewable Ionic Skin Based on Edible Glutinous Rice Gel.

Traditional wearable devices are commonly nonrecyclable and nondegradable, resulting in energy waste and environmental pollution. Here, a household degradable and renewable ionic skin based on edible glutinous rice gel is developed for a strain, temperature and salivary enzyme activity sensor. This gel depends on intermolecular and intramolecular H-bonds among amylopectin and amylose, and this presents excellent skin-like properties, including stretchability, self-healing property, and adhesion to various substrates. The glutinous rice gel-based skin sensor can be used to monitor vital signs and physiological parameters such as body temperature and heart rate. The sensor also achieves specific speech recognition and detects temperature and body micromovements, which provides the potential to reconstruct language or sensory/motor functions. More importantly, because of the excellent biocompatibility and degradability, the sensor can directly detect the activity of human salivary amylase, which is useful for diagnosing pancreas-, kidney-, and spleen-related diseases in the elderly. Finally, the raw material of ionic skin that originates from traditional grains is degradable and renewable as well as it can be used to prepare household wearable devices. Hence, this work not only extends the application of wearable electronics in daily life but also facilitates health monitoring in the elderly and improves their quality of life.

Antifouling Fibrous Membrane Enables High Efficiency and High-Flux Microfiltration for Water Treatment.

Membrane biofouling has long been a major obstacle to highly efficient water treatment. The modification of the membrane surface with hydrophilic materials can effectively enhance biofouling resistance. However, the water flux of the membranes is often compromised for the improvement of antifouling properties. In this work, a composite membrane composed of a zwitterionic hydrogel and electrospinning fibers was prepared by a spin-coating and UV cross-linking process. At the optimum conditions, the composite membrane could effectively resist the biofouling contaminations, as well as purify polluted water containing bacteria or diatoms with a high flux (1349.2 ± 85.5 L m-2 h-1 for 106 CFU mL-1 of an Escherichia coli solution). Moreover, compared with the commercial poly(ether sulfone) (PES) membrane, the membrane displayed an outstanding long-term filtration performance with a lower water flux decline. Therefore, findings in this work provide an effective antifouling modification strategy for microfiltration membranes and hold great potential for developing antifouling membranes for water treatment.

A Zwitterionic-Aromatic Motif-Based ionic skin for highly biocompatible and Glucose-Responsive sensor.

Electronic skins that can sense external stimuli have been of great significance in artificial intelligence and smart wearable devices in recent years. However, most of current skin materials are unable to achieve high biocompatibility and anti-bacterial activity, which are particularly critical to wearable sensors for neonatal/premature monitoring or tissue-interfaced biosensors (such as electronic wound dressing and smart contact lens). Herein, a zwitterionic-aromatic motif-based conductive hydrogel with electrostatic and π-π interactions is designed for the development of ionic skin sensors. The hydrogel possesses high biocompatibility, anti-bacterial activity, especially glucose-responsive property which has not been achieved by previous ionic skins. Due to its unique molecular design, the zwitterionic-aromatic skin sensor exhibits excellent mechanical properties (robust elasticity and large stretchability) and high-sensitive pressure detection (including a gentle finger touch, small water droplets, and vocal cord vibration). More importantly, aromatic motives in phenylboronic acid segments endow the skin with glucose-responsive property. This skin sensor not only shows great potential in wearable e-skins, but also possesses a promising property for the tissue-interfaced and implantable continuous-glucose-monitor biosensors such as smart wound dressing with a high demand of biocompatibility.

Universal Intraductal Surface Antifouling Coating Based on an Amphiphilic Copolymer.

Surface modification on the inner wall of medical or industrial polymeric catheters with a high length/diameter ratio is highly desired. Herein, a universal and facile method based on an amphiphilic copolymer was developed to immobilize an intraductal surface antifouling coating for a variety of polymeric catheters. A fouling-repelled thin layer was formed by swelling-driven adsorption via directly perfusing an amphiphilic copolymer [polyvinylpyrrolidone-polydimethylsiloxane-polyvinylpyrrolidone (PVP-PDMS-PVP)] solution into catheters. In this copolymer, hydrophobic PDMS was embedded into a shrinking cross-linked network of catheters; also, PVP segments migrated to the surface under driving water to form a hydrophilic antifouling coating. Moreover, because of the coordination between I2 and pyrrolidone of PVP, the copolymer-modified intraductal surface was then infused with aqueous I2 to form the PVP-I2 complex, endowing this coating with bactericidal activity. Notably, diverse catheters with arbitrary shapes (circular, rectangular, triangular, and hexagonal) and different components (silicone, polyurethane, and polyethylene) were also verified to work using this interfacial interpenetration strategy. The findings in this work provide a new avenue toward facile and universal fabrication of intraductal surface antifouling catheters, creating a superior option for decreasing the consumable costs in industrial production and alleviating the pain of replacing catheters for patients.

Amphiphilic Marine Antifouling Coatings Based on a Hydrophilic Polyvinylpyrrolidone and Hydrophobic Fluorine-Silicon-Containing Block Copolymer.

The development of environmentally friendly and highly efficient antifouling coatings is vastly desirable in the marine industry. Herein, we prepared a novel amphiphilic block copolymer that combined hydrophilic polyvinylpyrrolidone (PVP) with hydrophobic poly(1-(1H,1H,2H,2H-perfluorodecyloxy)-3-(3,6,9-trioxadecyloxy)-propan-2-yl acrylate) (PFA) and polydimethylsiloxane (PDMS). The amphiphilic copolymer (PVP-PFA-PDMS) was blended into a cross-linked PDMS matrix to form a set of controlled surface composition and surface-renewal coatings with efficient antifouling and fouling-release properties. These coatings incorporated the biofouling settlement resistance ability attributed to the hydrophilic PVP segments and the reduced adhesion strength attributed to the low surface energy of fluorine-silicon-containing segments. As expected, the coatings showed an excellent antifouling performance against bacteria and marine unicellular Navicula parva diatoms (98.1 and 98.5% of reduction, respectively) and fouling-release performance against pseudobarnacle adhesion (84.3% of reduction) compared to the pristine PDMS coating. Moreover, a higher-content PVP-based coatings presented higher ability to resist biofouling adhesion. The nontoxic antifouling coating developed in this paper hold the potential to be applied in a variety of marine industrial facilities.

MOF-Based Antibiofouling Hemoadsorbent for Highly Efficient Removal of Protein-Bound Bilirubin.

A metal-organic framework (MOF)-based antibiofouling hemoadsorbent (PCB-MIL101) was developed through a facile encapsulation of MIL-101(Cr) in zwitterionic poly carboxybetaine (PCB) hydrogel. PCB-MIL101 possessed strong mechanical strength and superior hemocompatibility, ensuring its safety in hemoperfusion applications. In addition, it showed efficient and effective adsorption toward bilirubin (BR), and its maximum adsorption capacity was ∼583 mg g-1. Moreover, due to the protection of antibiofouling PCB hydrogel, PCB-MIL101 showed ability to resist protein adsorption, thus working effectively to remove BR molecules from their binding albumin in biological solutions. The finding in this study provides a novel insight into developing MOF-based hemoadsorbents for the improvement of hemoperfusion therapies.

Metal-Organic Framework Traps with Record-High Bilirubin Removal Capacity for Hemoperfusion Therapy.

Adsorption-based hemoperfusion has been widely used to remove toxins from the blood of patients suffering acute liver failure (ALF). However, its detoxification effect has been severely hampered by the unsatisfactory adsorption performance of clinically used porous adsorbents, such as activated carbon (AC) and adsorption resin. Herein, two cage-based metal-organic frameworks (MOFs), PCN-333 (constructed from 4,4,4-s-triazine-2,4,6-triyl-tribenzoic acid (H3TATB) ligands and Al3 metal clusters) and MOF-808 (constructed from 1,3,5-benzenetricarboxylic acid (H3BTC) ligands and Zr6 metal clusters), are introduced for highly efficient hemoperfusion. They possess negligible hemolytic activity and can act as "bilirubin traps" to achieve outstanding adsorption performance toward bilirubin, a typical toxin related to ALF. Notably, PCN-333 shows a record-high adsorption capacity (∼1003.8 mg g-1) among various bilirubin adsorbents previously reported. More importantly, they can efficiently adsorb bilirubin in bovine serum albumin (BSA) solution or even in 100% fetal bovine serum (FBS) due to their high selectivity. Strikingly, the adsorption rate and capacity of PCN-333 in biological solutions are approximately four times faster and 69 times higher than those of clinical AC, respectively. Findings in this work pave a new avenue to overcome the challenge of low adsorption efficiency and capacity in hemoperfusion therapy.

Universally autonomous self-healing elastomer with high stretchability.

Developing autonomous self-healing materials for applications in harsh conditions is challenging because the reconstruction of interaction in material for self-healing will experience significant resistance and fail. Herein, a universally self-healing and highly stretchable supramolecular elastomer is designed by synergistically incorporating multi-strength H-bonds and disulfide metathesis in polydimethylsiloxane polymers. The resultant elastomer exhibits high stretchability for both unnotched (14000%) and notched (1300%) samples. It achieves fast autonomous self-healing under universal conditions, including at room temperature (10 min for healing), ultralow temperature (-40 °C), underwater (93% healing efficiency), supercooled high-concentrated saltwater (30% NaCl solution at -10 °C, 89% efficiency), and strong acid/alkali environment (pH = 0 or 14, 88% or 84% efficiency). These properties are attributable to synergistic interaction of the dynamic strong and weak H-bonds and stronger disulfide bonds. A self-healing and stretchable conducting device built with the developed elastomer is demonstrated, thereby providing a direction for future e-skin applications.

Environmentally Friendly Marine Antifouling Coating Based on a Synergistic Strategy.

The development of environmentally friendly and long-term marine antifouling coating remains a huge challenge in the maritime industry. For this purpose, we developed a novel and efficient antifouling coating based on a synergistic strategy, incorporating contact inhibition, fouling repelling, and antifouling properties. Results demonstrated that the coating could efficiently resist the adhesion of protein, bacteria, and Navicula diatoms. More importantly, marine field tests showed the coating could efficiently inhibit biofouling for at least 8 months. This approach paves a new way for the development of environmentally friendly and long-term antifouling coating.

Dimethyl Sulfoxide-Free Cryopreservation of Chondrocytes Based on Zwitterionic Molecule and Polymers.

Cartilage tissue engineering highly relies on the ability to store and transport chondrocytes in order to be clinically successful. Cryopreservation is a most reliable technology for chondrocyte storage, but it suffers from the intrinsic toxicity of current state-of-the-art cryoprotectant, dimethyl sulfoxide (DMSO). In this work, we used the first fully zwitterionic compound-based approach for effective chondrocyte cryopreservation. A zwitterionic molecule combined with zwitterionic polymers could balance intra/extracellular osmotic stress and prevent ice formation, which were the keys of successful cryopreservation. Moreover, this zwitterionic combination showed noncytotoxicity due to its high biocompatibility, superior to cytotoxic DMSO. On the basis of these performances, chondrocytes could be well cryopreserved (∼90% post-thaw survival efficiency) for a long time without any addition of DMSO, and the recovered cells could maintain their normal functionalities. In view of the association between polymer molecular weight and cryopreservation efficacy, further mechanism of cryoprotection provided by zwitterionic molecule/polymer was proposed. This work opens a new window of opportunity for DMSO-free cryopreservation using biocompatible zwitterionic materials.

Beetle-Inspired Hierarchical Antibacterial Interface for Reliable Fog Harvesting.

The microdroplets in fog flow have been considered as an important resource for supplying fresh drinking water. Most of the reported works of fog collection focus on the water-collecting ability rather than the environmental reliability of selected materials. In this work, a beetle-inspired hierarchical fog-collecting interface based on the antibacterial needle-array (ABN) and hydrophilic/hydrophobic cooperative structure is displayed. The hydrophilic ABN is coated with zwitterionic carboxybetaine (CB) brushes that endow the fog collector with a long-term cleaning in harsh environment. Due to its strong affinity to water molecules, the tilted needles with a CB coating can facilitate the capture of fog and the rapid delivery of condensed water driven by gravity. After being transported to the connected hydrophobic sheet, the collected droplets can be rapidly detached and stored in the container, achieving a high fog-harvesting rate. Furthermore, CB-patterned channels are integrated on the hydrophobic sheet for the pathway-controlled water delivery. The CB coating is able to efficiently resist bacterial adhesion and contamination during fog harvesting, protecting the device from microbiological corrosion. The current design provides a promising method to incorporate antibacterial ability into fog collectors, which offer great opportunity to develop water harvesters for real-world applications.

Hemocompatible hemoadsorbent for effective removal of protein-bound toxin in serum.

Resin hemoperfusion is a life-saving treatment for drug intoxication or hepatic failure of patients. However, current resin adsorbents exhibit a limited hemocompatibility or low adsorption efficiency, representing a major roadblock to successful clinical applications. In this work, we developed a hemocompatible and effective hemoadsorbent based on polystyrene resin (H103) microparticles encapsulated in anti-biofouling zwitterionic poly(carboxybetaine) (PCB) hydrogels. Apart from a strong mechanical stability, this PCB-based adsorbent (PCB-H103) exhibited excellent hemocompatibility (hemolysis ratio was ∼0.64%), which was attributed to the anti-biofouling property of PCB hydrogel. In addition, it can efficiently adsorb both small and middle molecular weight molecules in phosphate-buffered saline, and the efficiencies were significantly higher than poly(ethylene glycol) methacrylate-based and poly(2-hydroxyethyl methacrylate)-based adsorbent counterparts, indicating the favorable permeability of PCB hydrogel coating. More importantly, PCB-H103 could effectively remove protein-bound toxins including phenol red and bilirubin in bovine serum albumin solution or even in 100% fetal bovine serum (FBS). In 100% FBS, the adsorption capacity of PCB-H103 towards bilirubin was 8.3 times higher than that of pristine clinical-scale resin beads. Findings in this work may provide a new strategy for the development of modern resin hemoperfusion technology.

Bioinspired Multifunctional Protein Coating for Antifogging, Self-Cleaning, and Antimicrobial Properties.

A multifunctional coating with antifogging, self-cleaning, and antimicrobial properties has been prepared based on a mussel-inspired chimeric protein MP-KE, which is the first example that these proteins were successfully applied to fabricate antifogging surfaces. The coating exhibits super hydrophilic properties, as indicated by contact angles less than 5° and high light transmittance similar to bare glass substrates about 90%. The zwitterionic peptides of MP-KE empower water molecules to expand into thin hydrated films rapidly, providing the protein coating with diverse surface functions. Moreover, the coatings have excellent stability and a convenient preparation process because of the mussel adhesive motif of MP-KE which makes the coating anchor onto the surface strongly. As a protein material, this multifunctional coating possesses remarkable biocompatibility and has a potential application prospects in the biomedical and pharmaceutical fields.

A Robust Cotton Textile-Based Material for High-Flux Oil-Water Separation.

PDMS-based materials have been extensively studied in oil-water separation. However, their successful application is commonly limited by low efficiency, vulnerability to acid/alkali, complex processing procedures, incapability for emulsion separation, etc. Here, a highly durable and robust separation material is developed by coating PDMS-based copolymers on cotton textiles with a facile sol-gel approach. Solely driven by gravity, this new material not only can enable effective separation of oil-water mixture with a flux as high as ∼7500 L m-2 h-1 but also can separate surfactant-stabilized water-in-oil emulsion. Moreover, it remains fully functional even in the environments with high concentrations of acid, alkali, or salt. This novel and versatile strategy holds great promise to be widely used in practical applications of oil-water separation, including oil/chemical spill accidents and industrial sewage emission.