Double Network Hydrogels Research Articles

Chitosan-Promoted TiO2-Loaded Double-Network Hydrogels for Dye Removal and Wearable Sensors.

The loading of photocatalysts on hydrogels can significantly reduce the loss of catalysts and effectively prevent secondary contamination, thus demonstrating great application potential and advantages in the field of wastewater treatment, especially in the removal of dyes. Herein, the semiconductor TiO2 was successfully loaded into a polyacrylic acid/chitosan (PAA/CS) double-network (DN) hydrogel, which exhibited superior removal of dyes in wastewater such as MG, MB, MV, and RhB. The dye degradation process followed first-order kinetics, and the first-order rate constants for dye degradation were further calculated under UV light irradiation. Furthermore, the photocatalytic mechanism of the hydrogel was explored and analyzed. More interestingly, the PAA/CS-TiO2 DN hydrogel has excellent tensile properties and superior electrical conductivity, which can be assembled into flexible sensors for real-time monitoring of mechanical deformations and human joint motions. It is envisioned that these excellent properties make hydrogel photocatalysts promising for a wide range of applications.

Study on the mechanical properties of Polyacrylic Acid/Chitosan double network hydrogels in dynamic water content

Abstract Hydrogels have demonstrated significant potential in wound dressings, owing to their adjustable water content, excellent biocompatibility, and other advantages. An ideal wound dressing requires absorbing exudate while maintaining mechanical properties to prevent secondary damage to the wound under external pressure. In this study, Polyacrylic Acid (PAA)/Chitosan (CS) double network hydrogels were prepared via radical polymerization, and the swelling ratio, compressive modulus, and other parameters were experimentally measured. A hyperelastic finite element model of the hydrogel was then established, and its rationality was validated by experiments. Based on the model, the impacts of CS content and dynamic water content on the compressive properties of PAA/CS hydrogels were analyzed. Tetracycline hydrochloride was loaded into PAA/CS hydrogels, the drug release performance and adhesion experiments were carried out. The results indicated that, compared with the hydrogels with 2.5% and 5% CS content, the hydrogel with 1% CS content had the highest swelling ratio, which was 1774%. Meanwhile, its equilibrium water content could attain 94.6%. When the water content varied within the range from 45% to 75%, the compressive strength of the hydrogel with 5% CS content ranged from 0.33 MPa to 1.22 MPa, similar to that of skin tissue. Additionally, the prepared drug-loaded PAA/CS hydrogels exhibited a drug release pattern approximately following the Korsmeyer-Peppas model within 7 days. They also exhibited remarkable adhesion to porcine skin and different substrate surfaces. This study provides a basis for the clinical application of PAA/CS double network hydrogels as wound dressings in the repair of infected wounds.

One-step soaking strategy toward mechanical double-network hydrogel

Double-network (DN) hydrogels, which comprise noncovalent interacting networks, are highly sought after due to their controlled compositions and environmental friendliness. However, the complex preparation methods hinder the application of these hydrogels. In this study, we present a simple and feasible approach for fabricating hybrid PAA-CS DN hydrogels by post-treating the PAA-CS composite hydrogels with CuSO4 solutions to induce the formation of physical networks through CS chain entanglement. The composite hydrogel, composed of chitosan (CS) and polyacrylic acid (PAA), readily transforms into a DN hydrogel after soaking in a CuSO4 solution, thanks to in situ formation of chain entanglements, hydrogen bonds, and ionic coordination. The resulting hybrid DN hydrogels exhibit porous networks, high tensile strength, and exceptional toughness. This facile but effective soaking method can be universally applied to fabricate mechanically robust hydrogels, modulate noncovalent interactions, and broaden their potential applications.

One-pot fabrication of sodium deoxycholate based supramolecular self-healing antibacterial double network hydrogels

Double network (DN) hydrogels have emerged as a significant technology for enhancement of mechanical strength of weak supramolecular gels. In the present study, we report the one-pot route for design of a low molecular weight gelator based DN hydrogel wherein sodium deoxycholate (NaDC) forms the primary network entangled with agar matrix. Various compositions of the reported agar-NaDC hydrogels were examined through FTIR, sol-gel transition temperature (Tsg), XRD, circular dichroism (CD), scanning electron microscopy (SEM), hydrophobicity probe studies, Zeta potential studies and rheology measurements. Analysis of all studies together reveal that 1 mg/ml agar-NaDC DN hydrogel is the optimum composition that exhibits dense networking with primarily β-sheet like structure, highest mechanical strength as well as self-healing characteristics with reversed optical activity and highest Tsg. Antibacterial activity studied using inhibition zone method suggests that 1 mg/ml agar-NaDC gel demonstrates significant bactericidal effect unlike the pure gel with an inhibition zone of ∼25 mm against E.coli after 24 h and ∼32 mm after 48 h incubation. The antibacterial activity was unique for this composition of the DN hydrogel which is attributed to its reversal in optical activity exhibiting positive cotton effect resulting in stronger interaction with the bacterial cell wall. Additionally, nearly 2 times reduced water absorption capacity of the 1 mg/ml agar-NaDC DN hydrogel compared to pure NaDC hydrogel ensures the retention of its mechanical strength as well as other properties in high moisture containing environment. Hence, the 1 mg/ml agar-NaDC DN hydrogel holds appreciable potential as a novel strong supramolecular self-healing antibacterial hydrogel with sustained release characteristics primarily important for biomedical applications.

A highly sensitive and stable MXene/bacterial cellulose double network hydrogel flexible strain sensor for human activities monitoring

A highly sensitive and stable <scp>MXene</scp>/bacterial cellulose double network hydrogel flexible strain sensor for human activities monitoring

Double network hydrogel confined MXene/Liquid metal by dynamic hydrogen bond for high-performance wearable sensors

Double-network (DN) hydrogels, which integrate long-chain and short-chain molecular structures, exhibit significant potential in wearable sensors due to their exemplary mechanical properties. However, conventional hydrogels often suffer from poor conductivity and low sensitivity. In this study, we develop a novel DN hydrogel (comprising polyacrylamide/sodium alginate) that encapsulates MXene (Ti3C2Tx) and liquid metal (LM). This configuration leverages the conductive properties of two-dimensional MXene and zero-dimensional liquid metal embedded within the DN hydrogel networks. The Ti3C2Tx MXene sheets enhance the binding capacity with LM by serving as a conductive bridge, thereby improving interfacial interactions and reducing hysteresis. The resultant strain sensor, fabricated from this composite DN hydrogel, achieves high sensitivity (gauge factor up to 12.84), a broad detection range (0 %-1500 %), rapid response time (262 ms), and excellent repeatability and stability. We have integrated this strain sensor into wearable flexible devices, such as contact lenses, enabling real-time monitoring of human physiological pressures.

Mechanical properties and development of silver Nanoparticle-enhanced Alginate-polyacrylamide double network Hydrogel

Mechanical properties and development of silver Nanoparticle-enhanced Alginate-polyacrylamide double network Hydrogel

Rapid preparation of bioadhesive hydrogels containing catechol moieties at room temperature with reproducible adhesion to wet tissues, antimicrobial, antioxidant capacity for noncompressive hemostasis.

In order to cope with the massive tissue bleeding caused by sudden trauma and the demand for bioengineering materials with adjustable wet adhesion properties, this study formed the first layer of network by adding galactomannan (GG) and collagen (Col) structure, and then use the Fe3+-urushiol (UH) redox system to activate free radicals to initiate the polymerization of acrylic acid (AA) to quickly form an interpenetrating double network hydrogel. The cis hydroxyl group in GG and the hydroxyl group of UH form dynamic covalent borate ester bonds with borate ions in the borax solution, and use their responsiveness to pH to control the catechol group to achieve controllable adhesion. UH and Fe3+ endowed the hydrogel with excellent antibacterial ability, while adding Col enhanced the mechanical properties of the hydrogel. The elastic modulus and toughness increased from 4.32 kPa and 92.9 kJ/m3 to 18.90 kPa and 264.54 kJ/m3. In addition, due to the joint action of UH and Col, the hydrogel dressing can achieve rapid hemostasis within 20 s. In short, this hydrogel dressing has good biocompatibility, inherent antibacterial ability, adjustable moist tissue adhesion properties and rapid hemostatic ability, and is expected to become a candidate for wound hemostasis dressing.

Construction and characterization of sodium alginate/polyvinyl alcohol double-network hydrogel beads with surfactant-tailored adsorption capabilities for efficient tetracycline hydrochloride removal

The extensive use of tetracycline (TC) for disease control and the residuals in wastewater has resulted in the spread and accumulation of antibiotic resistance genes, posing a severe threat to the human health and environmental safety. To solve this problem, a series of double-network hydrogel beads based on sodium alginate and polyvinyl alcohol were constructed with the introduction of various surfactants to modulate the morphology. The results showed that the introduction of surfactants can modulate the surface morphology and internal structure, which can also regulate the adsorption ability of the hydrogel beads. The SDS-B beads with SDS as surfactant exhibited highest adsorption efficiency for removal of TC with a maximum adsorption capacity up to 121.6 mg/g, which possessed a resistance to various cations and humic acid. The adsorption mechanism revealed that the superior adsorption performance of the hydrogel beads was primarily attributed to hydrogen bonding, electrostatic attraction, and π-π EDA interactions. Adsorption kinetics demonstrated that the pseudo-second-order model fitted the adsorption process well and adsorption isotherm showed the adsorption of TC occurred through both chemical and physical interactions. Moreover, the adsorption efficiency remained approximately 87.5 % after three adsorption-desorption cycles, which may have potential application and practical value in TC adsorption.

High-performance conductive double-network hydrogel base on sodium carboxymethyl cellulose for multifunctional wearable sensors

High-performance conductive double-network hydrogel base on sodium carboxymethyl cellulose for multifunctional wearable sensors

Hyaluronic acid methacrylate/Pluronic F127 hydrogel enhanced with spermidine-modified mesoporous polydopamine nanoparticles for efficient synergistic periodontitis treatment

Bacterial infection, reactive oxygen species (ROS) accumulation, and persistent inflammation pose significant challenges in the treatment of periodontitis. However, the current single-modal strategy makes achieving the best treatment effect difficult. Herein, we developed a double-network hydrogel composed of Pluronic F127 (PF-127) and hyaluronic acid methacrylate (HAMA) loaded with spermidine-modified mesoporous polydopamine nanoparticles (M@S NPs). The PF-127/HAMA/M@S (PH/M@S) hydrogel was injectable and exhibited thermosensitivity and photocrosslinking capabilities, which enable it to adapt to the irregular shape of periodontal pockets. In vitro, the PH/M@S displayed multiple therapeutic effects, such as photothermal antibacterial activity, a high ROS scavenging capacity, and anti-inflammatory effects, which are beneficial for the multimodal treatment of periodontitis. The underlying anti-inflammatory mechanism of this hydrogel involves suppression of the extracellular regulated protein kinase 1/2 and nuclear factor kappa-B signalling pathways. Furthermore, in lipopolysaccharide-stimulated macrophage conditioned media, the PH/M@S effectively restored the osteogenic differentiation potential. In a rat model of periodontitis, the PH/M@S effectively reduced the bacterial load, relieved local inflammation and inhibited alveolar bone resorption. Collectively, these findings highlight the versatile functions of the PH/M@S, including photothermal antibacterial activity, ROS scavenging, and anti-inflammatory effects, indicating that this hydrogel is a promising multifunctional filling material for the treatment of periodontitis.

Wearable Multifunctional Hydrogel for Oral Microenvironment Visualized Sensing Coupled with Sonodynamic Bacterial Elimination and Tooth Whitening.

Bacterial-driven dental caries and tooth discoloration are growing concerns as the most common oral health problems. Current diagnostic methods and treatment strategies hardly allow simultaneous early detection and non-invasive treatment of these oral diseases. Herein, a wearable multifunctional double network hydrogel combined with polyaniline and barium titanate (PANI@BTO) nanoparticles is developed for oral microenvironment visualized sensing and sonodynamic therapy. Due to the colorimetric properties of polyaniline, the hydrogel displays a highly sensitive and selective response for visualized sensing of oral acidic microenvironment. Meanwhile, the barium titanate in the hydrogel efficiently generates reactive oxygen species (ROS) under ultrasound irradiation, realizing non-invasive treatment in the oral cavity. Through bacterial elimination experiments and tooth whitening studies, the hydrogel can achieve the dual effect of effectively inhibiting the growth of cariogenic bacteria and degrading tooth surface pigments. Owing to the visualized sensing of the oral acidic microenvironment and efficient sonodynamic therapy function, the proposed hydrogel system offers a solution for the prevention of caries and tooth whitening, which is promising in developing the biomedical system targeting the simultaneous sensing and therapy for oral diseases.

Soft hydrogel semiconductors with augmented biointeractive functions.

Hydrogels, known for their mechanical and chemical similarity to biological tissues, are widely used in biotechnologies, whereas semiconductors provide advanced electronic and optoelectronic functionalities such as signal amplification, sensing, and photomodulation. Combining semiconducting properties with hydrogel designs can enhance biointeractive functions and intimacy at biointerfaces, but this is challenging owing to the low hydrophilicity of polymer semiconductors. We developed a solvent affinity-induced assembly method that incorporates water-insoluble polymer semiconductors into double-network hydrogels. These semiconductors exhibited tissue-level moduli as soft as 81 kilopascals, stretchability of 150% strain, and charge-carrier mobility up to 1.4 square centimeters per volt per second. When they are interfaced with biological tissues, their tissue-level modulus enables alleviated immune reactions. The hydrogel's high porosity enhances molecular interactions at semiconductor-biofluid interfaces, resulting in photomodulation with higher response and volumetric biosensing with higher sensitivity.

Periosteum-bone inspired hierarchical scaffold with endogenous piezoelectricity for neuro-vascularized bone regeneration

The development of scaffolds for repairing critical-sized bone defects heavily relies on establishing a neuro-vascularized network for proper penetration of nerves and blood vessels. Despite significant advancements in using artificial bone-like scaffolds infused with various agents, challenges remain. Natural bone tissue consists of a porous bone matrix surrounded by a neuro-vascularized periosteum, with unique piezoelectric properties essential for bone growth. Drawing inspiration from this assembly, we developed a periosteum-bone-mimicking bilayer scaffold with piezoelectric properties for regeneration of critical-sized bone defects. The periosteum-like layer of this scaffold features a double network hydrogel composed of chelated alginate, gelatin methacrylate, and sintered whitlockite nanoparticles, emulating the viscoelastic and piezoelectric properties of the natural periosteum. The bone-like layer is composed of a porous structure of chitosan and bioactive hydroxyapatite created through a biomineralization process. Unlike conventional bone-like scaffolds, this bioinspired bilayer scaffold significantly enhances osteogenesis, angiogenesis, and neurogenesis combined with low-intensity pulsed ultrasound-assisted piezoelectric stimulation. Such a scheme enhances neuro-vascularized bone regeneration in vivo. The results suggest that the bilayer scaffold could serve as an effective self-powered electrical stimulator to expedite bone regeneration under dynamic physical stimulation.

Double-Network Hydrogel 3D BioPrinting Biocompatible with Fibroblast Cells for Tissue Engineering Applications

The present study examines the formulation of a biocompatible hydrogel bioink for 3D bioprinting, integrating poly(ethylene glycol) diacrylate (PEGDA) and sodium alginate (SA) using a double-network approach. These materials were chosen for their synergistic qualities, with PEGDA contributing to mechanical integrity and SA ensuring biocompatibility. Fibroblast cells were included in the bioink and printed with a Reg4Life bioprinter employing micro-extrusion technology. The optimisation of printing parameters included needle size and flow velocities. This led to precise structure development and yielded results with a negligible deviation in printed angles and better control of line widths. The rheological characteristics of the bioink were evaluated, demonstrating appropriate viscosity and shear-thinning behaviour for efficient extrusion. The mechanical characterisation revealed an average compressive modulus of 0.38 MPa, suitable for tissue engineering applications. The printability of the bioink was further confirmed through the evaluations of morphology and diffusion rates, confirming structural integrity. Biocompatibility assessments demonstrated a high cell viability rate of 82.65% following 48 h of incubation, supporting the bioink’s suitability for facilitating cell survival. This study introduced a reliable technique for producing tissue-engineered scaffolds that exhibit outstanding mechanical characteristics and cell viability, highlighting the promise of PEGDA–SA hydrogels in bioprinting applications.

Fabrication of Microstructured Hydrogels via Dehydration for On-Demand Applications.

Microstructured hydrogels show promising applications in various engineering fields from micromolds to anisotropic wetting surfaces and microfluidics. Although methods like molding by, e.g., casting as well as 3D printing are developed to fabricate microstructured hydrogels, developing fabrication methods with high controllability and low-cost is an on-going challenge. Here, a method is presented for creating microstructures through the dehydration of double network hydrogels. This method utilizes common acrylate monomers and a mask-assisted photopolymerization process, requiring no complex equipment or laborious chemical synthesis process. The shape and profile of microstructures can be easily controlled by varying the exposure time and the mask used during photopolymerization. By altering the monomer and the mask used for fabricating the second network hydrogel, both convex and concave microstructures can be produced. To showcase the utility of this method, the patterned hydrogel is utilized as a mold to fabricate a polydimethylsiloxane microlens array via soft lithography for imaging application. In addition, a patterned hydrogel surface exhibiting obvious anisotropic wetting properties and open microfluidic devices which can achieve fast directional superspreading within milliseconds are also fabricated to demonstrate the versatility of the method for different engineering fields.

Sulfonated corn stalk enhanced hydrogel adsorption for heavy metal from metal mine gallery effluent

There are various of abandoned metal mines in China, and a considerable amount of heavy metal contaminated water is generated through water–rock interactions and accumulated within metal mine gallery. Therefore, the effective removal of heavy metals from metal mine gallery effluent holds significant importance. In this study, sulfonated corn stalk (SCS) and acrylic acid was used to prepare the double network hydrogel SCS-gel. The maximum allowable compression force for the SCS-gel was about 3 times than that of raw hydrogel. The SCS-gel exhibited a stable adsorption capacity within the pH range from 2.0 to 6.0. The maximal adsorption capacities of Pb2+ and Cu2+ on the SCS-gel were 111.6 and 370.2 mg/g, respectively. The functional groups of –OH, C-O, C = O, COOH, and −SO3- were participated in the adsorption process through coordination and electrostatic interactions. The SCS-gel exhibited promising reusability as the adsorption efficiency for Pb2+ and Cu2+ remained at approximately 100 % within 10 cycles of adsorption–desorption. The SCS-gel had an excellent removal efficiency for Pb2+ (99.8 %), Cu2+ (99.1 %), Mn2+ (97.4 %), Zn2+ (98.8 %), and Al3+ (95.7 %) from actual metal mine gallery effluent by dosage of 5 g/L with the initial concentrations of Pb2+, Cu2+, Mn2+, Zn2+, and Al3+ were 4.352, 29.20, 13.02, 7.016, and 30.47 mg/L, respectively. In the fixed-bed experiments, the Thomas model has a good description for the breakthrough curves of these heavy metals. These results confirmed the possibility of adopting SCS ethers for hydrogel fabrication and verified its great potential for the practical application for the removal of heavy metals from metal mine gallery effluent.

Developing biomimetic PVA/PAA hydrogels with cellulose nanocrystals inspired by tree frog structures for superior wearable sensor functionality

This study developed a wearable sensor device featuring biomimetic structures inspired by tree frog toe pads to measure shoulder joint movements effectively. A PVA/PAA double-network hydrogel was formulated by mixing PVA and PAA in a 3:7 ratio, resulting in a Young's modulus of 7.2 kPa, closely matching human skin's mechanical properties. To enhance moisture retention, the hydrogel was supplemented with 20 mL glycerin, increasing its weight retention rate to 95 % after 28 days, a 5.6-fold improvement over glycerin-free hydrogels. Additionally, the incorporation of 0.2 wt% cellulose nanocrystals (CNC) increased the cross-linking density, reducing the swelling ratio from 124 % to 106 % and minimizing the impact of swelling cycles on mechanical properties from 22 % to 4 %. Treefrog-inspired microstructures were fabricated on the sensor surface using laser cutting and casting techniques, significantly enhancing adhesion under humid conditions, with normal, lateral, and peel-off adhesion forces improving by 500, 700, and 700 %, respectively. The sensor demonstrated accurate measurement of shoulder joint movements with an error margin of 6.3 % for polar angles (45°-135°) and 7.8 % for azimuth angles (0°-45°). The accompanying smartphone application provided real-time feedback, helping to prevent exercise injuries and improve user awareness and control of shoulder movements, making it suitable for both rehabilitation and athletic training.

Congelation- and dehydration-tolerant, mechanically robust hydrogel electrolyte for durable iontronic sensors operating in open air and freezing temperatures over wide strain and pressure ranges

Conventional hydrogels have limitations in mechanical properties and are susceptible to loss of elasticity and conductivity caused by congelation and dehydration, limiting their practical uses for application in high-stress environments, open air, and freezing temperatures. This study introduces a mechanically robust, dehydration- and congelation-tolerant, and ionically conductive hydrogel electrolyte, practical for iontronic sensors working in wide pressure and strain ranges under open-air and freezing temperatures. This hydrogel electrolyte is fabricated through a reconstruction process comprising a drying-induced densification of double-network hydrogel of alginate and polyacrylamide, a structure fixation by Fe3+ crosslinking, and a Li+ infiltration. The resultant hydrogel electrolyte is tolerant to dehydration and congelation and mechanically robust, with strength and elastic modulus of a few mega-pascals comparable to those of non-conductive elastomers/rubbers used as dielectric materials. Therefore, the hydrogel electrolyte-based iontronic sensors demonstrate exceptional sensitivity and stability under compression and tension and across a wide temperature range. Further, the sensor demonstrates their practical applicability in high-stress environments from kg-range human weight to ton-range car weight. These achievements evince that iontronic sensors, based on mechanically robust and ionically conductive hydrogel electrolytes tolerant to congelation and dehydration, can be employed for practical applications.

Super-Tough, Non-Swelling Zwitterionic Hydrogel Sensor Based on the Hofmeister Effect for Potential Motion Monitoring of Marine Animals.

Hydrogel-based electronic devices in aquatic environments have sparked widespread research interest. Nevertheless, the challenge of developing hydrogel electronics underwater has not been profoundly surmounted because of the fragility and swelling of hydrogels in aquatic environments. In this work, a zwitterionic double network hydrogel comprisedof polyvinyl alcohol (PVA), poly(sulfobetaine methacrylate) (PSBMA), and sulfuric acid (H2SO4) demonstrates super-tough and non-swelling performance. The Hofmeister effect of H2SO4 and PSBMA induces the PVA chains to form numerous nanocrystalline domains, which serve as the primary physical crosslinking points and provide effective energy dissipation. H2SO4 induces a strong salting-out effect to facilitate PVA crystallization and the formation of a dense and stable network structure that inhibits swelling. The resulting hydrogel exhibits an ultra-high toughness of 4.61MJm-3, non-swelling, and long-term stability for up to a month in pure water and seawater. Based on this, a hydrogel-based seawater strain sensor has been developed to monitor the underwater movements of marine animal models. Reliable and stable sensing performance ensures real-time collection of underwater motion signals, despite the impacts of water flow and the interference of ions. This study provides a facile approach to designing super-tough and non-swelling hydrogels and further expands the application of underwater electronic devices.