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.

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.

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.

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.

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.

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.

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.