The Recent Advances of Polymer-POSS Nanocomposites With Low Dielectric Constant.

This study provides a comprehensive overview of the preparation methods for polyhedral oligomeric silsesquioxane (POSS) monomers and polymer/POSS nanocomposites. It focuses on the latest advancements in using POSS to design polymer nanocomposites with reduced dielectric constants. The study emphasizes exploring the potential of POSS, either alone or in combination with other materials, to decrease the dielectric constant and dielectric loss of various polymers, including polyimides, bismaleimide resins, poly(aryl ether)s, polybenzoxazines, benzocyclobutene resins, polyolefins, cyanate ester resins, and epoxy resins. In addition, the research investigates the impact of incorporating POSS on improving the thermal properties, mechanical properties, surface properties, and other aspects of these polymers. The entire study is divided into two parts, discussing systematically the role of POSS in reducing dielectric constants during the preparation of POSS composites using both physical blending and chemical synthesis methods. The goal of this research is to provide valuable strategies for designing a new generation of low dielectric constant materials suitable for large-scale integrated circuits in the semiconductor materials domain.

Stabilizing Liquid in Precise Nonequilibrium Shapes via Fast Interfacial Polymerization.

Due to the minimization of interface area caused by surface tension, the stabilization of liquid in complex and precise nonequilibrium shapes is challenging. In this work, a simple, surfactant-free, and covalent strategy to stabilize liquid in precise nonequilibrium shapes via fast interfacial polymerization (FIP) of highly reactive n-butyl cyanoacrylate (BCA) monomer triggered by water-soluble nucleophiles is described. Full interfacial coverage can be achieved instantly, and the resultant polyBCA film anchored at the interface can support the unequal interface stress, which allows the production of non-spherical droplets with complex shapes. Notably, the formulation of internal aqueous phase is nearly unaffected since no specific additive is required. Moreover, considering the excellent biocompatibility of BCA and polyBCA, the produced droplets can be used as micro-bioreactor for enzyme catalysis and even bacterial culture, which well mimic the morphology of cells and bacteria to achieve the biochemical reaction in non-spherical droplets. The present work not only opens a new sight for the stabilization of liquid in nonequilibrium shapes, but may also promote the development of synthetic biology based on non-spherical droplets, and tremendous potential applications are anticipated.

Early Braking of Overwarmed Lithium-Ion Batteries by Shape-Memorized Current Collectors.

In the context of the constant impending energy crisis, the lithium-ion battery as a burgeoning energy storage means is showing extraordinary talents in many energy relevant investigations. However, fire and explosion would probably occur when the battery is encountered with overheating, at which the shrinking of the separator routinely causes an internal short circuit. Herein, we develop a kind of novel shape-memorized current collector (SMCC), which can successfully brake battery thermal runaway at the battery internal overheating status. Unlike traditional current collectors made of commercial copper foils, SMCC is made of a micropatterned shape memory micron-sized film with copper deposition. SMCC displays ideal conductivity at normal temperatures and turns to be insulative at overheating temperatures. Following this principle, the battery consisting of an SMCC can run normally at temperatures lower than 90 °C, while it quickly achieves self-shutdown before the occurrence of battery combustion and explosion.

A Novel Ionic Conductive Polyurethane Based on Deep Eutectic Solvent Continuing Traditional Merits.

Artificial intelligence (AI) has become increasingly popular along with the development of the bionic neural system. Ionic conductors play an important role in the AI system due to the ability of bionic sensing and signal transporting. Traditional low-polarity elastomers possess outstanding mechanical strength and stability, such as polyurethane, which is difficult to be directly endowed with ionic conductivity without impairing its properties. Herein, we have first put forward a new approach to synthesize a liquid-free ionic conductive polyurethane (CPU) through one-step copolymerization between a green deep eutectic solvent (DES) and a prepolymer of polyurethane. The as-prepared CPU can retain the native properties of the traditional polyurethane (PU) such as the homogeneous phase, ease of molding, high transparency (about 93.3%), and excellent mechanical properties. By introducing the DES as the covalent cross-linking agent and ionic conductor at the same time, the CPU also has fine ionic conductivity (3.78 × 10-5 S cm-1), environmental resistance like anti-freezing (-20 °C), and solvent resistance. Based on the excellent conductivity and mechanical strength, the flexible CPU can be applied as a sensing element in pressure sensors. The CPU-based sensor has presented long-term stability, high sensitivity, and wide-ranging response (0.17-3.28 MPa) to the applied pressure, which will be suitable for the industrial demands for practical applications.

Iodine-Oxidized Diene-Based Rubbers as Anti-icing and Deicing Polymer Coatings.

In an effort to prevent or minimize icing hazards, techniques and materials for icing inhibition and deicing have always been highly favored throughout human history. This work discovers the integrated anti-icing and deicing effects of poly(styrene-b-butadiene-b-styrene) triblock rubber (SBS) after its easy oxidation in iodine vapor. Iodine oxidation happens on the block of polybutadiene, featured by the conversion of SBS from hydrophobic to amphiphilic and the improved capability of photothermal conversion. The oxidized SBS can serve as a polymer coating, which possesses intriguing abilities to delay the kinetics of icing on its surface and repel the ice under light illumination. According to characterizations of surface chemistry and mechanical performance, iodine oxidation is assumed to involve the processes of iodine coordination to unsaturated bonds, the formation of radical cations as a result of the redox reaction between iodine and unsaturated carbon-carbon bonds, improved light absorption owing to the formation of polyiodide anions, and intermolecular coupling of radical cations. The appearance of polar moieties/species within the oxidized SBS is attributed to the delayed ice nucleation. The significant photothermal capacity in visible and near-infrared windows enables the iodine-oxidized SBS coating to remove the adhered ice by melting under light illumination when the icing process is inevitable, even at an extremely low temperature (-25 °C).

Floating Hydrogel Beads Made by Droplet Impact.

Droplet impact is a ubiquitous natural phenomenon that has been widely utilized to inspire and facilitate many industrial applications. Compared to the widely studied water droplet impact onto identical liquid surfaces, the water droplet impact onto an oil layer floating on a water bath (OLW) receives far less attention and its potential application has never been exploited. Herein, the process of water droplet impact onto the OLW is investigated with emphasis on the metastable states and potential applications. It is found that the dramatic deformation of the oil-water interface caused by the water droplet impact leads to two metastable states: oil in water in oil in water (O/W/O/W) and oil in water in oil (O/W/O). Through the subsequent introduction of gelation process, the metastable states can be frozen into floating hydrogel beads with similar shape to the roly-poly toys, which are attempted in gastric retentive drug delivery and algae bloom control. Specifically, the floating hydrogel beads perform well in gastric retentive drug delivery in vitro due to their inherent slow-release properties and floating capability. In addition, the floating hydrogel beads loading photocatalysts can capture more sunshine, and exhibit high photocatalytic efficiency, which is thus responsible for efficient algae bloom control.

Controllable Degradation of Polyurethane Thermosets with Silaketal Linkages in Response to Weak Acid.

Polyurethane (PU) thermosets offer great favors to our daily life on account of their excellent mechanical, physical, and chemical properties as well as appreciable biocompatibility. Nevertheless, PU waste is increasingly causing environmental and health-related problems as it is mostly resistant to chemical degradation under mild conditions. Herein, we report a kind of PU thermoset with silaketal leakages in its main chains to enable polymer degradation in response to weak acids, even in edible vinegar. The degradation rate is significantly influenced by the alkyl substituents on the silicon atoms, with entire degradation in hours, days, weeks, or months. Besides controllable degradation, investigations are also provided into the recycling of PU thermosets by means of thermal reprocessing based on carbamate bond exchange or repolymerization of degradation residuals. Because of the controllable degradation and easy recycling, this particular kind of PU thermoset exhibits great potential in manufacturing green polymer products that can be decomposed by nature or reutilized after disposal.

Artificial Kidney Capsule Packed with Mesenchymal Stem Cell-Laden Hydrogel for the Treatment of Rhabdomyolysis-Induced Acute Kidney Injury.

Acute kidney injury (AKI) has emerged as a major public health problem affecting millions of people worldwide without specific and satisfactory therapies due to the lack of an effective delivery approach. In the past few decades, hydrogels present infinite potential in localized drug delivery, while their poor adhesion to moist tissue and isotropic diffusion character always restrict the therapeutic efficiency and may lead to unwanted side effects. Herein, we proposed a novel therapeutic strategy for AKI via a customizable artificial kidney capsule (AKC) together with a mesenchymal stem cell (MSC)-laden hydrogel. Specifically, an elastic capsule owning an inner chamber with the same size and shape as the kidney is designed and fabricated through three-dimensional (3D) modeling and printing, serving as an outer wrap for kidney and cell-laden hydrogels. According to the in vitro experiment, the excellent biocompatibility of gelatin-based hydrogel ensures viability and proliferation of MSCs. In vivo mice experiments proved that this concept of AKC-assisted kidney drug delivery could efficiently reduce epithelial cell apoptosis and minimize the damage of the renal tubular structure for mice suffering AKI. Such a strategy not only provides a promising alternative in the treatment of AKI but also offers a feasible and versatile approach for the repair and recovery of other organs.

An injectable bioink with rapid prototyping in the air andin-situmild polymerization for 3D bioprinting.

Bioprinting is an attractive technology for building tissues from scratch to explore entire new cell configurations, which brings numerous opportunities for biochemical research such as engineering tissues for therapeutic tissue repair or drug screening. However, bioprinting is faced with the limited number of suitable bioinks that enable bioprinting with excellent printability, high structural fidelity, physiological stability, and good biocompatibility, particularly in the case of extrusion-based bioprinting. Herein, we demonstrate a composite bioink based on gelatin, bacterial cellulose (BC), and microbial transglutaminase (mTG enzyme) with outstanding printing controllability and durable architectural integrity. BC, as a rheology modifier and mechanical enhancer component, endows the bioink with shear-thinning behavior. Moreover, the printed structure becomes robust under physiological conditions owing to thein situchemical crosslinking catalyzed by mTG enzyme. Lattice, bowl, meniscus, and ear structures are printed to demonstrate the printing feasibility of such a composite bioink. Furthermore, the 3D-printed cell-laden constructs are proved to be a conducive biochemical environment that supports growth and proliferation of the encapsulated cellsin vitro. In addition, thein vivostudies convince that the composite bioink possesses excellent biocompatibility and biodegradation. It is believed that the innovation of this new composite bioink will push forward the bioprinting technology onto a new stage.

An Ultra-Low-Temperature Elastomer with Excellent Mechanical Performance and Solvent Resistance.

Elastomers presenting good elasticity, ductility, and chemical resistance at low temperatures can serve as superior performers for explorations in extremely cold environments. However, no commercially available elastomer to date can comprehensively fulfill those demands. Here, a perfluoropolyether (PFPE)-based network crosslinked by dynamic urethane chemistry is demonstrated, which may satisfy the demands of application in ultracold environments. As the crucial constitute in such a crosslinked network, PFPE provides the elastomer with excellent elasticity at a temperature down to -110 °C and outstanding ductility within the cryogenic temperature range. Importantly, the high proportion of fluorocarbon segment also provides wonderful compatibility to most organic solvents, accounting for the low-swelling characteristics of the elastomer in sealing applications. Furthermore, the dynamic crosslinking feature allows the cured elastomer to be reprocessed like thermoplastic polymers, which affords great promise to recycle and reuse the elastomer after its disposal. Inherently, this elastomer would inspire a worldwide interest in the design of elastic devices that are adaptable to extremely low temperature.

Renatured hydrogel painting.

Hydrogel coatings pave an avenue for improving the lubricity, biocompatibility, and flexibility of solid surfaces. From the viewpoint of practical applications, this work establishes a scalable method to firmly adhere hydrogel layers to diverse solid surfaces. The strategy, termed as renatured hydrogel painting (RHP), refers to adhering dehydrated xerogel to a surface with appropriate glues, followed by the formation of a hydrogel layer after rehydration of the xerogel. With the benefits of simplicity and generality, this strategy can be readily applied to different hydrogel systems, no matter what the substrate is. Hydrogel adhesion is demonstrated by its tolerance against mechanical impact with hydrodynamic shearing at 14 m/s. This method affords powerful supplements to renew the surface chemistry and physical properties of solid substrates. In addition, we show that the RHP technique can be applied to living tissue, with potential for clinical applications such as the protection of bone tissue.

Effect of pH or Metal Ions on the Oil/Water Interfacial Behavior of Humic Acid Based Surfactant.

Humic acid, a kind of widespread organic macromolecule on earth, is naturally formed through the microbial biodegradation of plant, animal, and microorganism residues. Because of the large number of active functional groups (phenolic hydroxyl and carboxyl), humic acid has been considered as a biocompatible, green, and low-cost biosurfactant recently. In this work, based on the sensitivity of humic acid to the external chemical environment, the oil/water interfacial behavior of sodium humate at different pH or in the presence of metal ions is closely investigated. Sodium humate is significantly enriched toward the oil/water interface at either low pH or high metal-ion concentration to adjust the properties of the prepared emulsion, but the mechanisms are proved to be different when considering the influence of pH and metal ions. Besides, to the best of our knowledge, humic acid based surfactant is proposed as a Pickering emulsifier for the first time, known as solid surfactant. This work promises the great potential of humic acid as a natural environment-responsive surfactant and has important implications for the application of humic acid based surfactant in industry and understanding of the role of humic acid in the natural environment.

Three Birds with One Stone: Injectable CaC2 Nanobombs with Triple Effects for Minimally Invasive Tumor Chemical Ablation.

Percutaneous chemical ablation (PCA) is the oldest and most established technique for treating small solid tumors in organs. It has been widely used in clinics even on an outpatient basis. However, compared with the emerging microwave or magnetic hyperthermal ablation, PCA is faced with relatively poor necrosis results and needs to repeat multiple sessions. Inspired by the three effects in the bomb's explosive process, we herein expect to combine calcium carbide (CaC2) nanoparticles into the PCA technique to generate local explosion within tumor tissues, leading to three killing effects against tumors to further improve the ablation efficacy of PCA. Through an efficient wet milling procedure with poly(ethylene glycol), three kinds of nanobombs including CaC2, calcium oxide (CaO), and calcium hydroxide (Ca(OH)2) were fabricated, and they all exhibited desirable suspension stability. Among these nanobombs, in particular CaC2 nanobombs showed a synergistic effect that the generation of ethyne gas bubbles could facilitate the most rapid diffusion of hyperthermia. Also, CaC2 nanobombs offered the powerful ability to cause the sudden rise of local high temperature and pH value. According to the in vivo mice tumor excision trial, the tumors of 75% of cases that received CaC2 treatment were destroyed and eradicated, exhibiting the excellent ablation ability of CaC2 nanobombs against small solid tumors planted in mice.

Inherently magnetic hydrogel for data storage based on the magneto-optical Kerr effect.

In this data explosion age, a large amount of data is generated every day. Such a fast data growth has aroused great interest in the field of data storage. Conventional data storage materials are mainly composed of hard and brittle materials but they may break in the case of mechanical operations, causing irreversible data loss. In this work, efforts have been devoted to fabricating a flexible and stretchable double network hydrogel for data storage based on the magneto-optical Kerr effect. The hydrogel possesses a storage modulus of over 104 Pa and remains unbroken under a strain of 3000%. The surface of the hydrogel is patterned with diamagnetic parts and paramagnetic parts alternately. When placed under a magnetic field, the surface of the hydrogel reflects the incident laser beam and changes the polarization plane of the reflected light. The outstanding flexibility and inherent magnetic properties of this hydrogel lay the groundwork for data storage and guarantee data safety.

Interfacial Diffusion Printing: An Efficient Manufacturing Technique for Artificial Tubular Grafts.

Despite great progresses in bioprinting materials and technologies, immense challenges still remain when printing tubular tissues or organs with satisfying mechanical and chemical properties, such as blood vessel, colon, and trachea. Herein, a promising extrusion system based on an interfacial diffusion printing (IDP) technique for one-step printing of tubular tissue grafts is proposed. Specifically, this technique offers great convenience to prepare hollow hydrogel fibers with excellent mechanical properties and satisfactory biocompatibility. The tubular diameter can be readily adjusted within 6 mm, which renders the possibility of these hydrogel tubes to serve as small-diameter vascular grafts. In the model of animal trials, the hydrogel grafts with the capability of enduring arterial pressure are mechanically stable in rabbit carotid artery replacement. Because of its intrinsic simplicity and generality, the IDP technique is considered to be one of the reliable choices for more complicated bioengineering.

Body Compatible Thermometer Based on Green Electrolytes.

With the use of coordinated complexes between aliphatic diols and calcium chloride (CaCl2) as green electrolytes, a body compatible, ecofriendly and low-cost thermometer is successfully developed. This particular conductive liquid possesses unique features of ultrafast response and high sensitivity against temperature change. The influences of CaCl2 concentration and the category of aliphatic diols on conductivity change reveal that the thermal sensing abilities of such green electrolytes are positively relevant to the viscosity change along with temperature change. Owing to the advantages of stability, reliability, and security, the thermometer can implement long-term and continuous temperature monitoring, which can fully meet the requirements of application of medical monitors, diagnostics, and therapies. Moreover, the inherent advantages of thermometers, including satisfactory biocompatibility and nontoxicity, afford great promise for applications in invasive and inflammatory devices.

Interfacial Emulsification: An Emerging Monodisperse Droplet Generation Method for Microreactors and Bioanalysis.

The generation of uniform droplets has been extensively investigated owing to its profound potentials both in scientific research and engineering applications. Although various methods have been put forward to expand this area, new innovations are still needed to improve the technical convenience and save instrumental cost. In this feature article, we highlight an interfacial emulsification technique that we developed in the past several years. This technique serves as a platform for preparing uniform droplets that are formed on the air-liquid interface of the continuous phase based on interfacial shearing. Three specific aspects of interfacial emulsification are reviewed, including its basic design and principle, the preparation of droplets with controllable size and adjustable components, and practical applications of the method in bioanalysis, microreactors, and particle synthesis. Compared to other droplet generation methods, several attractive advantages and perspectives for further development have been summarized.

A Polypyrrole Elastomer Based on Confined Polymerization in a Host Polymer Network for Highly Stretchable Temperature and Strain Sensors.

For the purpose of stretchable electronics, broad interests have been paid to elastic conductors by which high tensile strain over 100% can be readily achieved. Here, a scalable-processing, dyeing-like strategy for highly stretchable polypyrrole elastomer (1450% in strain) is conceived without particular topological design. This approach effectively improves the mechanical properties of the classic insoluble polypyrrole by confined polymerization within an elastic polymer network. In terms of the easy processing, it is technically possible to prepare stretchable electronics with arbitrary shape and size for wearable electronics with low cost. The mechanism of interpenetrated networks coexisting with microphase separation is comprehensively illustrated at molecular scale. The as-fabricated polypyrrole elastomers are utilized as temperature or strain sensors for automatic fishing and region-distinct dual signal sensing. Further integration of multiple sensors offers immediate alarm for old people falling at home, which thereby proves its promising potential in practical applications.

Spider-Inspired Multicomponent 3D Printing Technique for Next-Generation Complex Biofabrication.

The shortage of tissue resources is currently a serious challenge that limits the clinical therapy to patients with tissue loss or end-stage organ failure. The booming development of 3D printing offers unprecedented hope for tissue engineering since it can construct cells and biomaterials into a 3D tissue-mimicking object with precise control over size and shape. However, it is still challenging to fabricate artificial living tissues or organs due to the extreme complexity of biological tissues. Herein, we propose a new concept of spider-inspired 3D printing technique (SI-3DP) for continuous multicomponent 3D printing based on in situ gelation at a multibarrel printing nozzle. The printing process allows for rapid construction of 3D architectures composed of different inks in the desired position. To present the potential in biomedical applications, the SI-DIP also prints vessel-like hollow hydrogel microfibers and cell-laden hollow fibers, indicating good biocompatibility of this technique. The newly developed SI-3DP technique is envisioned to promote the development of next-generation complex biofabrication.

Multichannel Dynamic Interfacial Printing: An Alternative Multicomponent Droplet Generation Technique for Lab in a Drop.

Generation of uniform emulsion droplets mixed with multiple components is one of the key issues in the field of lab in a drop. Traditionally, droplet microfluidic chips are often served as the prime choice while designing and fabricating microfluidic chips always rely on skilled technician and specialized equipment, severely restricting its wide accessibility. In this work, an alternative technique, called multichannel dynamic interfacial printing (MC-DIP), was proposed for multicomponent droplet generation. The MC-DIP device was designed modularly and could be set up manually without any microfabrication process, exhibiting full accessibility for freshmen after a brief training. This new technique owns advantages in the generation of droplets with predictable sizes and composites. Quantitative experiments of measuring minimum inhibitory concentration (MIC) value via mixing microbes and antibiotics into droplet were conducted to proving its application potential for lab in a drop. Further research on a clinical pathogenic strain revealed that this technique could be potentially applied in the clinical laboratory for antibiotic susceptibility testing.