Single Network Hydrogels Research Articles

Injectable Dual Fenton/Enzymatically Cross-Linked Double-Network Hydrogels Based on Acrylic/Phenolic Polymers with Highly Reinforced and Tunable Mechanical Properties.

Injectable hydrogels have been extensively used as promising therapeutic scaffolds for a wide range of biomedical applications, such as tissue regeneration and drug delivery. However, their low fracture toughness and brittleness often limit their scope of application. Double-network (DN) hydrogel, which is composed of independently cross-linked rigid and ductile polymer networks, has been proposed as an alternative technique to compensate for the weak mechanical properties of hydrogels. Nevertheless, some challenges still remain, such as the complicated and time-consuming process for DN formation, and the difficulty in controlling the mechanical properties of DN hydrogels. In this study, we introduce a simple, rapid, and controllable method to prepare in situ cross-linkable injectable DN hydrogels composed of acrylamide (AAm) and 4-arm-PPO-PEO-tyramine (TTA) via dual Fenton- and enzyme-mediated reactions. By varying the concentration of Fenton's reagent, the DN hydrogels were rapidly formed with controllable gelation rate. Importantly, the DN hydrogels showed a 13-fold increase in compressive strength and a 14-fold increase in tensile strength, compared to the single network hydrogels. The mechanical properties, elasticity, and plasticity of DN hydrogels could also be modulated by simply varying the preparation conditions, including the cross-linking density and reagent concentrations. At low cross-linker concentration (<0.05 wt %), the plastic DN hydrogel stretched to over 6,500%, whereas high cross-linker concentration (≥0.05 wt %) induced fully elastic hydrogels, without hysteresis. Besides, DN hydrogels were endowed with rapid self-recovery and highly enhanced adhesion, which can be further applied to wearable devices. Moreover, human dermal fibroblasts treated with DN hydrogels retained viability, demonstrating the biocompatibility of the cross-linking system. Therefore, we expect that the dual Fenton-/enzyme-mediated cross-linkable DN hydrogels offer great potential as advanced biomaterials applied for hard tissue regeneration and replacement.

Crosslinking and Swelling Properties of pH-Responsive Poly(Ethylene Glycol)/Poly(Acrylic Acid) Interpenetrating Polymer Network Hydrogels.

This study investigates the crosslinking dynamics and swelling properties of pH-responsive poly(ethylene glycol) (PEG)/poly(acrylic acid) (PAA) interpenetrating polymer network (IPN) hydrogels. These hydrogels feature denser crosslinked networks compared to PEG single network (SN) hydrogels. Fabrication involved a two-step UV curing process: First, forming PEG-SN hydrogels using poly(ethylene glycol) diacrylate (PEGDA) through UV-induced free radical polymerization and crosslinking reactions, then immersing them in PAA solutions with two different molar ratios of acrylic acid (AA) monomer and poly(ethylene glycol) dimethacrylate (PEGDMA) crosslinker. A subsequent UV curing step created PAA networks within the pre-fabricated PEG hydrogels. The incorporation of AA with ionizable functional groups imparted pH sensitivity to the hydrogels, allowing the swelling ratio to respond to environmental pH changes. Rheological analysis showed that PEG/PAA IPN hydrogels had a higher storage modulus (G') than PEG-SN hydrogels, with PEG/PAA-IPN5 exhibiting the highest modulus. Thermal analysis via thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) indicated increased thermal stability for PEG/PAA-IPN5 compared to PEG/PAA-IPN1, due to higher crosslinking density from increased PEGDMA content. Consistent with the storage modulus trend, PEG/PAA-IPN hydrogels demonstrated superior mechanical properties compared to PEG-SN hydrogels. The tighter network structure led to reduced water uptake and a higher gel modulus in swollen IPN hydrogels, attributed to the increased density of active network strands. Below the pKa (4.3) of acrylic acid, hydrogen bonds between PEG and PAA chains caused the IPN hydrogels to contract. Above the pKa, ionization of PAA chains induced electrostatic repulsion and osmotic forces, increasing water absorption. Adjusting the crosslinking density of the PAA network enabled fine-tuning of the IPN hydrogels' properties, allowing comprehensive comparison of single network and IPN characteristics.

Dual crosslinked interpenetrating polymer network-based porous hydrogel membrane for solid-state supercapacitor applications

Hydrogel membranes have emerged as promising candidates for solid-state supercapacitors (SSCs), overcoming limitations associated with traditional liquid electrolytes like leakage, thermal hazards, and flammability. However, single-network hydrogels often suffer from poor mechanical properties, making them inadequate for wearable applications. Herein, solution casting technique is used to develop a novel dual-crosslinked semi-interpenetrating polymer network (semi-IPN) hydrogel membrane through in-situ polymerisation of acrylic acid (AA) in a polyvinyl alcohol (PVA) matrix, followed by doping with KOH solution. By adjusting the composition between PVA and AA, the phase separation pathway is controlled, resulting in a homogeneously distributed porous architecture that enhances ion-conductive pathways. The hydrogel exhibited excellent properties, including high ionic conductivity (174 mS cm−1), considerable tensile strength (5 MPa), and significant elongation at break (460 %). Dielectric studies confirmed its significantly improved capacitive behaviour and low conductivity relaxation characteristics. Additionally, the resulting pseudocapacitor assembled with graphite-silvernanowire-polyaniline based composite electrode demonstrated a high specific capacitance (302 F g−1 at 0.2 A g−1) with outstanding capacity retention (75 % up to 500 cycles). Overall, the incorporation of this novel material provides great potential for high-performance SSC applications.

Phase transition in polymer hydrogels investigated by swelling, DSC, FTIR and NMR

AbstractThe swelling and thermal behavior of single (SN) and double network (DN) hydrogels containing polyacrylamide (PAAm) and temperature sensitive poly(N, N-diethylacrylamide) (PNNDEAAm) were investigated by gravimetry and differential scanning calorimetry (DSC). Changes of the hydration of carbonyl groups and mobility of polymer network chains in the hydrogels with temperature were studied by Fourier-transformed infrared and proton nuclear magnetic resonance (1H NMR) spectroscopy. The enthalpy of dissociation of the hydrophobic interaction, minimum and maximum numbers of water molecules per monomer unit in PNNDEAAm SN hydrogel involved in the hydrophobic hydration were determined by DSC. The volume phase transition accompanied by expulsion/uptake of water and heat absorption/release in heating/cooling was exhibited by all DN hydrogels containing PNNDEAAm. In these hydrogels, above the phase transition temperature, the population of hydrated carbonyls is enriched with the free and single hydrated ones in the same way as in the aqueous solution of linear PNNDEAAm and mobility of the PNNDEAAm chains is strongly reduced. Presence of the PAAm network does not influence the phase transition temperature but strongly reduces the enthalpy of the phase transition, promotes higher degrees of hydration of carbonyls, and increases mobility of the PNNDEAAm chains in the mixed hydrogels above the phase transition temperature.

Highly Sensitive Flexible Capacitive Pressure Sensor Based on a Multicross-Linked Dual-Network Ionic Hydrogel for Blood Pressure Monitoring Applications.

Flexible capacitive pressure sensors based on ionic hydrogels (IHs) have garnered significant attention in the field of wearable technology. However, the vulnerability of traditional single-network hydrogels to mechanical damage and the complexity associated with preparing double-network hydrogels present challenges in developing a highly sensitive, easily prepared, and durable IH-based flexible capacitive pressure sensor. This study introduces a novel multicross-linked dual-network IH achieved through the physical and chemical cross-linking of polymers polyvinyl alcohol (PVA) and chitosan (CS), ionic solution H3PO4, and cross-linking agent gum arabic. Flexible capacitive pressure sensors, characterized by high sensitivity and a broad pressure range, are fabricated by employing mesh as templates to design cut-corner cube microstructures with high uniformity and controllability on the IHs. The sensor exhibits high sensitivity across a wide pressure range (0-290 kPa) and with excellent features such as high resolution (∼1.3 Pa), fast response-recovery time (∼11 ms), and repeatable compression stability at 25 kPa (>2000 cycles). The IHs as a dielectric layer demonstrate long-term water retention properties, enabling exposure to air for up to 100 days. Additionally, the developed sensor shows the ability to accurately measure the pulse wave within the small pressure range. By combining the pulse wave acquired by the sensor with a trained neural network model, we achieve successful blood pressure (BP) prediction, meeting the standards set by the Association for the Advancement of Medical Instrumentation and the British Hypertension Society. Ultimately, the sensor proposed in this study holds promising prospects for broad applications in high-precision wearable medical electronic devices.

Tough double-network hydrogels with excellent frictional properties based on the in-suit inhibition strategy for biomedical applications

Osteoarthritis (OA) is one of the most common joint disorders all over the world and hydrogels could be an effective tool to solve this problem. In this work, we explore the mechanism of tribology properties of double-network hydrogel (DN hydrogel) under effect of free radical polymerization inhibitors. Fe3+ is added to the DN hydrogel as highly efficient and easily adjustable inhibitor, and the friction coefficient can be reduced to 0.0038 by adjusting the concentration. Even after 6 h of continuous tribological testing, the DN hydrogel remains a surprising sustained superlubricity. Furthermore, the strength of the hydrogel can reach 2.36 MPa, which is 20 times higher than that of the single-network hydrogel (SN hydrogel). The introduction of the inhibitor reduces covalent crosslinking that enables the hydrogel to form a sparser mesh structure conducive to the reduction of the friction coefficient, especially the additional physical cross-linking delivered from the electrostatic interaction between Fe3+ and carboxyl groups increases strength. The optimum concentration of Fe3+ is explored to achieve the synergetic improvement of lubricative and mechanical properties. This work opens innovative technology routes for developing superlubricious and tough hydrogels, which is a brighter future for artificial cartilage applications.

Mechanics of single-network hydrogels with network imperfection

Polymer network is a crucial component of hydrogels, and network imperfection is a prominent feature of polymer networks, significantly influencing the performance of hydrogels. Two essential features of network imperfection are unequal chain lengths and dangling chains, both of which have a significant impact on the mechanical properties of single-network (SN) hydrogels. However, a theoretical framework considering network imperfection in SN hydrogels is still lacking. Here, we propose a theoretical model for SN hydrogels with network imperfection to study the damage behavior during deformation, in which we adopt different chain length distributions to accurately depict the real physical characteristics of the polymer network and incorporate the normalized critical chain force for a more precise measurement of network damage. To verify our theory, we discuss the effects of model parameters on the stress-stretch responses of SN hydrogels and predict the results of uniaxial loading-unloading tests of SN hydrogels, which agree well with experimentally measured stress-stretch behaviors. Finally, we implement the constitutive model into ABAQUS as a user subroutine to study the inhomogeneous deformation of hydrogels.

Developing a gel-col heterogeneous network hydrogel scaffold for tissue-engineered skin with enhanced basement membrane formation

Tissue-engineered skin is constructed utilizing biocompatible matrix materials as scaffolds, and incorporating human epidermal keratinocytes (HEKs), dermal fibroblasts (HDFs), and bioactive molecules, addressing clinical issues such as skin graft rejection and donor scarcity. Conventional fabrication methods of tissue-engineered skin typically rely on homogeneous single-network scaffolds, which may not adequately address the distinct requirements of epidermal and dermal cells or the critical formation of the basement membrane, potentially impacting the development and functional integrity of the skin tissue. Cell culture studies employing GelMA hydrogels of varied concentrations have elucidated that epidermal cells exhibit increased viability on scaffolds with higher concentrations (15 %), whereas fibroblasts show increased proliferation within scaffolds of lower concentrations (5 %). Consequently, we have engineered a GelMA-collagen (Gel-Col) hydrogel scaffold with a heterogeneous network of dense and sparse matrices, conducive to the growth of both fibroblasts and epidermal cells. Culturing epidermal cells on this innovative scaffold, coupled with histological section staining, RT-PCR, and Western blot analyses, has demonstrated that the scaffold significantly enhances cellular adhesion and promotes the development of the epidermal basement membrane compared to single-network hydrogels. Mouse wound transplantation experiments have further confirmed the scaffold’s effectiveness in accelerating wound repair, supporting the development of the basement membrane, and enhancing epidermal regeneration. This research provides a reference for constructing tissue-engineered skin that more precisely emulates the intricate architecture and cellular dynamics of natural skin, propelling the advancement of tissue-engineered skin grafts in the clinical treatment of skin injuries.

MXene Crosslinked Hydrogels with Low Hysteresis Conferred by Sliding Tangle Island Strategy.

Single-network hydrogels are often too fragile to withstand mechanical loading, whereas double-network hydrogels typically exhibit significant hysteresis during cyclic stretching-releasing process due to the presence of a sacrificial network. Consequently, it is a considerable challenge for designing hydrogels that are both low in hysteresis and high in toughness for applications requiring dynamic mechanical loads. Herein, the study introduced a novel "sliding tangle island" strategy for creating tough and low-hysteresis hydrogels, which are prepared through in situ polymerization of highly concentrated acrylamides (AM) to form numerous entanglements within the MXene spacing without any chemical crosslinker. The MXene entangled with long polyacrylamide (PAM) chains to form tangle island that served as a relay station to transmit stress to neighboring molecular chains. This mechanism helps alleviate stress concentration and enhances energy dissipation efficiency, thereby reducing mechanical hysteresis. The resulting hydrogel exhibited exceptional properties, including high stretchability (≈900%), low hysteresis (less than 7%), high toughness (1.34MJm-3), and excellent sensing performance to rival the commercial hydrogel electrode. Therefore, this work sheds light on feasible design of energy dissipation structure to reduce the hysteresis of the composite hydrogels.

Spermidine-Functionalized Injectable Hydrogel Reduces Inflammation and Enhances Healing of Acute and Diabetic Wounds In Situ.

The inflammatory response is a key factor affecting tissue regeneration. Inspired by the immunomodulatory role of spermidine, an injectable double network hydrogel functionalized with spermidine (DN-SPD) is developed, where the first and second networks are formed by dynamic imine bonds and non-dynamic photo-crosslinked bonds respectively. The single network hydrogel before photo-crosslinking exhibits excellent injectability and thus can be printed and photo-crosslinked in situ to form double network hydrogels. DN-SPD hydrogel has demonstrated desirable mechanical properties and tissue adhesion. More importantly, an "operando" comparison of hydrogels loaded with spermidine or diethylenetriamine (DETA), a sham molecule resembling spermidine, has shown similar physical properties, but quite different biological functions. Specifically, the outcomes of 3 sets of in vivo animal experiments demonstrate that DN-SPD hydrogel can not only reduce inflammation caused by implanted exogenous biomaterials and reactive oxygen species but also promote the polarization of macrophages toward regenerative M2 phenotype, in comparison with DN-DETA hydrogel. Moreover, the immunoregulation by spermidine can also translate into faster and more natural healing of both acute wounds and diabetic wounds. Hence, the local administration of spermidine affords a simple but elegant approach to attenuate foreign body reactions induced by exogenous biomaterials to treat chronic refractory wounds.

Designing Ultratough Single-Network Hydrogels with Centimeter-Scale Fractocohesive Lengths via Inelastic Crack Blunting.

Fractocohesive length, defined as the ratio of fracture toughness to work of fracture, measures the sensitivity of materials to fracture in the presence of flaws. The larger the fractocohesive length, the more flaw-tolerant and crack-resistant the hydrogel. For synthetic soft materials, the fractocohesive length is short, often on the scale of 1 mm. Here, highly flaw-insensitive (HFI) single-network hydrogels containing an entangled inhomogeneous polymer network of widely distributed chain lengths are designed. The HFI hydrogels demonstrate a centimeter-scale fractocohesive length of 2.21cm, which is the highest ever recorded for synthetic hydrogels, and an unprecedented fracture toughness of ≈13300 J m-2 . The uncommon flaw insensitivity results from the inelastic crack blunting inherent to the highly inhomogeneous network. When the HFI hydrogel is stretched, a large number of short chains break while coiled long chains can disentangle, unwind, and straighten, producing large inelastic deformation that substantially blunts the crack tip in a plastic manner, thereby deconcentrating crack-tip stresses and blocking crack extension. The flaw-insensitive design strategy is applicable to various hydrogels such as polyacrylamide and poly(N,N-dimethylacrylamide) hydrogels and enables the development of HFI soft composites.

Strong, tough and conductive single-network hydrogels based on deswelling and the salting-out effect.

In recent years, the continuous attention given to increasing the fracture toughness and Young's modulus of polymeric gels has gradually shifted from toughening strategies on double-network (DN) gels to single-network (SN) gels. The salt-soaking method has been adopted to realize the toughening of SN gels through the salting-out effect and deswelling, constructing dense network structures with simultaneously precipitated polymer chains and cross-links. By comparing the mechanical properties between salt-treated hydrogels and air-dried hydrogels, the increased polymer chain concentration is proved to promote energy transfer by enlarging the dissipation region size due to the unwinding and slippage of coiled chains during stretching. The newly formed cross-link points in salt-treated hydrogels are considered to consume more deformation energy during stretching. The synergistic effect in energy transfer and dissipation arising from increases in polymer fraction and cross-linking plays an indispensable role in toughening SN hydrogels. In addition, the soaking process introduces abundant free ions to endow hydrogels with prominent conductivity. Thus, this salt-soaking method provides a general approach to synthesize strong, tough and conductive hydrogels with applications in flexible electrical devices.

Application of Solvent-Assisted Dual-Network Hydrogel in Water-Based Drilling Fluid for Lost Circulation Treatment in Fractured Formation.

During oil and gas well construction, lost circulation caused substantial nonoperation time and extra costs, and hydrogel, resilient and environmentally friendly, was one of the major types of material for lost circulation treatment. To migrate the weak bonding and hydrothermal degradation of conventional single network hydrogels, dual network (DN) hydrogel was prepared and immersed in solvents of polyethylene glycol (PEG), ethylene glycol, and glycerol. The swelling of DN gels at different temperatures was studied with water content and swelling rate tests, and the gel structural and morphology was characterized with attenuated total reflectance infrared spectroscopy (ATR-IR) and scanning electron microscopy test. Then, the compression test and fracture plugging performance test were conducted to study the strength of the gel. The results show that compared to those in ethylene glycol and glycerin, DN gel after immersion in PEG (DN-PEG) exhibits greater compression strength and better plugging performance even at high temperatures. The compression strength of DN-PEG was twice that of DN hydrogel before immersion, and its fracture plug breaking pressure can reach over 10.0 MPa. After undergoing hydrothermal treatment at 90 °C, the compression strength of the DN-PEG was nearly 20 times that of the DN hydrogel, and the fracture plug breaking pressure was still 2.81 MPa. According to ATR-IR spectroscopy, as the molecular weight of the solvent increases, more hydroxyl groups in the PEG have better ability to bind with hydrogen bonds, which greatly inhibits the swelling and polymer chain breakage, thereby reducing hydrothermal degradation in the strength of the dual-network hydrogel. Our work proposed an effective method to reduce the degradation of hydrogel in water at high temperature, and the prepared DN-PEG hydrogel was a promising material for lost circulation treatments in fractured formation.

A novel low-voltage responsive NIPAAm/CNTs/Fe(phen)3 double network shape-changing hydrogel with a balance between mechanical properties and deformation ability

The trade-off of electro-induced shape-changing hydrogels (EISCHs) between mechanical properties and deformation ability limited its further applications. In this work, the double network technique of reinforcing nondeformable hydrogels’ mechanical properties was introduced into EISCHs, and the NIPAAm/CNTs/Fe(phen)3 double network low-voltage-induced shape-changing hydrogel (DN) was synthesized. The experimental results indicated that the DN gained the balance between mechanical properties and deformation ability compared to the NIPAAm-Fe(phen)3 single network and NIPAAm-Fe(phen)3-CNTs nanocomposite single network hydrogels. The DN was found to have the ability to undergo swelling and shrinking as a result of the transition between Fe(phen)3 network iron (Ⅱ) and iron (Ⅲ) states under low-voltage stimulation. The hydrogen bonding and physical entanglement structure between CNTs and polymer chain segments, and physical entanglements between different network, which enable effective energy dissipation. Meanwhile, the special double network structure enabled the hydrogel could decrease the resistance to deformation stress by the slide between two networks.

Physical dynamic double-network hydrogels as dressings to facilitate tissue repair.

Double-network hydrogels can be tuned to have high mechanical strength, stability, elasticity and bioresponsive properties, which can be combined to create self-healing, adhesive and antibacterial wound dressings. Compared with single-network hydrogel, double-network hydrogel shows stronger mechanical properties and better stability. In comparison with chemical bonds, the cross-linking in double networks makes them more flexible than single-network hydrogels and capable of self-healing following mechanical damage. Here, we present the stepwise synthesis of physical double-network hydrogels where hydrogen bonds and coordination reactions provide self-healing, pH-responsive, tissue-adhesive, antioxidant, photothermal and antibacterial properties, and can be removed on demand. We then explain how to carry out physical, chemical and biological characterizations of the hydrogels for use as wound dressings, yet the double-network hydrogels could also be used in different applications such as tissue engineering scaffolds, cell/drug delivery systems, hemostatic agents or in flexible wearable devices for monitoring physiological and pathological parameters. We also outline how to use the double-network hydrogels in vivo as wound dressings or hemostatic agents. The synthesis of the ureido-pyrimidinone-modified gelatin, catechol-modified polymers and the hydrogels requires 84 h, 48 h and 1 h, respectively, whereas the in vivo assays require 3.5 weeks. The procedure is suitable for users with expertise in biomedical polymer materials.

All-Natural, Robust, and pH-Responsive Glycyrrhizic Acid-Based Double Network Hydrogels for Controlled Nutrient Release.

Supramolecular hydrogels self-assembled from naturally occurring small molecules (e.g., glycyrrhizic acid, GA) are promising materials for controlled bioactive delivery due to their facile fabrication processes, excellent biocompatibility, and versatile stimuli-responsive behaviors. However, most of these natural hydrogels suffer from poor mechanical strength and processability for practical applications. In this work, through adopting a multicomponent gel approach, we developed a novel mechanically robust GA-based hydrogel with an interpenetrating double network (DN) that is composed of a Ca2+-enhanced hydrogen-bond supramolecular GA nanofibril (GN) network and a Ca2+cross-linked natural polysaccharide sodium alginate (ALG) network. Compared to the single GN network (SN) hydrogel, the GN-ALG hybrid hydrogels (GN-ALG-DN) with the hierarchical double-network structure possess excellent mechanical properties and shaping adaptation, encouraging small and large amplitude oscillatory shear (SAOS and LAOS) rheological performances, better thermal stability, higher resistance to large compression deformations, and lower swelling behaviors. Furthermore, the GN-ALG-DN hydrogels exhibit a pH-responsive and sustained release behavior of nutrients (i.e., vitamin B12, VB12), showing a faster VB12 release rate with a higher swelling ratio in an alkaline condition (pH 7.5) than in an acidic condition (pH 2.5). This is ascribed to the fact that the higher dissociation degree of carboxylic groups in GA and ALG molecules in an alkaline environment induces the erosion and looseness of the self-assembled GN network and the ionic-cross-linked ALG network, which can lead to the decomposition of the hybrid hydrogels and thereby increases the release of nutrients. Cytotoxicity tests further demonstrate the excellent biocompatibility of the GN-ALG-DN hydrogels. This study highlights the design of robust shaped and structured supramolecular hydrogels from natural herb small molecules, which can serve as solid, edible, and stimuli-responsive active cargo delivery platforms for food, biomedical, and sustainable applications.

Preparation of polyethylene glycol/polyacrylamide interpenetrating network hydrogel for simultaneously enhancing the fire protection and aging resistance of fireproof glass

AbstractTo enhance the flame retardancy and aging resistance of grouting fireproof glass, different molecular weights of polyethylene glycol (PEG) were mixed with acrylamide (AM) to construct interpenetrating network hydrogels, then the obtained hydrogels were mixed with flame retardants to prepare a series of transparent flame‐retarded hydrogels applied in the fireproof glass. The effects of PAM/PEG hydrogel with varying PEG molecular weight on the optical transparency, heat insulation and aging resistance of fireproof glass were investigated. Optical transparency analysis shows that the light transmittance of grouting fireproof glass decreases with the increase of PEG molecular weight in the PAM/PEG interpenetrating network. Fire tests show that PAM/PEG hydrogel significantly enhances the heat insulation and aging resistance of the grouting fireproof glass compared to the single PAM network hydrogel. The flame‐retarded and anti‐aging effects of PAM/PEG hydrogel in the fireproof glass varies with the PEG molecular weight, and the order is PAM/PEG2000 &gt; PAM/PEG1500 &gt; PAM/PEG1000 &gt; PAM/PEG800. Accelerated aging test shows that PAM/PEG interpenetrating network hydrogel is less affected by aging conditions and exerts durable heat insulation and transmittance. Especially, the backside temperature of 3600 s and transmittance of PAM/PEG2000 system after 264 h aging test only changed 38.3°C and 1.3%, respectively, compared to the unaged PAM/PEG2000 system.

Hyaluronic acid single-network hydrogel with high stretchable and elastic properties

Stretchable materials have demonstrated great interest in wearable or implantable applications. Most of the existing hydrogels with high stretchability characteristics are based on double networks, exhibit large hysteresis loops, and cannot recover after deformation due to permanent rupture of network. Elastic, biodegradable, and biocompatible hydrogels are desirable for wound dressing of joints with frequent motions or post-surgical healing of mobile tissues. Here, we show a simple strategy for the preparation of a hyaluronic acid (HA) single-network hydrogel that can be stretchable and highly elastic without the addition of other components/partners or complicated processes of preparation. Our strategy relies on the use of high Mw HA to create a chemical hydrogel in which densely entangled HA chains are tied together by a small number of covalent bonds. While the presence of covalent cross-links can prevent disintegration of the HA network, entanglements endow the hydrogel with high stretchability through transmission of tension along the length of the long HA chains. The stretching-relaxation cycles show negligible hysteresis and perfect recovery of material after the release of force. The diminution of Mw together with increasing the concentration or cross-linker amount leads to brittle hydrogels.

Biomass-based single- and double-network hydrogels derived from cellulose microfiber and chitosan for potential application as plant growing substrate

A series of hydrogels were synthesized from renewable and low-cost micro-sized cellulose fiber. The single-network hydrogel was composed of cellulose fiber and a small amount of another polysaccharide, chitosan, which ‘glued’ individual cellulose fiber pieces together through Schiff-base bonding. The double-network hydrogel was constructed by adding a secondary network, the covalently crosslinked polyacrylamide, into the single-network hydrogel, which was synthesized by conducting Schiff-base reaction and free radical polymerization at the same time in a facile one-pot process. In both single- and double-network hydrogels, cellulose fiber constituted the dominant component. Both types of hydrogels exhibited good swelling properties. The double-network hydrogel showed much improved stability against soaking in water and higher salt tolerance. Germination experiment with choy sum seeds sowed on hydrogel surface showed that the seeds were able to germinate and further develop roots, shoots, and true leaves, demonstrating the potential of the biomass-derived hydrogels for soilless plant growing applications.

Highly stretchable, fast self-healing nanocellulose hydrogel combining borate ester bonds and acylhydrazone bonds

Self-healing hydrogels have received considerable attention as a promising material for flexible electronic devices given their mechanical durability and structurally tunable properties. In this study, a highly stretchable self-healing hydrogel with dual cross-linking network was developed via borate ester bonds generated by polyvinyl alcohol and borax, and acylhydrazone bonds formed by aldehyde nanocellulose with adipic acid dihydrazide-modified alginate. Compared with the single network hydrogel composed of polyvinyl alcohol and borax, the introduction of dynamic acylhydrazone bonds greatly increases the flexibility of the hydrogel. The elongation rate increased from 480 % to approximately 1440 %, and the self-healing efficiency increased from 84.6 % to 92.7 % after healing for 60 min at ambient temperature without any stimulus. Moreover, the longer the self-healing time, the more evident the self-healing effect of the acylhydrazone bonds. In addition, electrical measurements confirmed a wide working strain range (ca.1000 %), durability, and reliability. Once assembled as a strain sensor, the hydrogel is able to monitor both large and subtle human motions. Besides, this hydrogel exhibited desirable biocompatibility, as demonstrated by in vitro cytotoxicity towards NIH 3T3 cells. These integrated properties make this nanocomposite hydrogel a promising candidate for future applications as green, flexible, and smart sensors.