Network Structure Of Hydrogels Research Articles

The fracture and toughening mechanism of double-network hydrogel using the network mechanics method

Double-network hydrogels have received considerable attention due to their superior mechanical properties. However, a comprehensive understanding of their fracture and toughening mechanisms is still lacking, primarily due to the complex network structures of double-network hydrogels and the highly non-linear characteristics of the fracture. In this study, we address this gap by developing a mesoscopic model for double-network hydrogels using the network mechanics method, in which the fracture of polymer chains is realized by introducing the stretch criterion to each polymer chain. Through numerical analysis, we find that the stretch criterion ratio of polymer chains in two networks λ2c/λ1c is the key factor that influences the necking and hardening phenomena of double-network hydrogels. By changing this stretch criterion ratio, the fracture mode of double-network hydrogels can transit between ductile and brittle. When the fracture stretching criteria of the polymer chains in the first and second networks are 1.8 and 6, the necking and hardening phenomena can be observed. It is also found that a more uniform network structure of the first network enhances the toughness of double-network hydrogels. This study sheds light on the fundamental fracture and toughening mechanisms of double-network hydrogels, providing new insights for their further applications.

Green synthesized silver nanoparticles based on N-3-(dimethylamino)propyl methacrylamide/2-hydroxyethyl methacrylate hydrogels for antibacterial wound dressing material

In this study, hydrogels were synthesized using Prunus persica ev. Bayramiç Beyazı extract as a crosslinker. N-3-(Dimethylamino)propyl methacrylamide (DMAPMA) and 2-Hydroxyethyl methacrylate (HEMA) monomers were used in hydrogels synthesized by redox polymerization. Hydrogel@Ag composites were created by synthesizing Ag0 nanoparticles within hydrogel network structures cross-linked with plant extract using an in-situ green synthesis method. These hydrogels and composites were characterized by swelling, FTIR, TEM, XRD, TGA methods. The synthesized hydrogels and hydrogel@Ag composites were loaded with Naproxen and Cefazolin drugs. The in-vitro drug release profiles of the hydrogels were examined in a pH = 5.5 and PBS environment, and it was determined that approximately 75% of the drugs were released within 5 h. The release kinetics model for the hydrogels was the Higuchi model, followed by the Korsmeyer-Peppas model. Ag0 nanoparticle encapsulation significantly affected the degree of swelling. The hydrogel cross-linked with MBA showed a swelling capacity of 370.16% by mass, while the hydrogel cross-linked with fruit extract exhibited a swelling capacity of 1000.78% by mass. The silver-encapsulated hydrogel demonstrated an even higher swelling capacity of 2313% by mass. Additionally, antibacterial tests against Staphylococcus aureus, Pseudomonas aeruginosa, and Enterococcus faecalis microorganisms, showed that Ag-free hydrogels did not exhibit antibacterial activity.

Exploration on the multifunctional hydrogel dressings based on collagen and oxidized sodium: A novel approach for dynamic wound treatment and monitoring

Collagen-based hydrogels have attracted growing interest as a promising type of wound dressing. However, designing a multifunctional hydrogel dressing capable of both treating and monitoring dynamic wounds remains a bottleneck. This issue is facilely addressed by developing hydrogel dressings based on collagen and oxidized sodium alginate (OSA) using an innovative biphasic solvent system of acetic acid/1-ethyl-3-methylimidazolim acetate (AA/[EMIM][Ac]). Compatible hydrogel network structure can be achieved by adopting highly polar solvent of AA/[EMIM][Ac] to shield strong electrostatic adsorption between two polyelectrolytes with opposite charges. Through the simple Schiff base click reaction, various compositions ratios of OSA/collagen in the resultant hydrogels were systematically examined. Sufficient covalent crosslinking bonds endowed collagen-based hydrogels with expected physicochemical properties including stable mechanical properties (1007.87 Pa), improved thermal stability (66.59 °C), reduced degradation rate (23.51 %) and compact porous microstructure (44.17 μm). Meanwhile, the biological hydrogels with advantageous responses demonstrated favorable injectability, desirable self-healing capacity, satisfactory biocompatibility and accelerated wound healing performance. More interestingly, the electronic biosensor assembled by the resultant hydrogels was able to precisely monitor human activity. Our findings revealed that the multifunctional OSA-crosslinked collagen hydrogels were ideal candidates for wound dressings in the field of biomedical materials.

3D skeletal muscle tissue culture in vitro by using hydrogel interpenetrating network

Abstract Muscle cells can not only be used for pathological research and drug detection, but also can be combined with soft robots to form biological hybrid robots. Mature muscle tissue had advantages such as good elasticity, self-repair, and multi-signal perception. Although there are many methods for 3D muscle tissue culture, muscle tissue is difficult to be used due to the insufficient material properties and long culture period. In this study, we exploited the excellent physicochemical properties of hydrogel materials to develop a new novel interpenetrating hydrogel network structure as a culture framework, and 3D cell culture and tissue induction culture were combined to culture 3D muscle tissue in hydrogel environment and induce differentiation into muscle tissue. The results successfully induce cell proliferation, differentiation and myotube formation in vitro, provide a new idea for the rapid cultivation of muscle tissue in vitro and provide a basis for the assembly of soft robots in the future.

High specific surface area carbon aerogel derived from starch for methylene blue adsorption and supercapacitors

Starch based carbon aerogel has attracted significant attention due to the wide source, environmental friendliness and low price of raw materials. Here, starch based carbon aerogel was fabricated by graft reaction and cross-linking reaction of starch. The network structure of starch hydrogel was optimized through graft and cross-linking reaction. After freeze drying and high temperature carbonization, the obtained carbon aerogel that carbonized at 800 °C showed a specific surface area of 1508 m2·g−1 without activation which is far higher than that of other unactivated carbon aerogels. The starch based carbon aerogel carbonized at 800 °C exhibited superior methylene blue adsorption ability with a maximum adsorption capacity of 963.5 mg·g−1 as a result of its rich surface functional groups, high specific surface area, and reasonable pore size distribution. Furthermore, the carbon aerogel carbonized at 700 °C exhibited excellent electrochemical performance with a specific capacitance of 180.1 F·g−1 at a current density of 1 A·g−1as electrode materials for supercapacitors. Overall, this work provides a new method to prepare high performance starch based carbon aerogel.

Development of interpenetrating network hydrogels: Enhancing the release and bioaccessibility of green tea polyphenols

Green Tea polyphenols (GTP) are important bioactive compounds with excellent physiological regulation functions. However, they are easily destroyed by the gastric environment during digestion. In this work, a sodium alginate (SA)-gellan gum (GG) interpenetrating network (IPN) hydrogel was synthesized to protect and delivery GTP. The ratio of SA/GG significantly affects the network structure of IPN hydrogels and the performance of delivering GTP. The hydrogel formed by interpenetrating 20 % GG with 80 % SA as the main network had the highest water uptake (55 g/g), holding capacity (950 mg/g), and freeze-thaw stability, with springiness reaching 0.933 and hardness reaching 1300 g, which due to the filling effect and non-covalent interaction. Rheological tests showed that the crosslink density of IPN hydrogel in SA-dominated network was improved by the addition of GG to make it better bound to GTP, and the higher water uptake meant that the system could absorb more GTP-containing solution. This IPN hydrogel maintained 917.3 mg/g encapsulation efficiency at the highest loading capacity (1080 mg/g) in tests as delivery system. In in vitro digestion simulations, owing to the pH responsiveness, the IPN hydrogel reduced the loss of GTP in gastric fluid, achieving a bioaccessibility of 71.6 % in the intestinal tract.

Liquid‐Metal‐Loaded Hydrogel with Antibacterial Effect and Sustained Release of Growth Factor for Wound Healing

AbstractMultifunctional medical hydrogels play an important role in wound healing because of their excellent biocompatibility, convenient operation, and drug release capacity. So far, many efforts have been exploited to developing new‐generation hydrogels with distinctive capabilities in promoting wound healing. Herein, the liquid‐metal (LM)‐loaded hydrogels are reported with antibacterial effect under an 808 nm near‐infrared laser irradiation for wound healing therapeutic strategies. The addition of LM droplets enables the hydrogel to control the temperature rise and plays an antibacterial effect with the release of gallium3+ under laser irradiation. Benefiting from the porous network structure of hydrogels, the encapsulated growth factors can be released stably at the wound site. Under the synergistic effect of LM and growth factors in the wound tissue, the hydrogel displays antibacterial features and promotes the regeneration of epithelial tissue and neovascularization, thereby further accelerating wound healing. This hydrogel has proven biosafety and low toxicity in vitro and in vivo. With these advantages, such hydrogel is a promising candidate to be developed as a new medical product for future clinical medicine.

Optimization of method for cross section hydrogels preparation using high-pressure freezing.

High-pressure water freeze fracturing (HPWFF) is a method for preparing water-containing samples such as hydrogels for scanning electron microscopy, in which a sample is placed in a divisible pressure vessel, filled with water, sealed, frozen with liquid nitrogen, then vacuum dried after the vessel is divided. The pressure (about 200 MPa) generated by the phase transition from water to ice is expected to inhibit ice crystal formation that causes large deformation of microstructure in the sample. To maximize the useable sample size, where SEM observation is not affected by ice crystal growth, preparation conditions including the size of pressure vessel were examined in this work. Using pressure vessels 8.0 mm, 5.5 mm and 4.5 mm in diameter, agarose gel, gelatin gel, wheat starch hydrogel, wheat flour noodle and cellulose hydrogel were used to prepare SEM samples. With agarose gel, an area of 3.6 mm in diameter in the 5.5 mm vessel was achieved as the maximum size of the area observable without ice crystal growth. The observable size of other samples was comparable, except for gelatin gel. As a result, observation of the three-dimensional network structure of hydrogels could be performed over a wider range than with the conventional method without shredding or chemical treatment of the samples. Additionally, usability of agarose gel for sample support matrix in HPWFF was demonstrated.

Preparation of CMC-poly(N-isopropylacrylamide) semi-interpenetrating hydrogel with temperature-sensitivity for water retention

The CMC-PNIPAM hydrogel with semi-interpenetrating structure and temperature-sensitivity was prepared by in-situ polymerization of N-isopropylacrylamide (NIPAM) in sodium carboxymethylcellulose (CMC) solution at room temperature. The mass ratio of CMC to NIPAM was a key factor influencing the network structure and property of CMC-PNIPAM hydrogel. The low critical phase transition temperature (LCST) of CMC-PNIPAM hydrogels increased from 34.4 °C to 35.8 °C with the mass ratio of CMC to NIPAM rising from 0 to 1.2. The maximum compressive stress of CMC-PNIPAM hydrogel reached to 26.7 kPa and the relaxation elasticity was 52 % at strain of 60 %. The viscoelasticity of CMC-PNIPAM hydrogel was consistent with the generalized Maxwell model. The maximum swelling ratio in deionized water was 170.25 g·g−1 (dried hydrogel) with swelling rate of 2.57 g·g−1·min−1 at 25 °C. CMC-PNIPAM hydrogel hardly absorbed water above LCST, but the swollen hydrogel could release water at the rate of 0.36 g·g−1·min−1 once exceeding LCST. The test of water retention showed that soil mixed with 2 wt% dried CMC-PNIPAM hydrogel could retain 13.08 wt% water after 30 days at 25 °C that was 4.4 times than that of controlled soil without CMC-PNIPAM hydrogel. The semi-interpenetrating CMC-PNIPAM hydrogel showed a potential to conserve water responding to temperature.

Molecular simulation-guided and physics-informed constitutive modeling of highly stretchable hydrogels with dynamic ionic bonds

Adaptive polymers are being designed with dynamic molecular bonds or chain interactions to respond with external stimuli with unparalleled mechanical properties and multifunctionality. An elegant example is to substantially enhance the stretchability and toughness of hydrogels through the use of ionic bond interactions. To assist the materials design and applications, a predictive theory is in high demand. However, existing multi-scale mechanics models often rely on empirical assumptions and relationships derived from polymer chemistry or physics to describe the evolution of microscale details under external stimuli, which are challenging to be validated experimentally. This study introduces a new methodology to develop constitutive theories for stretchable hydrogels based on insights garnered from molecular dynamics (MD) simulations. The continuum-level viscoelastic theory establishes the thermodynamics framework for stress-strain relationships, while MD simulations inform the evolution mechanisms of microscale bond interactions and network rearrangements, such as the bond distance and network relaxation time. These insights are then properly formulated based on polymer physics principles and fed into the continuum-level model. The resulting constitutive theory closely captures the stress responses at various loading conditions observed in experiments, as well as the microscale system volume and bond distance uncovered in MD simulations. Parametric studies are conducted to investigate the influences of various loading and material parameters on the mechanical properties of the materials, including loading rates, network crosslinking density, maximum strain, and bonding strength. Overall, the study establishes the connection between microscale network structure and mechanical responses of stretchable hydrogels with dynamic ionic bonds. It also offers practical guidance for optimizing material structures and loading conditions to enhance energy absorption and dissipation capabilities. The modeling approach can be extended to the study of other adaptive polymers with different dynamic bonds to create more precise and physically meaningful constitutive models.

Regulation of rheological properties of soy protein isolate-beeswax based bigel inks for high-precision 3D printing

Bigel inks were developed for high-precision 3D food printing using soy protein isolate (SPI) hydrogel and beeswax oleogel. The ratio of hydrogel to oleogel played a crucial role in determining the rheology and moisture state of the inks. When the ratio of hydrogel to oleogel reached 7:3, the ink was softer and showed stronger shear-thinning properties, which resulted in better recoverability and stronger self-supportability. These were demonstrated by the lowest flow index (n value) of 0.135, the largest recovery viscosity of 10.920 × 105 mPa s, and the biggest yield stress (1034.200 Pa), complex modulus (G* of 6608.066 Pa), and gel strength (A value of 488.34 × 103 Pa s1/z). Additionally, the ink contained more semi-solid water (T22) and had a higher proportion of moisture freedom (A23). Consequently, the ink had a smooth extrusion while exhibiting strong mechanical properties and better structure stability. As a result, a hollow-rotating structure was achieved with a height of 20.05 mm, a gap diameter of 10.11 mm, and an inclination angle of 46.13° with precision beyond 99%. This was attributed to the presence of more β′ and β crystals with high oleogel content, which might protect the completeness of the SPI hydrogel network structure and prevent the aggregation of oleogel particles. In this turn, it improved the microstructure of the SPI-based bigel inks and made them more resistant to shearing during extrusion. This work provides a new insight into the application of SPI in personalized diets.

Multifunctional graft-IPN hydrogels of cellulose nanofibers and poly(N-isopropyl acrylamide) via silver-promoted decarboxylative radical polymerization

Interpenetrating polymer networks (IPNs) have emerged as innovative materials for a wide range of applications. Owing to the crosslinked structure of their polymer components, IPNs exhibit superior properties relative to their single component counterparts. Here, we report a new class of multifunctional graft-interpenetrating polymer network (graft-IPN) hydrogel composites of poly(N-isopropylacrylamide) (PNIPAM) grafted onto cellulose nanofibers (CNFs) via silver(I)-promoted decarboxylative polymerization. This novel approach involves the Ag-promoted graft polymerization and the crosslinking of PNIPAM in the CNF network, forming a hybrid of semi-IPN and graft-copolymer hydrogel. Different from conventional PNIPAM-CNF IPNs, the CNFs in graft-IPN hydrogels form an interconnected network as a result of crosslinking between neighboring grafted PNIPAM. Silver nanoparticles (AgNPs) are also formed in situ in the graft-IPN hydrogel matrix, demonstrating the dual functionality of silver as both a catalyst in the polymerization and an eventual antibacterial agent in the hydrogel. The network structure of graft-IPN hydrogels can be controlled by crosslinker and Ag(I) concentration, therefore modulating their thermo-responsive, mechanical, and swelling properties. The grafting of PNIPAM from CNFs shifts the volume phase transition to 36 °C and significantly improves the mechanical strength and swelling capacity of the hydrogels. Ultimately, this work demonstrates the excellent potential of these multifunctional graft-IPN hydrogels with controllable thermosensitivity, mechanical strength and anti-microbial activity as engineered biomaterials for advanced applications in biomedicine, engineering, and industry.

An ultrasound-triggered injectable sodium alginate scaffold loaded with electrospun microspheres for on-demand drug delivery to accelerate bone defect regeneration

Biological processes, such as bone defects healing are precisely controlled in both time and space. This spatiotemporal characteristic inspires novel therapeutic strategies. The sustained-release systems including hydrogels are commonly utilized in the treatment of bone defect; however, traditional hydrogels often release drugs at a consistent rate, lacking temporal precision. In this study, a hybrid hydrogel has been developed by using sodium alginate, sucrose acetate isobutyrate, and electrospray microspheres as the base materials, and designed with ultrasound response, and on-demand release properties. Sucrose acetate isobutyrate was added to the hybrid hydrogel to prevent burst release. The network structure of the hybrid hydrogel is formed by the interconnection of Ca2+ with the carboxyl groups of sodium alginate. Notably, when the hybrid hydrogel is exposed to ultrasound, the ionic bond can be broken to promote drug release; when ultrasound is turned off, the release returned to a low-release state. This hybrid hydrogel reveals not only injectability, degradability, and good mechanical properties but also shows multiple responses to ultrasound. And it has good biocompatibility and promotes osteogenesis efficiency in vivo. Thus, this hybrid hydrogel provides a promising therapeutic strategy for the treatment of bone defects.

Thermally Reversible Gel-Sol Transition of Hydrogels via Dissociation and Association of an Artificial Protein Nanocage.

Oligomeric protein nanocages often disassemble into their subunits and reassemble by external stimuli. Thus, using these nanocages as cross-linkers for hydrogel network structures is a promising approach to allow hydrogels to undergo stimuli-responsive gel-sol transitions or self-healing. Here, we report hydrogels that show a reversible gel-sol transition resulting from the heat-induced dissociation and reassociation of protein nanocages. The hydrogel contained the 60-mer artificial protein nanocage, TIP60, as a supramolecular cross-linker for polyethylene glycol network structures. The hydrogel showed a gel-to-sol transition upon heating at a temperature above the melting point of TIP60 and immediately returned to a gel state upon cooling to room temperature. During the heating and cooling treatment of the hydrogel, small-angle X-ray scattering analysis suggested the dissociation and reassociation of TIP60. Furthermore, we demonstrated redox-responsive cargo release from TIP60 in the hydrogel. These results showed the potential of TIP60 as a component of multi-stimuli-responsive hydrogels.

Construction and tribological properties of poly acrylic acid‐poly(3‐(methacryloylamino)propyl) dimethyl(3‐sulfopropyl)ammonium hydroxide hydrogel coatings embedded with SiO2 nanoparticles on Ti6Al4V substrate

AbstractThe development of highly effective bio‐lubricant coatings for arthritis treatment is extremely demanded. Herein, inspired by the efficient lubrication of articular cartilage, acrylic acid (AA) with (3‐(methacryloylamino) propyl) dimethyl (3‐sulfopropyl) ammonium hydroxide (MPDSAH) hydrogel coatings containing nanoparticles on Ti6Al4V substrate were designed and fabricated via UV grafting technology. SiO2 and SiO2 grafted with PAA polymer brushes (SiO2‐g‐PAA) were separately doped into the PAA‐PMPDSAH hydrogel. The PAA‐PMPDSAH/SiO2‐g‐PAA exhibits good tensile and compressive properties compared with PAA‐PMPDSAH/SiO2 hydrogel, with an enhancement of 183.4% in tensile modulus and 60.8% in compressive modulus. The PAA‐PMPDSAH/SiO2‐g‐PAA hydrogel coatings exhibit a low wear volume, 2.9 ± 0.16 × 106 μm3, representing a decline of 32.1% and 61.3% compared with the PAA‐PMPDSAH and PAA‐PMPDSAH/SiO2 hydrogel coatings, respectively. The antiwear performance has obviously improved. The hydrophilic PAA polymer brushes prevent the agglomeration of nanoparticles and promote homogeneously dispersion within the hydrogel. The three‐dimensional crosslinked network structure of hydrogel effectively protects the structural integrity of the polymer brushes, thereby facilitating enduring lubrication properties. This work provides a strategy for promising artificial joint lubrication in biomedical fields.

Hybridized cellulose nanocrystals enhanced the temperature resistance and viscoelasticity of the fracturing fluid network

This study aimed to fabricate a novel, low-cost, and environmental-friendly cellulose composite hydrogels based on cellulose nanocrystals (CNCs) and carboxymethyl cellulose (CMC-Na) via hybridizing methods. The performance of composite hydrogels was characterized and the nanocrystals enhancing hydrogels performance mechanism was analyzed, which showed that the apparent viscosity, temperature tolerance, elastic modulus, and tensile strength of cellulose hydrogels were improved by CNCs. Compared with the cellulose hydrogels, the viscosity of the cellulose composite hydrogels at 120 °C reached 195 mPa·s, with an increase of 200 %, and the elastic modulus was 30 Pa, with an increase of about 253 %. Furthermore, the microscopic analysis revealed that CNCs can play the role of nucleus and skeleton in the network structure of cellulose composite hydrogels and obviously enhanced the strength of the network structure. It is obvious to improve the performance of cellulose hydrogels by adding CNCs into the cellulose composite hydrogels. This method provides a new idea for the development of fracturing fluids suitable for unconventional reservoirs.

Low solid content mouldable chitin physical hydrogel prepared by atypical rupture-free swelling.

In this study, the atypical swelling gelation of chitin physical hydrogels was investigated. Just by tuning the amount of the N-acetylation reagent, the degree of acetylation varied and mouldable chitin hydrogels with a wide variety of gel concentrations (0.2-6.4 wt%) were obtained. In response to the gel concentration, the mechanical properties ranged from swollen soft gels to shrunken rigid gels (compressive moduli of 4-310 kPa). The thus-prepared chitin hydrogels, which were composed of only chitin and water, exhibited high transparency and integrity. The swelling gelation of chitin physical hydrogels was achieved owing to both the positive charges of the amino groups inducing the osmotic pressure and the toughness of the crystalline nanofibrous network structure of the chitin hydrogels that endured the large volume change. These previously unnoticed advantageous aspects of chitin have pioneered a novel area of swellable physical gels that has been exclusive to chemical gels so far.

New insights into pure zwitterionic hydrogels with high strength and high toughness.

Zwitterionic hydrogels are electrically neutral materials with both cationic and anionic groups that impart excellent anti-fouling properties and ion channel orientations. However, pure zwitterionic hydrogels generally exhibit low strength and toughness. In this study, it has been discovered that polymerizable zwitterionic monomers in aqueous solution exhibit a unique liquid-liquid phase separation phenomenon at a high monomer concentration of ≥50 wt%, resulting in pure and commercial zwitterionic hydrogels with high compressive strength (6.5 MPa) and high toughness (2.12 kJ m-2). This phase separation and the corresponding aggregations might be caused by strong dipole-dipole interactions among residual zwitterionic monomers under the lack of free-water condition. The synergistic effect of liquid-liquid phase separation and polymer entanglement enhances the mechanical strength, toughness, self-recovery, and anti-freezing properties of pure polyzwitterionic hydrogels. Moreover, the high fracture energy of highly elongated yet tough polyzwitterionic hydrogels facilitates the development of high crack propagation resistance, which supports an expanded role in tissue engineering, soft flexible devices, and electronics applications with improved durability. A wide range of applications for the proposed polyzwitterionic hydrogels is demonstrated by the development and testing of a strain sensor and a triboelectric nanogenerator device. Our findings provide novel insights into the network structure of pure polyzwitterionic hydrogels.

Tuning network structures of hydrophobic hydrogels by controlling polymerization solvent

Hydrophobic hydrogels with various copolymer sequences and network structures are prepared by tuning the solvent condition of the reaction solution, which exhibit different appearance and properties under the same monomer composition.

Humidity-adjustable functional gelatin hydrogel/ethyl cellulose bilayer films for active food packaging application

A sustainable functional bilayer film composed of gelatin hydrogel/ethyl cellulose was fabricated using a simple LBL casting method. The outer layer was hydrophobic ethyl cellulose (EC), while the inner layer was hydrophilic gelatin (GEL) hydrogel. Tannic acid (TA) served as a green cross-linker for GEL hydrogel preparation and as a reductant for AgNPs synthesis in-situ within the hydrogel network. Physicochemical and functional properties of the bilayer films containing different TA content were studied. When 3 wt% TA was added, the AgNPs@GT-3/EC bilayer film exhibited superior UV-light barrier, possessed desirable humidity-adjustable capability and oxygen barrier due to denser hydrogel network structure, and effectively inactivated foodborne pathogens S. aureus and E. coli with bacteriostatic rates of 99 %. The application results indicated that this bilayer film effectively maintained the postharvest quality of white button mushrooms and prolonged their shelf-life to 7 days under ambient storage, demonstrating its promising potential for fresh food packaging.