Fluorescent Double Network Hydrogels with Ionic Responsiveness and High Mechanical Properties for Visual Detection

We developed a fluorescent double network hydrogel with ionic responsiveness and high mechanical properties for visual detection.The nanocomposite hydrogel of laponite and polyacrylamide serves as the first network,while the ionic cross-linked hydrogel of terbium ions and sodium alginate serves as the second network.The double-network structure,the introduction of nanoparticles and the reversible ionic crosslinked interactions confer high mechanical properties to the hydrogel.Terbium ions are not only used as the ionic cross-linked points,but also used as green emitters to endow hydrogels with fluorescent properties.On the basis of the “antenna effect” of terbium ions and the ion exchange interaction,the fluorescence of the hydrogels can make selective responses to various ions(such as organic acid radical ions,transition metal ions) in aqueous solutions,which enables a convenient strategy for visual detection toward ions.Consequently,the fluorescent double network hydrogel fabricated in this study is promising for use in the field of visual sensor detection.

Nanozyme‑Engineered Hydrogels for Anti‑Inflammation and Skin Regeneration

Inflammatory skin disorders can cause chronic scarring and functional impairments,posing a significant burden on patients and the healthcare system.Conventional therapies,such as corticosteroids and nonsteroidal anti-inflammatory drugs,are limited in efficacy and associated with adverse effects.Recently,nanozyme(NZ)-based hydrogels have shown great promise in addressing these challenges.NZ-based hydrogels possess unique therapeutic abilities by combining the therapeutic benefits of redox nanomaterials with enzymatic activity and the water-retaining capacity of hydrogels.The multifaceted therapeutic effects of these hydrogels include scavenging reactive oxygen species and other inflammatory mediators modulating immune responses toward a pro-regenerative environment and enhancing regenerative potential by triggering cell migration and differentiation.This review highlights the current state of the art in NZ-engineered hydrogels(NZ@hydrogels)for anti-inflammatory and skin regeneration applications.It also discusses the underlying chemo-mechano-biological mechanisms behind their effectiveness.Additionally,the challenges and future directions in this ground,particularly their clinical translation,are addressed.The insights provided in this review can aid in the design and engineering of novel NZ-based hydrogels,offering new possibilities for targeted and personalized skin-care therapies.

Development of biomedical hydrogels for rheumatoid arthritis treatment

Rheumatoid Arthritis(RA)is an autoimmune disorder that hinders the normal functioning of bones and joints and reduces the quality of human life.Every year,millions of people are diagnosed with RA worldwide,particularly among elderly individuals and women.Therefore,there is a global need to develop new biomaterials,medicines and therapeutic methods for treating RA.This will improve the Healthcare Access and Quality Index and also relieve administrative and financial burdens on healthcare service providers at a global scale.Hydrogels are soft and cross-linked polymeric materials that can store a chunk of fluids,drugs and biomolecules for hydration and therapeutic applications.Hydrogels are biocompatible and exhibit excellent mechanical properties,such as providing elastic cushions to articulating joints by mimicking the natural synovial fluid.Hence,hydrogels create a natural biological environment within the synovial cavity to reduce autoimmune reactions and friction.Hydrogels also lubricate the articulating joint surfaces to prevent degradation of synovial surfaces of bones and cartilage,thus exhibiting high potential for treating RA.This work reviews the progress in injectable and implantable hydrogels,synthesis methods,types of drugs,advantages and challenges.Additionally,it discusses the role of hydrogels in targeted drug delivery,mechanistic behaviour and tribological performance for RA treatment.

Tuning mechanical behaviors of highly entangled hydrogels with the random distribution of mobile entanglements

Highly entangled hydrogels exhibit excellent mechanical properties,including high toughness,high stretchability,and low hysteresis.By considering the evolution of randomly distributed entanglements within the polymer network upon mechanical stretches,we develop a constitutive theory to describe the large stretch behaviors of these hydrogels.In the theory,we utilize a representative volume element(RVE)in the shape of a cube,within which there exists an averaged chain segment along each edge and a mobile entanglement at each corner.By employing an explicit method,we decouple the elasticity of the hydrogels from the sliding motion of their entanglements,and derive the stress-stretch relations for these hydrogels.The present theoretical analysis is in agreement with experiment,and highlights the significant influence of the entanglement distribution within the hydrogels on their elasticity.We also implement the present developed constitutive theory into a commercial finite element software,and the subsequent simulations demonstrate that the exact distribution of entanglements strongly affects the mechanical behaviors of the structures of these hydrogels.Overall,the present theory provides valuable insights into the deformation mechanism of highly entangled hydrogels,and can aid in the design of these hydrogels with enhanced performance.

Ionization Engineering of Hydrogels Enables Highly Efficient Salt‑Impeded Solar Evaporation and Night‑Time Electricity Harvesting

Interfacial solar evaporation holds immense potential for brine desalination with low carbon footprints and high energy utilization.Hydrogels,as a tunable material platform from the molecular level to the macroscopic scale,have been considered the most promising candidate for solar evaporation.However,the simultaneous achievement of high evaporation efficiency and satisfactory tolerance to salt ions in brine remains a challenging scientific bottleneck,restricting the widespread application.Herein,we report ionization engineering,which endows polymer chains of hydrogels with electronegativity for impeding salt ions and activating water molecules,fundamentally overcoming the hydrogel salt-impeded challenge and dramatically expediting water evaporating in brine.The sodium dodecyl benzene sulfonate-modified carbon black is chosen as the solar absorbers.The hydrogel reaches a ground-breaking evaporation rate of 2.9 kg m−2 h−1 in 20 wt%brine with 95.6%efficiency under one sun irradiation,surpassing most of the reported literature.More notably,such a hydrogel-based evaporator enables extracting clean water from oversaturated salt solutions and maintains durability under different high-strength deformation or a 15-day continuous operation.Meantime,on the basis of the cation selectivity induced by the electronegativity,we first propose an all-day system that evaporates during the day and generates salinity-gradient electricity using waste-evaporated brine at night,anticipating pioneer a new opportunity for all-day resource-generating systems in fields of freshwater and electricity.

Biomimetic fibril-like injectable hydrogels for wound management

Soft tissue repair and regeneration present a significant clinical challenge.Soft hydrogels have emerged as a promising solution for promoting stem cell differentiation and facilitating soft tissue formation[1].Various materials,including synthetic polymers like polydimethyl siloxane and natural polymers like proteins,have been be used as hydrogel matrix for hydrogel preparation[2,3].However,the limited biodegradability,inhomogeneous network structure,and inadequate mechanical properties of these hydrogels hinder their long-term application in complex environments in vivo.Inspired by the nanostructure of collagen fibrils,Li et al.developed a strategy for creating injectable nanofibrillar hydrogels by combining self-assembly and chemical crosslinking of nanoparticles[4].Moreover,injectable hydrogels offer advantages as implantable materials,including better defect filling and reduced risk of infection compared to prefabricated hydrogels[5].

Self-Healing Liquid Metal Magnetic Hydrogels for Smart Feedback Sensors and High-Performance Electromagnetic Shielding

Hydrogels exhibit potential applications in smart wearable devices because of their exceptional sensitivity to various external stimuli.However,their applications are limited by challenges in terms of issues in biocompatibility,custom shape,and self-healing.Herein,a conductive,stretchable,adaptable,self-healing,and biocompatible liquid metal GaInSn/Ni-based composite hydrogel is developed by incorporating a magnetic liquid metal into the hydrogel framework through crosslinking polyvinyl alcohol(PVA)with sodium tetraborate.The excellent stretchability and fast self-healing capability of the PVA/liquid metal hydrogel are derived from its abundant hydrogen binding sites and liquid metal fusion.Significantly,owing to the magnetic constituent,the PVA/liquid metal hydrogel can be guided remotely using an external magnetic field to a specific position to repair the broken wires with no need for manual operation.The composite hydrogel also exhibits sensitive deformation responses and can be used as a strain sensor to monitor various body motions.Additionally,the multifunctional hydrogel displays absorption-dominated electromagnetic interference(EMI)shielding properties.The total shielding performance of the composite hydrogel increases to~62.5 dB from~31.8 dB of the pure PVA hydrogel at the thickness of 3.0 mm.The proposed bioinspired multifunctional magnetic hydrogel demonstrates substantial application potential in the field of intelligent wearable devices.

Thixotropic composite hydrogels based on agarose and inorganic hybrid gellants

Water can be used as oxidant in conjunction with metal particles to form metal-water propellant to increase the energy of propellant.For this application,water needs to be stored in form of solid and capable of becoming liquid when use.Stable and thixotropic hydrogel has good potential as water-retaining material and oxidant of metal-based propellant.In this study,we prepared organic/inorganic composite hydrogels by combining inorganic gellants hectorite and fumed silica with organic gellant agarose,respectively.The total content of the gellants can be reduced to less than 2%by adding agarose.The influence of agarose on water content,phase transition temperature,centrifugal stability and other basic physical properties of composite hydrogels were discussed.The results show that the composite hydrogels have better thixotropy and stability than pure inorganic hydrogels,and the gel-sol transformation can be realized by applying shear force or heating to the phase transition temperature.The composite hydrogels have good shear thinning ability and improved mechanical stability.Fumed silica/agarose hydrogels have better physical stability,while the thixotropy and shear thinning ability of hectorite/agarose hydrogels are better.

Engineering Smart Composite Hydrogels for Wearable Health Monitoring

Growing health awareness triggers the public's concern about health problems. People want a timely and comprehensive picture of their condition without frequent trips to the hospital for costly and cumbersome general check-ups. The wearable technique provides a continuous measurement method for health monitoring by tracking a person's physiological data and analyzing it locally or remotely.During the health monitoring process,different kinds of sensors convert physiological signals into electrical or optical signals that can be recorded and transmitted, consequently playing a crucial role in wearable techniques. Wearable application scenarios usually require sensors to possess excellent flexibility and stretchability. Thus, designing flexible and stretchable sensors with reliable performance is the key to wearable technology. Smart composite hydrogels, which have tunable electrical properties, mechanical properties, biocompatibility, and multi-stimulus sensitivity, are one of the best sensitive materials for wearable health monitoring. This review summarizes the common synthetic and performance optimization strategies of smart composite hydrogels and focuses on the current application of smart composite hydrogels in the field of wearable health monitoring.

Fabricating Cationic Lignin Hydrogels for Dye Adsorption

Due to the low content of adsorption-active groups in lignin,its application in the field of adsorption is limited.Herein,we first prepared cationic kraft lignin acrylate,from which a cationic lignin(CKLA)hydrogel was further prepared by cationic kraft lignin acrylate,acrylamide,and N,N’-methylenebisacrylamide.The morphology,compression properties and swelling properties of CKLA hydrogels were investigated.The prepared CKLA hydrogel was applied as an adsorbent for Congo red.The effect of CKLA hydrogel dosages,initial concentration of Congo red,and pH on adsorption efficiency was investigated.The maximum Congo red removal efficiency was obtained at the initial concentration of Congo red of 50 mg/L,pH 7,and 5 mg dosage of CKLA hydrogel with 20%cationic lignin content.After five cycles of adsorption,the adsorption efficiency of the hydrogel for Congo red still reached more than 80%.The CKLA hydrogel showed pseudo-second-order adsorption kinetics for Congo red adsorption.These results demonstrate the potential of the CKLA hydrogel as an adsorbent for water treatment.

Lignin-based Hydrogels for Biological Application

Lignin is the most abundant aromatic compound found in nature.The rich functional groups of lignin are responsible for its antibacterial,antioxidant,anti-ultraviolet,and biocompatible properties.As modified lignin has a higher molecular weight,water solubility,and better surface activity,it is a good candidate for the construction of new biological materials.Ligninbased hydrogels are a type of functional materials with broad application prospects in the biomedical field.This review aimed to introduce the biological properties of lignin and the application of lignin-based hydrogels in the biological field.

Preparation and Application of Biomass-based Sprayable Hydrogels

Hydrogels have three-dimensional network structures that have been widely applied owing to their high water content,excellent biocompatibility,and physicochemical properties.Compared with conventional hydrogels,sprayable hydrogels exhibit excellent temporal and spatial controllability.Biomass materials offer easy accessibility,biocompatibility,biodegradability,and other physicochemical properties that are extensively used in the formation of sprayable hydrogels.In situ formed biomass-based sprayable hydrogels are realized by chemical or physical crosslinking.Rapid spray filming,in situ drug delivery,high permeability,and flexible portability enable biomass-based sprayable hydrogels to show great potential for topical drug delivery,wound healing,and other applications.This review describes in detail the status of research on the preparation and application of biomassbased sprayable hydrogels and suggests prospects for their future development.

An Environment‑Tolerant Ion‑Conducting Double‑Network Composite Hydrogel for High‑Performance Flexible Electronic Devices

High-performance ion-conducting hydrogels(ICHs)are vital for developing flexible electronic devices.However,the robustness and ion-conducting behavior of ICHs deteriorate at extreme tempera-tures,hampering their use in soft electronics.To resolve these issues,a method involving freeze–thawing and ionizing radiation technology is reported herein for synthesizing a novel double-network(DN)ICH based on a poly(ionic liquid)/MXene/poly(vinyl alcohol)(PMP DN ICH)system.The well-designed ICH exhibits outstanding ionic conductivity(63.89 mS cm^(-1) at 25℃),excellent temperature resistance(-60–80℃),prolonged stability(30 d at ambient temperature),high oxidation resist-ance,remarkable antibacterial activity,decent mechanical performance,and adhesion.Additionally,the ICH performs effectively in a flexible wireless strain sensor,thermal sensor,all-solid-state supercapacitor,and single-electrode triboelectric nanogenerator,thereby highlighting its viability in constructing soft electronic devices.The highly integrated gel structure endows these flexible electronic devices with stable,reliable signal output performance.In particular,the all-solid-state supercapacitor containing the PMP DN ICH electrolyte exhibits a high areal specific capacitance of 253.38 mF cm^(-2)(current density,1 mA cm^(-2))and excellent environmental adaptability.This study paves the way for the design and fabrication of high-performance mul-tifunctional/flexible ICHs for wearable sensing,energy-storage,and energy-harvesting applications.

Mechanical reliable,NIR light-induced rapid self-healing hydrogel electrolyte towards flexible zinc-ion hybrid supercapacitors with low-temperature adaptability and long service life

Hydrogel electrolytes hold great potential in flexible zinc ion supercapacitors(ZICs)due to their high conductivity,good safety,and flexibility.However,freezing of electrolytes at low temperature(subzero)leads to drastic reduction in ionic conductivity and mechanical properties that deteriorates the performance of flexible ZICs.Besides,the mechanical fracture during arbitrary deformations significantly prunes out the lifespan of the flexible device.Herein,a Zn^(2+)and Li^(+)co-doped,polypyrrole-dopamine decorated Sb_(2)S_(3)incorporated,and polyvinyl alcohol/poly(N-(2-hydroxyethyl)acrylamide)double-network hydrogel electrolyte is constructed with favorable mechanical reliability,anti-freezing,and self-healing ability.In addition,it delivers ultra-high ionic conductivity of 8.6 and 3.7 S m^(-1)at 20 and−30°C,respectively,and displays excellent mechanical properties to withstand tensile stress of 1.85 MPa with tensile elongation of 760%,together with fracture energy of 5.14 MJ m^(-3).Notably,the fractured hydrogel electrolyte can recover itself after only 90 s of infrared illumination,while regaining 83%of its tensile strain and almost 100%of its ionic conductivity during−30–60°C.Moreover,ZICs coupled with this hydrogel electrolyte not only show a wide voltage window(up to 2 V),but also provide high energy density of 230 Wh kg^(-1)at power density of 500 W kg^(-1)with a capacity retention of 86.7%after 20,000 cycles under 20°C.Furthermore,the ZICs are able to retain excellent capacity even under various mechanical deformation at−30°C.This contribution will open up new insights into design of advanced wearable flexible electronics with environmental adaptability and long-life span.

Nano-CaO_(2)Promotes the Release of Carbon Sources from Municipal Sludge and the Preparation of Double-Network Hydrogels with High Swelling Ratios

In this study,hydrogels were prepared from municipal sludge to recycle and realize the value-added utilization of the carbon components in this abundant waste material.The carbon sources were extracted from the municipal sludge using synthesised nano CaO_(2)as an oxidant,and the carbon sources were graft copolymerised with acrylic acid monomer using N,N′-methylenebisacrylamide as a crosslinking agent and ammonium persulfate as an initiator.The factors influencing the hydrogel preparation were investigated by single-factor experiments.Based on the results of the single-factor experiments,a hydrogel with a swelling ratio of up to 19768.4%at 12 h was prepared with an oxidant dosage of 0.20 g,a monomer dosage of 5.8 g,a neutralisation degree of the monomer of 70%,an initiator dosage of 0.15 g,and a crosslinking agent dosage of 0.15 g.The hydrogel preparation conditions were optimized using the response surface method,and the interactions between the different reaction conditions were analysed to obtain the best preparation conditions.X-ray diffraction results showed that hydrogels were amorphous in structure.Scanning electron microscopy images showed that the SiO_(2)particles from the sludge acted as crosslinking points between different layers of hydrogel chains.The crosslinking polymerisation and crosslinking agent worked together to form hydrogels with an inorganic-organic double network structure,and this structure was highly stretchable,resulting in hydrogels with good swelling properties.

Construction of 3D Shape-Changing Hydrogels via Light-Modulated Internal Stress Fields

The 3D shape-changing hydrogels are highly pursued for numerous applications.However,up to now,the construction of complex 3D shape-changing hydrogels remains a challenge.The reported design strategies are mainly applied to fabricate 2D ones by introducing anisotropic microstructures into hydrogel sheets/membranes.Herein,we present a convenient photolithography strategy for constructing complex 3D shape-changing hydrogels by simultaneously modulating anisotropic microstructures and internal stress fields of gel sheets.When the precursor solution containing ultraviolet(UV)absorber is irradiated by single-side UV light,the attenuated polymerization rate can cause the generation of asymmetric internal stress field in the resulting hydrogel sheet.In the meantime,the directional diffusion of unpolymerized monomers allows for the formation of vertical gradient structure within hydrogel.Therefore,by applying different photomasks to modulate the local gradient structures and internal stress fields of the gel sheets,they can spontaneously transform into various complex 3D shape-changing hydrogels in the air.Response to the external stimuli,these 3D shape-changing hydrogels(e.g.,fighter plane,birdie,and multi-storey origami lattices)can deform in a novel 3D_(1)-to-3D_(2)-to-3D_(3)mode.This new design strategy contributes to the development of complex biomedical implants and soft robotics.

Adhesive hydrogels in osteoarthritis:from design to application

Osteoarthritis(OA)is the most common type of degenerative joint disease which affects 7%of the global population and more than 500 million people worldwide.One research frontier is the development of hydrogels for OA treatment,which operate either as functional scaffolds of tissue engineering or as delivery vehicles of functional additives.Both approaches address the big challenge:establishing stable integration of such delivery systems or implants.Adhesive hydrogels provide possible solutions to this challenge.However,few studies have described the current advances in using adhesive hydrogel for OA treatment.This review summarizes the commonly used hydrogels with their adhesion mechanisms and components.Additionally,recognizing that OA is a complex disease involving different biological mechanisms,the bioactive therapeutic strategies are also presented.By presenting the adhesive hydrogels in an interdisciplinary way,including both the fields of chemistry and biology,this review will attempt to provide a comprehensive insight for designing novel bioadhesive systems for OA therapy.

Synthesis and Properties of Rosin-Based Composite Acrylamide Hydrogels

Hydrogels have been widely applied in agricultural drought-resistance,pollution regulation,drug delivery and so on.Acrylamide(AM)is usually used as raw material to synthesize acrylamide hydrogels.However,inherently low mechanical strength greatly limits their applications in some special areas.Therefore,it is necessary to choose suitable functional monomers to optimize acrylamide hydrogels and improve their mechanical performances.In this paper,a novel acrylamide monomer modified by rosin was synthesized,and then polyacrylamide/rosinbased acrylamide(RAM)composite hydrogels were prepared via free radical polymerization using potassium persulfate as initiator,N,N′-methylene-bisacrylamide(MBA)as a crosslinker.The influence of RAM monomer was investigated in detail.The chemical structure,pore structure,swelling properties,thermal performances and mechanical properties of composite hydrogels were characterized by Fourier Transform Infrared spectrometer(FT-IR),thermogravimetric analysis(TG),scanning electron microscope(SEM),and universal testing,respectively.The results showed that the thermal stability and mechanical property of RAM hydrogels were improved significantly.The compressive strength of RAM hydrogels was increased to 3.5 times than that of AM hydrogels,and the tensile strength was 5.1 times compared with AM hydrogels as well.Moreover,RAM hydrogels exhibited a faster initial swelling rate due to the new pore structure formed after introducing the RAM monomer.

3D-printed engineered bacteria-laden gelatin/sodium alginate composite hydrogels for biological detection of ionizing radiation

Nuclear safety is a global growing concern,where ionizing radiation(IR)is a major injury factor resulting in serious damage to organisms.The detection of IR is usually conducted with physical dosimeters;however,biological IR detection methods are deficient.Here,a living composite hydrogel consisting of engineered bacteria and gelatin/sodium alginate was 3D-printed for the biological detection of IR.Three strains of PrecA::egfp gene circuit-containing engineered Escherichia coli were constructed with IR-dependent fluorescence,and the DH5αstrain was finally selected due to its highest radiation response and fluorescence.Engineered bacteria were loaded in a series of gelatin/sodium alginate matrix hydrogels with different rheology,3D printability and bacterial applicability.A high-gelatin-content hydrogel containing 10%gelatin/1.25%sodium alginatewas optimal.The optimal living composite hydrogelwas 3D-printedwith the special bioink,which reported significant green fluorescence underγ-ray radiation.The living composite hydrogel provides a biological strategy for the detection of environmental ionizing radiation.

Improving physical properties of poly(vinyl alcohol)/montmorillonite nanocomposite hydrogels via the Hofmeister effect

Hydrogel is a kind of three-dimensional crosslinked polymer material with high moisture content.However,due to the network defects of polymer gels,traditional hydrogels are usually brittle and fragile,which limits their practical applications.Herein,we present a Hofmeister effect-aided facile strategy to prepare high-performance poly(vinyl alcohol)/montmorillonite nanocomposite hydrogels.Layered montmorillonite nanosheets can not only serve as crosslinking agents to enhance the mechanical properties of the hydrogel but also promote the ion conduction.More importantly,based on the Hofmeister effect,the presence of(NH_(4))_(2)SO_(4)can endow nanocomposite hydrogels with excellent mechanical properties by affecting PVA chains'aggregation state and crystallinity.As a result,the as-prepared nanocomposite hydrogels possess unique physical properties,including robust mechanical and electrical properties.The as-prepared hydrogels can be further assembled into a high-performance flexible sensor,which can sensitively detect large-scale and small-scale human activities.The simple design concept of this work is believed to provide a new prospect for developing robust nanocomposite hydrogels and flexible devices in the future.