Muscle‐Inspired Highly Anisotropic,Strong, Ion‐Conductive Hydrogels

Biological tissues generally exhibit excellent anisotropic mechanical properties owing to their well‐developed microstructures. Inspired by the aligned structure in muscles, a highly anisotropic, strong, and conductive wood hydrogel is developed by fully utilizing the high–tensile strength of natural wood, and the flexibility and high‐water content of hydrogels. The wood hydrogel exhibits a high–tensile strength of 36 MPa along the longitudinal direction due to the strong bonding and cross‐linking between the aligned cellulose nanofibers (CNFs) in wood and the polyacrylamide (PAM) polymer. The wood hydrogel is 5 times and 500 times stronger than the bacterial cellulose hydrogels (7.2 MPa) and the unmodified PAM hydrogel (0.072 MPa), respectively, representing one of the strongest hydrogels ever reported. Due to the negatively charged aligned CNF, the wood hydrogel is also an excellent nanofluidic conduit with an ionic conductivity of up to 5 × 10^?4 S cm^–1 at low concentrations for highly selective ion transport, akin to biological muscle tissue. The work offers a promising strategy to fabricate a wide variety of strong, anisotropic, flexible, and ionically conductive wood‐based hydrogels for potential biomaterials and nanofluidic applications.     

A Hydrogel‐Film Casting to Fabricate Platelet‐Reinforced Polymer Composite Films Exhibiting Superior Mechanical Properties

The fabrication of mechanically superior polymer composite films with controllable shapes on various scales is difficult. Despite recent research on polymer composites consisting of organic matrices and inorganic materials with layered structures, these films suffer from complex preparations and limited mechanical properties that do not have even integration of high strength, stiffness, and toughness. Herein, a hydrogel‐film casting approach to achieve fabrication of simultaneously strong, stiff, and tough polymer composite films with well‐defined microstructure, inspired from a layer‐by‐layer structure of nacre is reported. Ca²⁺‐crosslinked alginate hydrogels incorporated with platelet‐like alumina particles are dried to form composite films composed of horizontally aligned alumina platelets and alginate matrix with uniformly layered microstructure. Alumina platelets are evenly distributed parallel without precipitations and contribute to synergistic enhancements of strength, stiffness and toughness in the resultant film. Consequentially, Ca²⁺‐crosslinked alginate/alumina (Ca²⁺‐Alg/Alu) films show exceptional tensile strength (267 MPa), modulus (17.9 GPa), and toughness (3.60 MJ m⁻³). Furthermore, the hydrogel‐film casting allows facile preparation of polymer composite films with controllable shapes and various scales. The results suggest an alternative approach to design and prepare polymer composites with the layer‐by‐layer structure for superior mechanical properties.     

Freezing Molecular Orientation under Stretch for High Mechanical Strength but Anisotropic Hydrogels

The poor mechanical strength of hydrogels has largely limited their wide applications, and improving hydrogels' mechanical strength is a hot and important topic in the hydrogel research field. Although many successful strategies have been proposed to improve hydrogels' mechanical strength during the past decades, a hydrogel with a tensile stress surpassing dozens of mega Pascal is desirable, yet still a big challenge. To address this issue, the Fe³⁺‐mediated physical crosslinking formed under stretch conditions was employed in a chemically crosslinked poly (acrylamide‐co‐acrylic acid) network to achieve a dual‐crosslinked hydrogel. The expected molecular orientation occurs under stretch and allows the maximumu chelating interaction between pendant carboxylic anions and Fe³⁺ and molecules conformation being frozen, leading to the mechanical strength improving dramatically. As a result, an unprecedentedly high mechanical strength, but anisotropic dual‐crosslinked hydrogel was obtained. By optimizing the experimental parameters, the nominal tensile stress along pre‐stretching direction can reach as high as ≈40 MPa with elastic modulus of ≈40 MPa at large strain (>200%). In addition, the molecular orientation also leads to big difference of mechanical performance between parallel and perpendicular direction.     

Stretchable All‐Gel‐State Fiber‐Shaped Supercapacitors Enabled by Macromolecularly Interconnected 3D Graphene/Nanostructured Conductive Polymer Hydrogels

Nanostructured conductive polymer hydrogels (CPHs) have been extensively applied in energy storage owing to their advantageous features, such as excellent electrochemical activity and relatively high electrical conductivity, yet the fabrication of self‐standing and flexible electrode‐based CPHs is still hampered by their limited mechanical properties. Herein, macromolecularly interconnected 3D graphene/nanostructured CPH is synthesized via self‐assembly of CPHs and graphene oxide macrostructures. The 3D hybrid hydrogel shows uniform interconnectivity and enhanced mechanical properties due to the strong macromolecular interaction between the CPHs and graphene, thus greatly reducing aggregation in the fiber‐shaping process. A proof‐of‐concept all‐gel‐state fibrous supercapacitor based on the 3D polyaniline/graphene hydrogel is fabricated to demonstrate the outstanding flexibility and mouldability, as well as superior electrochemical properties enabled by this 3D hybrid hydrogel design. The proposed device can achieve a large strain (up to ≈40%), and deliver a remarkable volumetric energy density of 8.80 mWh cm^?3 (at power density of 30.77 mW cm^?3), outperforming many fiber‐shaped supercapacitors reported previously. The all‐hydrogel design opens up opportunities in the fabrication of next‐generation wearable and portable electronics.     

Strong,Tough, and Anti-Swelling Supramolecular Conductive Hydrogels for Amphibious Motion Sensors

Conductive polymer hydrogels (CPHs) are widely employed in emerging flexible electronic devices because they possess both the electrical conductivity of conductors and the mechanical properties of hydrogels. However, the poor compatibility between conductive polymers and the hydrogel matrix, as well as the swelling behavior in humid environments, greatly compromises the mechanical and electrical properties of CPHs, limiting their applications in wearable electronic devices. Herein, a supramolecular strategy to develop a strong and tough CPH with excellent anti-swelling properties by incorporating hydrogen, coordination bonds, and cation-π interactions between a rigid conducting polymer and a soft hydrogel matrix is reported. Benefiting from the effective interactions between the polymer networks, the obtained supramolecular hydrogel has homogeneous structural integrity, exhibiting remarkable tensile strength (1.63 MPa), superior elongation at break (453%), and remarkable toughness (5.5 MJ m⁻³). As a strain sensor, the hydrogel possesses high electrical conductivity (2.16 S m⁻¹), a wide strain linear detection range (0–400%), and excellent sensitivity (gauge factor = 4.1), sufficient to monitor human activities with different strain windows. Furthermore, this hydrogel with high swelling resistance has been successfully applied to underwater sensors for monitoring frog swimming and underwater communication. These results reveal new possibilities for amphibious applications of wearable sensors.     

Effect of Multiwalled Carbon Nanotubes on the Conductivity and Swelling Properties of Porous Polyacrylamide Hydrogels

Multiwalled carbon nanotubes (MWCNTs) were added to polyacrylamide (PAM) hydrogels in different proportions to tune their electrical and mechanical properties. The choice of MWCNTs as a reinforcement is justified by the fact that these are highly conducting, fairly stable and flexible particles. A series of MWCNT/PAM hydrogels were prepared by freezing method. The characteristic absorption peaks at 1480 and 1213 cm^?1 in the FTIR spectra reveal that MWCNTs are embedded in the PAM hydrogels. Powder x-ray diffractograms and thermogravimetric analysis (TGA) images show that the MWCNT/PAM hydrogels are crystalline, more thermally stable and have a higher electrical conductivity than a traditional PAM hydrogel. Scanning electron micrographs reveal about reduced pore size, homogeneous and denser texture. The swelling properties of all these hybrid hydrogels were found to be better than those of the parent PAM hydrogel. The Li–Tanaka equation was employed to produce the swelling parameters. The diffusion coefficients (D _c ) of PAM hydrogel is 10 times higher than the literature value. 0.8% MWCNTs reinforced PAM hydrogel has excellent τ_c and electrical conductivity (0.76 mS/cm) with improvements in all properties. Lower D _c of 0.8% MWCNTs/PAM hydrogel reveal that extent of crosslinking is much important than density of the system for a better collective diffusion of the respective solvent.     

Highly Stretchable and Tough Hydrogels below Water Freezing Temperature

Hydrogels consist of hydrophilic polymer networks dispersed in water. Many applications of hydrogels rely on their unique combination of solid‐like mechanical behavior and water‐like transport properties. If the temperature is lowered below 0 °C, however, hydrogels freeze and become rigid, brittle, and non‐conductive. Here, a general class of hydrogels that do not freeze at temperatures far below 0 °C, while retaining high stretchability and fracture toughness, is demonstrated. These hydrogels are synthesized by adding a suitable amount of an ionic compound to the hydrogel. The present study focuses on tough polyacrylamide‐alginate double network hydrogels equilibrated with aqueous solutions of calcium chloride. The resulting hydrogels can be cooled to temperatures as low as ?57 °C without freezing. In this temperature range, the hydrogels can still be stretched more than four times their initial length and have a fracture toughness of 5000 J m^?2. It is anticipated that this new class of hydrogels will prove useful in developing new applications operating under a broad range of environmental and atmospheric conditions.     

Microfluidics‐Assisted Assembly of Injectable Photonic Hydrogels toward Reflective Cooling

Development of fast curing and easy modeling of colloidal photonic crystals is highly desirable for various applications. Here, a novel type of injectable photonic hydrogel (IPH) is proposed to achieve self‐healable structural color by integrating microfluidics‐derived photonic supraballs with supramolecular hydrogels. The supramolecular hydrogel is engineered via incorporating β‐cyclodextrin/poly(2‐hydroxypropyl acrylate‐co‐N‐vinylimidazole) (CD/poly(HPA‐co‐VI)) with methacrylated gelatin (GelMA), and serves as a scaffold for colloidal crystal arrays. The photonic supraballs derived from the microfluidics techniques, exhibit excellent compatibility with the hydrogel scaffolds, leading to enhanced assembly efficiency. By virtue of hydrogen bonds and host–guest interactions, a series of self‐healable photonic hydrogels (linear, planar, and spiral assemblies) can be facilely assembled. It is demonstrated that the spherical symmetry of the photonic supraballs endows them with identical optical responses independent of viewing angles. In addition, by taking the advantage of angle independent spectrum characteristics, the IPH presents beneficial effects in reflective cooling, which can achieve up to 17.4 °C in passive solar reflective cooling. The strategy represents an easy‐to‐perform platform for the construction of IPH, providing novel insights into macroscopic self‐assembly toward thermal management applications.     

Dynamic Coordination of Eu–Iminodiacetate to Control Fluorochromic Response of Polymer Hydrogels to Multistimuli

New fluorochromic materials that reversibly change their emission properties in response to their environment are of interest for the development of sensors and light‐emitting materials. A new design of Eu‐containing polymer hydrogels showing fast self‐healing and tunable fluorochromic properties in response to five different stimuli, including pH, temperature, metal ions, sonication, and force, is reported. The polymer hydrogels are fabricated using Eu–iminodiacetate (IDA) coordination in a hydrophilic poly(N,N‐dimethylacrylamide) matrix. Dynamic metal–ligand coordination allows reversible formation and disruption of hydrogel networks under various stimuli which makes hydrogels self‐healable and injectable. Such hydrogels show interesting switchable ON/OFF luminescence along with the sol–gel transition through the reversible formation and dissociation of Eu–IDA complexes upon various stimuli. It is demonstrated that Eu‐containing hydrogels display fast and reversible mechanochromic response as well in hydrogels having interpenetrating polymer network. Those multistimuli responsive fluorochromic hydrogels illustrate a new pathway to make smart optical materials, particularly for biological sensors where multistimuli response is required.     

Photodetachable Adhesion

Peeling from strong adhesion is hard, and sometimes painful. Herein, an approach is described to achieve both strong adhesion and easy detachment. The latter is triggered, on‐demand, through an exposure to light of a certain frequency range. The principle of photodetachable adhesion is first demonstrated using two hydrogels as adherends. Each hydrogel has a covalent polymer network, but does not have functional groups for bonding, so that the two hydrogels by themselves adhere poorly. The two hydrogels, however, adhere strongly when an aqueous solution of polymer chains is spread on the surfaces of the hydrogels and is triggered to form a stitching polymer network in situ, in topological entanglement with the pre‐existing polymer networks of the two hydrogels. The two hydrogels detach easily when the stitching polymer network is so functionalized that it undergoes a gel–sol transition in response to a UV light. For example, two pieces of alginate–polyacrylamide hydrogels achieve adhesion energies about 1400 and 10 J m^?2, respectively, before and after the UV radiation. Experiments are conducted to study the physics and chemistry of this strong and photodetachable adhesion, and to adhere and detach various materials, including hydrogels, elastomers, and inorganic solids.     

Highly Elastic and Ultratough Hybrid Ionic–Covalent Hydrogels with Tunable Structures and Mechanics

Hybrid ionically–covalently crosslinked double‐network (DN) hydrogels are attracting increasing attention on account of their self‐recovery ability and fatigue resistance, but their relative low mechanical strength and tedious performance adjustment severely limit their applications. Herein, a new strategy to concurrently fabricate hybrid ionic–covalent DN hydrogels and modulate their structures and mechanics is reported, in which an in situ formed chitosan ionic network is incorporated by post‐crosslinking the chitosan‐based composite hydrogel using multivalent anions solutions. The obtained hybrid DN hydrogels exhibit predominant mechanical properties including superior elastic modulus, high tensile strength, and ultrahigh fracture energy because of the more efficient energy dissipation of rigid short‐chain chitosan network. Notably, the swollen hydrogels still remain mechanically strong and tough even after immersion in water for 24 h. More significantly, simply changing the post‐crosslinking time can vary the compactness and rigidity of the chitosan network in situ, achieving flexible and efficient modulation of the structures and mechanics of the hybrid DN hydrogels. This study opens up a new horizon in the preparation and regulation of DN hydrogels for promising applications in tissue scaffolds, actuators, and wearable devices.     

Ultralight,Heat-Insulated,and Tough PVA Hydrogel Hybridized with SiO2@cellulose Nanoclaws Aerogel via the Synergy of Hydrophilic and Hydrophobic Interfacial Interactions

Lightweight porous hydrogels provide a worldwide scope for functional soft mateirals. However, most porous hydrogels have weak mechanical strength, high density (>1 g cm⁻³), and high heat absorption due to weak interfacial interactions and high solvent fill rates, which severely limit their application in wearable soft-electronic devices. Herein, an effective hybrid hydrogel-aerogel strategy to assemble ultralight, heat-insulated, and tough polyvinyl alcohol (PVA)/SiO₂@cellulose nanoclaws (CNCWs) hydrogels (PSCG) via strong interfacial interactions with hydrogen bonding and hydrophobic interaction is demonstrated. The resultant PSCG has an interesting hierarchical porous structure from bubble template (≈100 µm), PVA hydrogels networks introduced by ice crystals (≈10 µm), and hybrid SiO₂ aerogels (<50 nm), respectively. PSCG shows unprecedented low density (0.27 g cm⁻³), high tensile strength (1.6 MPa) & compressive strength (1.5 MPa), excellent heat-insulated ability, and strain-sensitive conductivity. This lightweight porous and tough hydrogel with an ingenious design provides a new way for wearable soft-electronic devices.     

Aggregation‐Induced Electrochemiluminescence by Metal‐Binding Protein Responsive Hydrogel Scaffolds

Functionalized hydrogels have aroused general interest due to their versatile applications in biomaterial fields. This work reports a hydrogel network composed of gold nanoclusters linked with bivalent cations such as Ca²⁺, Mg²⁺, and Zn²⁺. The hydrogel exhibits both aggregation‐induced emission (AIE) and aggregation‐induced electrochemiluminescence (AIECL) effects. Most noteworthy, the AIECL effect (≈50‐fold enhancement) is even more significant than the corresponding AIE effect (approximately fivefold enhancement). Calmodulin, a Ca²⁺ binding protein, may efficiently regulate the AIECL dynamics after specific binding of the Ca²⁺ linker, with the linear range from 0.3 to 50 µg mL^?1 and a limit of detection of 0.1 µg mL^?1. Considering the important roles of bivalent cations in the life system, these results may pave a new avenue for the design of a biomolecule‐responsive AIECL‐type hydrogel with multifunctional biomedical purposes.     

A high strength semi-degradable polysaccharide-based hybrid hydrogel for promoting cell adhesion and proliferation

Traditionally, practical applications of polysaccharide hydrogels have been limited for their weak mechanical properties under physiological conditions. In this study, we constructed a novel polysaccharide-based semi-degradable hydrogel whose network was constructed by chemical cross-linking of glycidyl methacrylate-modified laminarin and the hydrogen bonded physical cross-linking of poly(N-acryloyl glycinamide). In addition, the introduction of 1-vinyl-1,2,4-triazole content could increase the equilibrium water content of hydrogels and endow hydrogels with anti-bacterial and anti-inflammatory abilities. The prepared hydrogels exhibited comprehensive high mechanical properties up to 0.63 MPa tensile strength, 650% stretchability, and maximum 3.2 MPa compressive strength at swelling equilibrium state. The hydrogen bond interactions could well support the three-dimensional network of hydrogel after the degradation of modified laminarin. Meanwhile, the content of laminarin could facilitate cell adhesion and proliferation on the surface of hydrogel. It is anticipated that this high strength semi-degraded hydrogel may find a promising application as articular cartilage replacement.     

Swelling and mechanical behaviors of carbon nanotube/poly(vinyl alcohol) hybrid hydrogels

In this paper, carbon nanotubes (CNTs) were added into poly(vinyl alcohol) (PVA) hydrogels to modify their mechanical properties. A series of CNT/PVA hybrid hydrogels were prepared by freezing/thawing method. The mechanical and swelling properties of all hybrid hydrogels are better than those of the original PVA hydrogel. Especially, for CNTP-0.5 specimen with 0.5% w/w CNTs, its tensile modulus, tensile strength and strain at break are increased by 78.2%, 94.3% and 12.7%, respectively. And its swelling behavior is different from that of the pure PVA hydrogel. Its final swelling ratios at room temperature and 310 K are increased by 35.7% and 44.9%, respectively.     

Rapid and Superior Bacteria Killing of Carbon Quantum Dots/ZnO Decorated Injectable Folic Acid‐Conjugated PDA Hydrogel through Dual‐Light Triggered ROS and Membrane Permeability

One of the most difficult challenges in the biomedical field is bacterial infection, which causes tremendous harm to human health. In this work, an injectable hydrogel is synthesized through rapid assembly of dopamine (DA) and folic acid (FA) cross‐linked by transition metal ions (TMIs, i.e., Zn²⁺), which was named as DFT‐hydrogel. Both the two carboxyl groups in the FA molecule and catechol in polydopamine (PDA) easily chelates Zn²⁺ to form metal–ligand coordination, thereby allowing this injectable hydrogel to match the shapes of wounds. In addition, PDA in the hydrogel coated around carbon quantum dot‐decorated ZnO (C/ZnO) nanoparticles (NPs) to rapidly generate reactive oxygen species (ROS) and heat under illumination with 660 and 808 nm light, endows this hybrid hydrogel with great antibacterial efficacy against Staphylococcus aureus (S. aureus, typical Gram‐positive bacteria) and Escherichia coli (E. coli, typical Gram‐negative bacteria). The antibacterial efficacy of the prepared DFT‐C/ZnO‐hydrogel against S. aureus and E. coli under dual‐light irradiation is 99.9%. Importantly, the hydrogels release zinc ions over 12 days, resulting in a sustained antimicrobial effect and promoted fibroblast growth. Thus, this hybrid hydrogel exhibits great potential for the reconstruction of bacteria‐infected tissues, especially exposed wounds.     

Creating Stiff,Tough, and Functional Hydrogel Composites with Low‐Melting‐Point Alloys

Reinforcing hydrogels with a rigid scaffold is a promising method to greatly expand the mechanical and physical properties of hydrogels. One of the challenges of creating hydrogel composites is the significant stress that occurs due to swelling mismatch between the water‐swollen hydrogel matrix and the rigid skeleton in aqueous media. This stress can cause physical deformation (wrinkling, buckling, or fracture), preventing the fabrication of robust composites. Here, a simple yet versatile method is introduced to create “macroscale” hydrogel composites, by utilizing a rigid reinforcing phase that can relieve stress‐induced deformation. A low‐melting‐point alloy that can transform from a load‐bearing solid state to a free‐deformable liquid state at relatively low temperature is used as a reinforcing skeleton, which enables the release of any swelling mismatch, regardless of the matrix swelling degree in liquid media. This design can generally provide hydrogels with hybridized functions, including excellent mechanical properties, shape memory, and thermal healing, which are often difficult or impossible to achieve with single‐component hydrogel systems. Furthermore, this technique enables controlled electrochemical reactions and channel‐structure templating in hydrogel matrices. This work may play an important role in the future design of soft robots, wearable electronics, and biocompatible functional materials.     

Tough Bonding,On‐Demand Debonding,and Facile Rebonding between Hydrogels and Diverse Metal Surfaces

Hybrid systems of hydrogels and metals with tough bonding may find widespread applications. Here, a simple and universal method to obtain strong adhesion between hydrogels and diverse metal surfaces, such as titanium, steel, nickel, tantalum, argentum, and aluminum, with adhesion energy up to >1000 J m^?2 is reported. To achieve such, the metal surfaces are instantly modified with a linker molecule via soaking, dip‐coating, or drop‐casting. The designed linker molecule has a carboxylic acid group to bind with a metal surface, and a methacrylic group to crosslink with a hydrogel, thus bridging the interface between them. In addition, by introducing a stimulus‐responsive disulfide bond into the linker molecule, the on‐demand debonding between toughly bonded hydrogel and metal surface, which is enabled by reductive cleavage of the disulfide chemical linkage, is also demonstrated. More interestingly, after the reductive debonding, the resulting metal surface with free thiol groups can be easily rebonded with a second hydrogel without any further surface modification. The strategy may provide unique opportunities in designing hybrid devices that are suitable for complex and dynamic environments.     

Strain and stress mapping by mechanochemical activation of spiropyran in poly(methyl methacrylate)

The relationship between fracture‐induced mechanophore activation and the strain and stress ahead of a propagating crack in poly(methyl methacrylate) (PMMA) is studied. The mechanophore spiropyran is used as a secondary cross‐linker in rubber toughened PMMA, and the spiropyran‐linked material is subjected to fracture testing. Mechanophore activation is detected and analysed by fluorescence imaging. Digital image correlation is used to measure the strain field ahead of the crack tip, whereas the corresponding stress field is calculated using the Hutchinson–Rice–Rosengren singularity field equations. Mechanophore activation follows a power law dependence on distance from the crack tip and provides both a qualitative and quantitative measure of the strain and stress fields ahead of the crack.     

Customization of Conductive Elastomer Based on PVA/PEI for Stretchable Sensors

Conductive, stretchable, environmentally‐friendly, and strain‐sensitive elastomers are attracting immense research interest because of their potential applications in various areas, such as human–machine interfaces, healthcare monitoring, and soft robots. Herein, a binary networked elastomer is reported based on a composite hydrogel of polyvinyl alcohol (PVA) and polyethyleneimine (PEI), which is demonstrated to be ultrastretchable, mechanically robust, biosafe, and antibacterial. The mechanical stretchability and toughness of the hydrogels are optimized by tuning the constituent ratio and water content. The optimal hydrogel (PVA₂PEI₁‐75) displays an impressive tensile strain as high as 500% with a corresponding tensile stress of 0.6 MPa. Furthermore, the hydrogel elastomer is utilized to fabricate piezoresistive sensors. The as‐made strain sensor displays seductive capability to monitor and distinguish multifarious human motions with high accuracy and sensitivity, like facial expressions and vocal signals. Therefore, the elastomer reported in this study holds great potential for sensing applications in the era of the Internet of Things (IoTs).