Dual Regulation of Charge Separation and the Oxygen Reduction Pathway by Encapsulating Phosphotungstic Acid into the Cationic Covalent Organic Framework for Efficient Photocatalytic Hydrogen Peroxide Production.

Previous research on covalent organic framework (COF)-based photocatalytic H2O2 synthesis from oxygen reduction focuses more on charge carrier separation but less on the electron utilization efficiency of O2. Herein, we put forward a facile approach to simultaneously promote charge separation and tailor the oxygen reduction pathway by introducing phosphotungstic acid (PTA) into the cationic COF skeleton. Experiments verified that PTA, as an electron transport medium, establishes a fast electron transfer channel from the COF semiconductor conductor band to the substrate O2; meanwhile, the reaction path is optimized by its catalytic cycle for preferable dioxygen capture and reduction in oxygen reduction reaction (ORR) kinetics. The existence of PTA promotes the rate and tendency of converting O2 into •O2- intermediates, which is conducive to boosting the photocatalytic activity and selectivity toward the sequential two-step single-electron ORR. As expected, compared to the pristine TTB-EB, the optimal PTA0.5@TTB-EB achieves a 2.2-fold improvement of visible-light-driven photocatalytic performance with a H2O2 production rate of 897.94 µmol·L-1·h-1 in pure water without using any sacrificial agents. In addition, owing to the robust electrostatic interaction and the confinement effect of porous TTB-EB channels, the PTA@TTB-EB composite possessed favorable stability.

Shape and stiffness memory ionogels with programmable pressure-resistance response.

Flexible pressure sensors usually require functional materials with both mechanical compliance and appropriate electrical performance. Most sensors based on materials with limited compressibility can hardly balance between high sensitivity and broad pressure range. Here, we prepare a heterophasic ionogel with shape and stiffness memory for adaptive pressure sensors. By combining the microstructure alignment for stiffness changing and shape memory micro-inclusions for stiffness fixing, the heterophasic ionogels reveal tunable compressibility. This controllable pressure-deformation property of the ionogels results in the pressure sensors' programmable pressure-resistance behavior with tunable pressure ranges, varied detection limits, and good resolution at high pressure. Broad pressure ranges to 220 and 380 kPa, and tunable detection limit from 120 to 330 and 950 Pa are realized by the stiffness memory ionogel sensors. Adaptive detection is also brought out to monitor tiny pressure changes at low stiffness and distinguish different human motions at high stiffness. Using shape and stiffness memory materials in pressure sensors is a general design to achieve programmable performance for more complex application scenarios.

Diffusion-Freezing-Induced Microphase Separation for Constructing Large-Area Multiscale Structures on Hydrogel Surfaces.

Hydrogels with multiscale structured surface have attracted significant attention for their valuable applications in diverse areas. However, current strategies for the design and fabrication of structured hydrogel surfaces, which suffer from complicated manufacturing processes and specific material modeling, are not efficient to produce structured hydrogel surfaces in large area, and therefore restrict their practical applications. To address this problem, a general and reliable method is reported, which relies on the interplay between polymer chain diffusion and the subsequent freezing-induced gelation and microphase separation processes. The basic idea is systematically analyzed and further exploited to manufacture gel surfaces with gradient structures and patterns through the introduction of temperature gradient and shape control of the contact area. Moreover, the formed micro/nanostructured surfaces are exemplified to work as capillary systems and thus can uplift the liquid spontaneously indicating the potential application for anti-dehydration. It is believed that the proposed facile and large-area fabrication method can inspire the design of materials with various functionalized surfaces.

Conductive Hydrogels as Smart Materials for Flexible Electronic Devices.

Flexible conductive materials have gained considerable research interest in recent years because of their potential applications in flexible energy storage devices, sensors, touch panels, electronic skins, etc. With excellent flexibility, outstanding electric properties and tunable mechanical properties, conductive hydrogels as conductive materials offer plentiful insights and opportunities for flexible electronic devices. Numerous synthetic strategies have been developed to obtain various conductive hydrogels, and high-performance flexible electronic devices based on these conductive hydrogels have been realized. This review provides a comprehensive overview of conductive-hydrogel-based flexible electronics, ranging from conductive hydrogels synthesis to several important flexible devices applications, including touch panels, sensors and energy storage. Finally, we provide new future research directions and perspectives for conductive-hydrogel-based flexible and portable electronic devices.

General Strategy to Fabricate Highly Filled Microcomposite Hydrogels with High Mechanical Strength and Stiffness.

Conventional synthetic hydrogels are intrinsically soft and brittle, which severely limits the scope of their applications. A variety of approaches have been proposed to improve the mechanical strength of hydrogels. However, a facile and ubiquitous strategy to prepare hydrogels with high mechanical strength and stiffness is still a challenge. Here, we report a general strategy to prepare highly filled microcomposite hydrogels with high mechanical performance using an ultrasonic assisted strategy. The microparticles were dispersed in the polymer network evenly, resulting in homogeneous and closely packed structures. The as-prepared hydrogels with extraordinary mechanical performance can endure compressive stress up to 20 MPa (at 75% strain) and exhibit high stiffness (elastic modulus is around 18 MPa). By using our comprehensive strategy, different hydrogels can enhance their mechanical strength and stiffness by doping various microparticles, leading to a much wider variety of applications.

High-speed transport of liquid droplets in magnetic tubular microactuators.

Magnetic field-induced droplet actuation has attracted substantial research interest in recent years. However, current magnetic-controlled liquids depend primarily on magnetic particles added to a droplet, which serves as the actuator on an open surface. These liquids inevitably suffer from droplet splitting with the magnetic particles or disengaging with the magnet, possibly leading to sample contamination, which severely limits their transport speed and practical applications. Here, we report a simple and additive-free method to fabricate magnetic tubular microactuators for manipulating liquid droplets by magnetism-induced asymmetric deformation, which generates an adjustable capillary force to propel liquids. These magnetic tubular microactuators can drive various liquid droplets with controllable velocity and direction. A speed of 10 cm s-1 can be achieved, representing the highest speed of liquid motion driven by an external stimulus-induced capillary force in a closed tube found so far.

Bioinspired Nanocomposite Hydrogels with Highly Ordered Structures.

In the human body, many soft tissues with hierarchically ordered composite structures, such as cartilage, skeletal muscle, the corneas, and blood vessels, exhibit highly anisotropic mechanical strength and functionality to adapt to complex environments. In artificial soft materials, hydrogels are analogous to these biological soft tissues due to their "soft and wet" properties, their biocompatibility, and their elastic performance. However, conventional hydrogel materials with unordered homogeneous structures inevitably lack high mechanical properties and anisotropic functional performances; thus, their further application is limited. Inspired by biological soft tissues with well-ordered structures, researchers have increasingly investigated highly ordered nanocomposite hydrogels as functional biological engineering soft materials with unique mechanical, optical, and biological properties. These hydrogels incorporate long-range ordered nanocomposite structures within hydrogel network matrixes. Here, the critical design criteria and the state-of-the-art fabrication strategies of nanocomposite hydrogels with highly ordered structures are systemically reviewed. Then, recent progress in applications in the fields of soft actuators, tissue engineering, and sensors is highlighted. The future development and prospective application of highly ordered nanocomposite hydrogels are also discussed.

Anti-freezing, Conductive Self-healing Organohydrogels with Stable Strain-Sensitivity at Subzero Temperatures.

Conductive hydrogels are a class of stretchable conductive materials that are important for various applications. However, water-based conductive hydrogels inevitably lose elasticity and conductivity at subzero temperatures, which severely limits their applications at low temperatures. Herein we report anti-freezing conductive organohydrogels by using an H2 O/ethylene glycol binary solvent as dispersion medium. Owing to the freezing tolerance of the binary solvent, our organohydrogels exhibit stable flexibility and strain-sensitivity in the temperature range from -55.0 to 44.6 °C. Meanwhile, the solvent molecules could form hydrogen bonds with polyvinyl alcohol (PVA) chains and induce the crystallization of PVA, greatly improving the mechanical strength of the organohydrogels. Furthermore, the non-covalent crosslinks endow the conductive organohydrogels with intriguing remoldability and self-healing capability, which are important for practical applications.

Construction of a superior visible-light-driven photocatalyst based on a C3N4 active centre-photoelectron shift platform-electron withdrawing unit triadic structure covalent organic framework.

Herein, three functional factors inducing photocatalytic ability were artfully integrated into a covalent organic framework (COF), where triazine units served as photoactive centers, cyclic ketone units served as electron-withdrawing moieties, and the conjugated structure served as a photoelectron shift platform. This COF with segregated donor-acceptor alignments exhibits an excellent visible-light photocatalytic capacity for the decomposition of organic pollutants.

Covalent tethering of photo-responsive superficial layers on hydrogel surfaces for photo-controlled release.

The diffusion and transport of substances between a hydrogel and its environment have received tremendous research interest, due to the wide range of applications of hydrogel materials in fields related to drug carriers and drug delivery vehicles. To date, much research has been done to tailor the diffusion and transport of substances through hydrogels, where most efforts were focused on tuning the 3D network properties of the hydrogel including loop size, hydrophobicity of building blocks and the stimuli-responsive properties of backbones. These conventional strategies, however, usually suffer from complicated fabrication procedures and result in a homogeneous increase in hydrophobicity of the hydrogel network, leading to low efficiency control over the diffusion of substances through the hydrogel. Herein, a facile strategy that can functionalize the surfaces of hydrogels, while keeping the interior network unchanged, was reported, and is realized by quaternization reaction confined to the hydrogel/oil interface. Owing to the introduction of the photo-responsive molecule IBSP as a modifier, the surface wettability of the resulting hydrogel can be controlled by light both in air and underwater environments. Consequently, the diffusion rate of a substance through this modified hydrogel can be regulated by light, which brings convenience to the controlled release of hydrogels and other hydrogel-related fields.

Polyhydroquinone-graphene composite as new redox species for sensitive electrochemical detection of cytokeratins antigen 21-1.

Polyhydroquinone-graphene composite as a new redox species was synthesized simply by a microwave-assisted one-pot method through oxidative polymerization of hydroquinone by graphene oxide, which exhibited excellent electrochemical redox activity at 0.124 V and can remarkably promote electron transfer. The as-prepared composite was used as immunosensing substrate in a label-free electrochemical immunosensor for the detection of cytokeratins antigen 21-1, a kind of biomarker of lung cancer. The proposed immunosensor showed wide liner range from 10 pg mL(-1) to 200 ng mL(-1) with a detection limit 2.3 pg mL(-1), and displayed a good stability and selectivity. In addition, this method has been used for the analysis of human serum sample, and the detection results showed good consistence with those of ELISA. The present substrate can be easily extended to other polymer-based nanocomposites.

Metal ions doped chitosan-poly(acrylic acid) nanospheres: Synthesis and their application in simultaneously electrochemical detection of four markers of pancreatic cancer.

In this work, a one-pot method was designed to synthesize copper ions, cadmium ions, lead ions and zinc ions doped chitosan-poly(acrylic acid) nanospheres. Those nanospheres can not only produce independent electrochemical signals, but also react with glutaraldehyde (GA) to immobilize different labeled antibodies. Using the modified nanospheres as immunoprobes, a sandwich-type immunosensor was fabricated to simultaneous detection of four tumor markers (CEA, CA199, CA125 and CA242) of pancreatic cancer. This designed immunosensor exhibited good linear relationships in range from 0.1 to 100ng mL(-1) for CEA, 1 to 150UmL(-1) for CA199, CA125 and CA242, corresponding detection limits 0.02ng mL(-1), 0.4UmL(-1), 0.3UmL(-1) and 0.4UmL(-1), respectively. Meanwhile, the immunosensor was applied in analysis of clinical serum samples, whose results were well agreed with the enzyme-linked immunosorbent assay (ELISA), indicating that the proposed immunosensor gave a hope for the identification and validation of specific early cancer.

Network nanostructured polypyrrole hydrogel/Au composites as enhanced electrochemical biosensing platform.

In this work, a new network nanocomposite composed of polypyrrole hydrogel (PPy hydrogel) loaded gold nanoparticles (AuNPs) was prepared. The PPy hydrogel was directly synthesized by mixing the pyrrole monomer and phytic acid, and the mixed solution can be gelated to form hydrogel at once. The three-dimensional network nanostructured PPy hydrogel not only provided a greater effective surface area for increasing the quantity of immobilized biomolecules and facilitated the transport of electrons and ions, but also exhibited an improved conductivity. Meanwhile, the electrodeposited AuNPs on the PPy hydrogel can further increase the specific surface area to capture a large amount of antibodies as well as improve the capability of electron transfer. The network PPy hydrogel/Au nanocomposites were successfully employed for the fabrication of a sensitive label-free amperometric immunosensor. Carcinoembryonic antigen (CEA) was used as a model protein. The proposed immunosensor exhibited a wide linear detection range from 1 fg mL(-1) to 200 ng mL(-1), and an ultralow limit of detection of 0.16 g mL(-1) (S/N = 3), and it also possessed good selectivity. Moreover, the detection of CEA in ten human serums showed satisfactory accuracy compared with the data determined by ELISA, indicating that the immunosensor provided potential application for clinical diagnosis.

One-step synthesis of redox-active polymer/AU nanocomposites for electrochemical immunoassay of multiplexed tumor markers.

In this work, a simple and sensitive multiplexed immunoassay protocol for simultaneous electrochemical determination of alpha-fetoprotein (AFP) and carcinoembryonic antigen (CEA) was designed using redox-active nanocomposites. As the redox-active species, the poly(o-phenylenediamine) (POPD)/Au nanocomposite and poly(vinyl ferrocene-2-aminothiophenol) (poly(VFc-ATP))/Au nanocomposite were obtained by one-step method which HAuCl4 was used as the oxidant. With Au nanoparticles (AuNPs), the nanocomposites were successful to immobilize labeled anti-CEA and anti-AFP as the immunosensing probes. The proposed electrochemical immunoassay enabled the simultaneous monitoring of AFP and CEA in a wide range of 0.01-100ngmL(-1). The detection limits was 0.006ngmL(-1) for CEA and 0.003ngmL(-1) for AFP (S/N=3). The assay results of serum samples with the proposed method were well consistent with the reference values from standard ELISA method. And the negligible cross-reactivity between the two analytes makes it possesses potential promise in clinical diagnosis.