Polyelectrolyte Complex Hydrogels Research Articles

Non-swelling polyelectrolyte complex hydrogels with tissue-matchable mechanical properties for versatile wet wound closure

The stable adhesion of hydrogel-based bioadhesives with tissue-matchable mechanical properties in biological environments remains a significant challenge. In this work, we propose a polyethyleneimine-polyacrylic acid (PEI-PAA, PEA) double-network polyelectrolyte hydrogel with swelling resistant capacity and tunable mechanical properties via one-step UV-initiated polymerization. Driven by electrostatic interactions and polymer-chain entanglement, this PEA hydrogel displays a distinctive microphase separation behavior, which facilitates a wide tunability in mechanical properties. Specifically, the modulus varies from 0.4 MPa to 106 MPa, and the toughness ranges from 1479 kJ/m3 to 7641 kJ/m3, respectively. Besides, the microphase separation endows PEA hydrogel with notable anti-swelling properties in saline, TBS buffer, and blood, leading to consistent adhesion to diverse moist tissues. We further demonstrate that our PEA hydrogels provide matchable mechanical properties and long-lasting adhesion to rat skin and arteries, which promote skin injury healing and effectively halt artery rupture bleeding in vivo. This work presents a straightforward method to generate non-swelling hydrogels and offers novel insight into the development of bioadhesives to meet diverse mechanical requirements.

Additive manufacturing of wet-spun chitosan/hyaluronic acid scaffolds for biomedical applications

Additive manufacturing (AM) holds great potential for processing natural polymer hydrogels into 3D scaffolds exploitable for tissue engineering and in vitro tissue modelling. The aim of this research activity was to assess the suitability of computer-aided wet-spinning (CAWS) for AM of hyaluronic acid (HA)/chitosan (Cs) polyelectrolyte complex (PEC) hydrogels. A post-printing treatment based on HA chemical cross-linking via transesterification with poly(methyl vinyl ether-alt-maleic acid) (PMVEMA) was investigated to enhance the structural stability of the developed scaffolds in physiological conditions. PEC formation and the esterification reaction were investigated by infrared spectroscopy, thermogravimetric analysis, evolved gas analysis-mass spectrometry, and differential scanning calorimetry measurements. In addition, variation of PMVEMA concentration in the cross-linking medium was demonstrated to strongly influence scaffold water uptake and its stability in phosphate buffer saline at 37 °C. The in vitro cytocompatibility of the developed hydrogels was demonstrated by employing the murine embryo fibroblast Balb/3T3 clone A31 cell line, highlighting that PMVEMA cross-linking improved scaffold cell colonization. The results achieved demonstrated that the developed hydrogels represent suitable 3D scaffolds for long term cell culture experiments.

A unified viscoelastic constitutive model for studying the mechanical behaviors of polyelectrolyte complex hydrogels with different crosslinker degrees

Bio-based hydrogels formed by the chemically or physically cross-links are promising materials in the biological system. In this paper, we propose a constitutive model within the framework of finite-strain viscoelasticity to investigate the mechanical behaviors of bio-based polyelectrolyte complex (PEC) hydrogels from the ionic complexation of sodium hyaluronate (HA)/chitosan with and without chemical crosslinkers. The structure of the viscoelastic constitutive model consists of a spring and a Kelvin element, in which two softening factors are adopted to represent the states of ionic bonds and bridges in the hydrogels. Based on some constitutive assumptions and through the conventional approach of thermodynamics, the constitutive equation system of the model is derived. Corresponding to the hydrogels with different crosslinker concentrations, the values of material parameters in the model are identified. To show the validity of the model, it is applied to simulate the mechanical behaviors of the hydrogel samples in the uniaxial tensile tests and cyclic loading–unloading tests. It is found that the model predictions can fit the experimental data quite well. Based on the modeling results, some further analyses regarding the effects of softening factors on the response of HA/chitosan hydrogels have also been conducted.

Polyelectrolyte Complex Hydrogels from Controlled Kneading and Annealing-Induced Tightly Wound and Highly Entangled Natural Polysaccharides.

Hydrogels usually are fabricated by using monomers or preexisting polymers in precursor solutions. Here, a polyelectrolyte complex biohydrogel (Bio-PEC hydrogel) made from a precursor dough, by kneading, annealing, and crosslinking the dough of two oppositely charged polysaccharides, cationic chitosan quaternary ammonium salt (HACC) and anionic sodium hyaluronate (HA), photoinitiator (α-ketoglutaric acid), crosslinker glycidyl methacrylate (GMA), and water of very small quantity is reported. Controlled kneading and annealing homogenized the dough with respect to transforming randomly distributed, individual polymer chains into tightly wound double-stranded structures, which, upon UV irradiation, covalently sparsely crosslinked into a highly entangled network and subsequently, upon fully swollen in water, results in Bio-PEC hydrogel, HACC/HA, exhibiting near-perfect elasticity, high tensile strength, and high swelling resistance. Via the same kneading and annealing, tetracarboxyphenylporphyrin iron (Fe-TCPP) metal nanoclusters are incorporated into HACC/HA to obtain photocatalytic, antibacterial, and biocompatible Bio-PEC hydrogel composite, Fe-TCPP@HACC/HA. Using SD rat models, the efficacy of Fe-TCPP@HACC/HA in inhibiting Escherichia coli (E. coli) growth in vitro and the ability to promote wound healing and scar-free skin regeneration in vivo, or its high potential as a wound dressing material for biomedical applications are demonstrated.

Advances, Applications, and Emerging Opportunities in Electrostatic Hydrogels.

Polyelectrolyte complex (PEC) hydrogels, which self-assemble via complexation of oppositely charged block polymers, have recently risen to prominence owing to their unique characteristics such as hierarchical microstructure, tunable bulk properties, and the ability to precisely assimilate charged cargos (i.e., proteins and nucleic acids). Significant foundational research has delineated the structure-property relationship of PEC hydrogels for use in a wide range of applications. In this Perspective, we summarize key findings on the microstructure and bulk properties of PEC hydrogels and discuss how intrinsic and extrinsic factors can be tuned to create specifically tailored PEC hydrogels with desired properties. We highlight successful applications of PEC hydrogels while offering insight into strategies to overcome their shortcomings and elaborate on emerging opportunities in the field of electrostatic self-assemblies.

Preparation and in vitro characterization of curcumin loaded Chitosan-Hyaluronic acid polyelectrolyte complex based hydrogels

Objective The manuscript aims to prepare and comprehensively characterize curcumin-loaded chitosan-hyaluronic acid polyelectrolyte complex (PEC) hydrogels through in vitro assessments. By elucidating the formulation process, physicochemical attributes, and drug release kinetics, the study contributes to the producing of curcumin loaded new drug delivery system. Significance This approach shows the unique synergy of the chosen polymers with curcumin. The meticulous in vitro analysis of the hydrogels cements their novel attributes, underlining their potential as efficacious and biocompatible curcumin carriers. Methods To configure the optimum formulation variables, viscosity, swelling ratio, porosity, in vitro release, cell viability, and migration rate were determined. In addition, FTIR and SEM analyses were also carried out to define the characteristic of formulations. Results Release kinetic determination is essential in estimating the release behavior of formulation in the body. All formulations showed Higuchi release kinetics, indicating that drug release from the semi-solid matrix was diffusion controlled. Conclusion As a result, in this study, a new formulation was produced based on a simple concept with acceptable quality parameter results promising to be conducted in the industry.

Nanocomposite Hydrogels and Extracellular Matrix-Advantages and Associated Risks.

Hydrogels can be considered as mimics of the extracellular matrix (ECM). Through integrins, the cytoskeleton is connected to the ECM, and cytoskeleton tension depends on ECM stiffness. A number of age-related diseases depend on cellular processes related to cytoskeleton function. Some examples of cancer initiation and progression and heart disease in relation to ECM stiffness have been analyzed. The incorporation of rigid particles into the ECM can increase ECM stiffness and promote the formation of internal residual stresses. Water migration, changes in water binding energy to biomactomolecules, and changes in the state of water from tightly bound water to free and loosely bound water lead to changes in the stiffness of the ECM. Cardiac tissue engineering, ECM stiffness and cancer, the equivalence of ECM stiffness, oxidative stress, inflammation, multi-layer polyelectrolyte complex hydrogels and bioprinting, residual internal stresses, viscoelastic hydrogels, hydrogel nanocomposites, and the effect of water have been reported. Special attention has been paid to the role of bound water and internal stresses in ECM stiffness. The risks related to rigid particle incorporation into the ECM have been discussed. The potential effect of polyphenols, chitosan, and chitosan oligosaccharide on ECM stiffness and the potential for anti-TNF-α and anti-NF-κB therapies have been discussed.

Chitosan – dextran phosphate carbamate hydrogels for locally controlled co-delivery of doxorubicin and indomethacin: From computation study to in vivo pharmacokinetics

The development of synergistic drug combinations is a promising strategy for effective cancer suppression. Here, we report all-polysaccharide biodegradable polyelectrolyte complex hydrogels (DPCS) based on dextran phosphate carbamate (DP) and chitosan (CS) for controlled co-delivery of the anticancer drug doxorubicin (DOX) and the non-steroidal anti-inflammatory drug indomethacin (IND). IND can induce more apoptosis in tumor cells by reducing the level of multidrug resistance-associated protein 1. Based on calculations using density functional theory and zeta potential analysis data, carriers with high drug loading were obtained. The release profile of both drugs from the hydrogels was tuned by changing the molecular weight and functional groups content of the polysaccharides. The optimized DPCS showed a steady release of DOX both in vitro and in vivo, and a gradual release of IND, which constantly induced the action of DOX. Considering all of these benefits, DOX- and IND-loaded DPCS offer a promising long-acting polysaccharide-based antitumor platform.

Macroporous Hyaluronic Acid/Chitosan Polyelectrolyte Complex-Based Hydrogels Loaded with Hydroxyapatite Nanoparticles: Preparation, Characterization and In Vitro Evaluation

The aim of the study was to fabricate and characterize composite macroporous hydrogels based on a hyaluronic acid/chitosan (Hyal/Ch) polyelectrolyte complex (PEC) loaded with homogeneously distributed hydroxyapatite nanoparticles (nHAp), and to evaluate them in vitro using mouse fibroblasts (L929), osteoblast-like cells (HOS) and human mesenchymal stromal cells (hMSC). Hydrogel morphology as a function of the hydroxyapatite nanoparticle content was studied using scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM). The mean pore size in the Hyal/Ch hydrogel was 204 ± 25 μm. The entrapment of nHAp (1 and 5 wt. %) into the Hyal/Ch hydrogel led to a mean pore size decrease (94 ± 2 and 77 ± 9 μm, relatively). Swelling ratio and weight loss of the hydrogels in various aqueous media were found to increase with an enhancement of a medium ionic strength. Cell morphology and localization within the hydrogels was studied by CLSM. Cell viability depended upon the nHAp content and was evaluated by MTT-assay after 7 days of cultivation in the hydrogels. An increase of the hydroxyapatite nanoparticles loading in a range of 1–10 wt. % resulted in an enhancement of cell growth and proliferation for all hydrogels. Maximum cell viability was obtained in case of the Hyal/Ch/nHAp-10 sample (10 wt. % nHAp), while a minimal cell number was found for the Hyal/Ch/nHAp-1 hydrogel (1 wt. % nHAp). Thus, the proposed simple original technique and the design of PEC hydrogels could be promising for tissue engineering, in particular for bone tissue repair.

Polyelectrolyte Complex Hydrogels with Controlled Mechanics Affect Mesenchymal Stem Cell Differentiation Relevant to Growth Plate Injuries.

The growth plate is a complex cartilage structure in long bones that mediates growth in children. When injured, the formation of a "bony bar" can occur which impedes normal growth and can cause angular deformities or growth arrest. Current treatments for growth plate injuries are limited and result in poor patient outcomes, necessitating research toward novel treatments that can prevent bony bar formation and stimulate cartilage regeneration. This study investigates alginate-chitosan polyelectrolyte complex (PEC) hydrogels as an injectable biomaterial system to prevent bony bar formation. Biomaterial properties including stiffness and degradation are quantified, and the effect that material properties have on mesenchymal stem cell (MSC) fate is quantified in vitro. Specifically, this study aims to elucidate the effectiveness of biomaterial-based control over the differentiation behavior of MSCs toward osteogenic or chondrogenic lineages using biochemical metabolite assays and quantitative real time PCR. Further, the PEC hydrogels are employed in a rat growth plate injury model to determine their effectiveness in preventing bony bar formation in vivo. Results indicate that hydrogel composition and material properties affect the differentiation tendency of MSCs in vitro, and the PEC hydrogels show promise as an injectable biomaterial for growth plate injuries.

Smart Hydrogel Formed by Alginate-g-Poly(N-isopropylacrylamide) and Chitosan through Polyelectrolyte Complexation and Its Controlled Release Properties.

Smart hydrogels that can respond to external stimuli such as temperature and pH have attracted tremendous interest for biological and biomedical applications. In this work, we synthesized two alginate-graft-poly(N-isopropylacrylamide) (Alg-g-PNIPAAm) copolymers and aimed to prepare smart hydrogels through formation of polyelectrolyte complex (PEC) between the negatively charged Alg-g-PNIPAAm copolymers and the positively charged chitosan (Cts) in aqueous solutions. The hydrogels were expected to be able to respond to both temperature and pH changes due to the nature of Alg-g-PNIPAAm and chitosan. The hydrogel formation was determined by a test tube inverting method and confirmed by the rheological measurements. The rheological measurements showed that the PEC hydrogels formed at room temperature could be further enhanced by increasing temperature over the lower critical solution temperature (LCST) of PNIPAAm, because PNIPAAm would change from hydrophilic to hydrophobic upon increasing temperature over its LCST, and the hydrophobic interaction between the PNIPAAm segments may act as additional physical crosslinking. The controlled release properties of the hydrogels were studied by using the organic dye rhodamine B (RB) as a model drug at different pH. The PEC hydrogels could sustain the RB release more efficiently at neutral pH. Both low pH and high pH weakened the PEC hydrogels, and resulted in less sustained release profiles. The release kinetics data were found to fit well to the Krosmyer–Peppas power law model. The analysis of the release kinetic parameters obtained by the modelling indicates that the release of RB from the PEC hydrogels followed mechanisms combining diffusion and dissolution of the hydrogels, but the release was mainly governed by diffusion with less dissolution at pH 7.4 when the PEC hydrogels were stronger and stabler than those at pH 5.0 and 10.0. Therefore, the PEC hydrogels are a kind of smart hydrogels holding great potential for drug delivery applications.

Dynamic behavior of tough polyelectrolyte complex hydrogels from chitosan and sodium hyaluronate

In this work, we investigated the dynamics of hydrogels from the polyelectrolyte complexation of sodium hyaluronate (HA) and chitosan under various temperature and salt concentration. Raising temperature and adding salt remarkably reduce the mechanical behavior of hydrogels. The stress relaxation of semi-flexible chain segments is accelerated at high temperature and salt concentration, which is controlled by thermally activated bond disassociation process. The flow activation energy determined from temperature-dependent dynamic light scattering decorrelation and rheological relaxation are in very good agreement. Our results suggest that the chain aggregations are physical crosslinked by surrounded semi-flexible chains, and their diffusion is highly hindered by the topological entanglements and ionic associations. The synergistic effect of aggregations diffusion and chain dynamics causes the slow macroscopic stress relaxation behavior of hydrogels before yield, independent of applied strain. Above yield, the amplitude of strain accelerates the stress relaxation, resulting in chain disentanglements and slipping.

Compact poly-electrolyte complex hydrogels of gelatin and sodium alginate for sensing wound status

This work reports a facile, cost-effective and green strategy to develop pH sensitive complex coacervate hydrogel for sensing wound status. Gallic acid, the active sensory ingredient, induces the formation of the polyelectrolyte complex between ampholytic gelatin and anionic sodium alginate. This makes the hydrogel unique with a good mechanical integrity, having a gel strength of 453 ± 24 N, and a rupture force of 926 ± 36 N. The visual color change of the hydrogel confirms its alkaline nature, while the intact color indicates an acidic environment and makes it incredibly user-friendly. The antioxidant property and biocompatibility of the developed hydrogel augment its utility as a biosensor.

Controllable fabrication of alginate/poly-L-ornithine polyelectrolyte complex hydrogel networks as therapeutic drug and cell carriers

Polyelectrolyte complex (PEC) hydrogels are advantageous as therapeutic agent and cell carriers. However, due to the weak nature of physical crosslinking, PEC swelling and cargo burst release are easily initiated. Also, most current cell-laden PEC hydrogels are limited to fibers and microcapsules with unfavorable dimensions and structures for practical implantations. To overcome these drawbacks, alginate (Alg)/poly-L-ornithine (PLO) PEC hydrogels are fabricated into microcapsules, fibers, and bulk scaffolds to explore their feasibility as drug and cell carriers. Stable Alg/PLO microcapsules with controllable shapes are obtained through aqueous electrospraying technique, which avoids osmotic shock and prolongs the release time. Model enzyme and nanosized cargos are successfully encapsulated and continuously released for more than 21 days. Alg/PLO PEC fibers are then prepared to encapsulate brown adipose progenitors (BAPs) and Jurkat T cells. The electrostatic interactions between Alg and PLO are found to facilitate the printability and self-support ability of Alg/PLO bioinks. Alg/PLO PEC fibers and scaffolds support cell proliferation, differentiation, and functionalization. These results demonstrate new options for biocompatible PEC hydrogel preparation and improve the understanding of PEC hydrogels as drug and cell carriers. Statement of significanceIn this study, the concept of polyelectrolyte complex hydrogel networks as drug and cell carriers has been demonstrated. Their feasibility to achieve sustained drug release and cell functionality was explored, from microcapsules to fibers to three-dimension printed scaffolds. PEC microcapsules with controllable shapes were obtained. Therapeutic drugs can be encapsulated and continuously release for more than 21 days. Benefiting from the dynamic interactions of physically crosslinked PEC, self-healing fibers were achieved. Besides, the electrostatic interactions between polyelectrolytes were found to facilitate the printability and self-support ability of PEC bioinks. The PEC fibers and scaffolds with controllable structure supported cell proliferation, differentiation, and function. The outcome of current research promotes design of new biocompatible PEC hydrogels and potential drug and cell carriers.

Hydrogen-bonded network enables polyelectrolyte complex hydrogels with high stretchability, excellent fatigue resistance and self-healability for human motion detection

Polyelectrolyte complex hydrogel (PECH) is an emerging ion conductive hydrogel made from non-covalent interacted oppositely charged polyelectrolytes in water. However, the construction of PECH with high stretchability, excellent fatigue resistance and self-healability is heavily demanded while remaining a profound challenge. Herein, a hydrogen-bonded network densification strategy is presented for preparing a highly stretchable and deformation-tolerant PECH hydrogel (Fe/CS/PAA), which is composed of an anionic Fe3+-coordinated polyacrylic acid network (Fe-PAA) and cationic Fe3+-coordinated chitosan network (Fe-CS). Benefiting from the formation of dense hydrogen-bonded network between the Fe-PAA and Fe-CS networks activated by salt impregnation, the resultant densified hydrogen-bonded Fe/CS/PAA hydrogel (DHB-Fe/CS/PAA) exhibits large tensile strength (~0.34 MPa), high stretchability (~1370%), low-temperature resistance to −25 °C, and heat-accelerated self-healability. Due to its high stretchability, excellent fatigue resistance and high ionic conductivity, the DHB-Fe/CS/PAA can readily work as a stretchable ionic conductor for skin-inspired ionic strain sensor, displaying high sensitivity in a wide strain range (0.5%–500%), fast response time (<180 ms) and excellent durability for 500 cycles at a 100% strain. Besides, the as-assembled ionic sensor is capable of maintaining high ionic conductivity and mechanical robustness at a sub-zero temperature of −25 °C ascribing to the presence of high-concentration charged functional groups and impregnated salts. As a demonstration, a wearable DHB-Fe/CS/PAA ionic sensor in a resistive mode is assembled, demonstrating high sensitivity, wide response range and excellent cyclability in detecting and distinguishing complex human motions rapidly and in real-time.

Water-soluble poly(ethylene glycol) methyl ether-grafted chitosan/alginate polyelectrolyte complex hydrogels

This study aimed to fabricate polyelectrolyte complexes from water-soluble poly(ethylene glycol) methyl ether-grafted chitosan (mPEG-g-CTS) and alginate (ALG) in the absence of acetic acid. The complexes formed fibrous network macrogels when mPEG-g-CTS with short mPEG chains (mPEG750-g-CTS and mPEG2000-g-CTS) and mPEG-g-CTS:ALG weight ratios in the range from 1:0.14 to 1:1 were used. The macrogels at a weight ratio of mPEG-g-CTS:ALG of 1:1 possessed the highest elasticity with electrophoretic mobility close to 0 m2·V−1·s−1. Water uptake of the sponge-like lyophilized macrogels decreased with increasing ALG content, mPEG chain length, and degree of substitution of mPEG-g-CTS. In contrast, the polyelectrolyte complexes prepared using long mPEG chains of mPEG-g-CTS (mPEG5000-g-CTS) formed spherical nanoparticles (70–90 nm) and showed highly negative electrophoretic mobility (< −3.20 × 108 m2·V−1·s−1). The obtained mPEG-g-CTS/ALG polyelectrolyte complex hydrogels and nanoparticles have the potential to be applied as carriers for functional food additives, drugs, and bioactive compounds.

Construction and characterization of Mesona chinensis polysaccharide-chitosan hydrogels, role of chitosan deacetylation degree

A novel kind of polyelectrolyte complex hydrogels was generated through polymerization of Mesona chinensis polysaccharide (MCP) and chitosan (CH) on the basis of physical crosslinking without the addition of ionic crosslinking agents or heat. Rheological measurement, Fourier transform infrared spectroscopy, X-ray diffraction, thermo-gravimetric analysis, and scanning electron microscopy were used to explore the properties of MCP−CH hydrogels. The effects of CH deacetylation degree (DD) on the gel properties and structural characteristics of MCP−CH hydrogels were also studied. Results showed that 0.5 % MCP and 1% CH could form stable and homogeneous hydrogels with favorable properties via electrostatic interaction. The viscoelasticity, water holding capacity, and thermostability of hydrogels were promoted with the increase in DD. The new crystallization peaks appeared with the formation of MCP−CH hydrogels. Moreover, the honeycomb-liked microstructure of MCP−CH hydrogels improved with the increase in DD. These findings may lay the foundation for the further application of MCP−CH hydrogels.

Smart and functional polyelectrolyte complex hydrogel composed of salecan and chitosan lactate as superadsorbent for decontamination of nickel ions

Green and functional bio based adsorbents based on naturally derived polysaccharides have attracted considerable interest owing to their non-toxicity, biodegradability, flexible design, and wide origins. Here, smart polyelectrolyte complex (PEC SC1-SC4) hydrogels were developed by self-assembling of different ratios of salecan and chitosan lactate (CL) for clean-up of nickel ion (Ni2+) from wastewater. Preparation process was rapid and eco-friendly, without any toxic cross-linkers. The electrostatic attractions between polysaccharides were studied by FT-IR, XRD, XPS, and TGA. Particularly, the content of salecan and CL could be precisely modulated to tailor the swelling ability, micromorphology, and stiffness of the hydrogels. Ni2+ adsorption onto the hydrogels was dependent on salecan/CL ratio, pH, initial ion concentration, and contact time. SC4 showed the highest Ni2+ uptake, but it was too brittle. SC3 was selected for absorption studies. The equilibrium adsorption data commendably matched the pseudo-second-order and Langmuir models, demonstrating monolayer chemical adsorption mechanisms. The maximum Ni2+ adsorption derived from Langmuir model was 414.9 mg/g, superior to many reported Ni2+ adsorbents. Most strikingly, SC3 performed good recyclability, and the adsorption capacity still kept 95.3% even after five adsorption/desorption cycles. Hopefully, the prepared SC3 hydrogel is a potential agent for treatment of wastewater contaminated with Ni2+ ion.

Structure, Morphology, and Rheology of Polyelectrolyte Complex Hydrogels Formed by Self-Assembly of Oppositely Charged Triblock Polyelectrolytes

We present scattering and rheology studies on model polyelectrolyte complex (PEC) hydrogels that form upon self-assembly of symmetric oppositely charged triblock polyelectrolytes in aqueous media. The hydrogel assembly is driven by associative phase separation of charged end-blocks to form PECs while the neutral mid-blocks restrict bulk phase separation of the PECs, leading to three-dimensional networks with PEC domains surrounded by neutral polymer coronae at sufficiently high polymer concentrations. Comprehensive characterization of the hydrogel structure (PEC domain size, morphology, spacing, and ordering) was enabled by a series of triblock polyelectrolytes with independently varying block lengths, facilitating the construction of morphology maps that offered direct comparisons with earlier theoretical predictions and highlighted the contributions of the charged and neutral blocks in directing PEC morphologies and hydrogel microstructures. Comparisons between the microstructure and shear rheology response emphasize the interplay between PEC domain morphologies and hydrogel flow behaviors. Furthermore, by drawing parallels with rheological models for associating polymer networks, we present preliminary insights into the role of chain-exchange dynamics between the PEC domains and cooperative electrostatic interactions in influencing the hydrogel flow properties.

Ionically crosslinked chitosan/poly(acrylic acid) hydrogels with high strength, toughness and antifreezing capability

A dual physically crosslinking (DPC) strategy is used to construct hydrogels with ultrahigh strength. First, polyelectrolyte complex (PEC) hydrogels were prepared through in situ polymerization of acrylic acid monomers in chitosan solutions. Subsequently, cations and anions were introduced into the PEC hydrogels to form strong electrostatic interactions with the polymer chains. The mechanical properties of the DPC hydrogels strongly depended on the ionic concentration and the valence state of the loading ions. The tensile strength of DPC-Na 8-20-2.0, DPC-Mg 8-20-2.0, DPCAl 8-20-2.0 and DPC-Sul 8-20-0.8 reached to 2.36, 12.59, 65.1 and 2.80 MPa, respectively, which were significantly higher than that of PEC 8-20 (0.29 MPa). Moreover, DPC-Na, DPC-Mg and DPC-Sul still maintained a good flexibility. Specifically, hydrogels of DPC-Ca exhibited ionic conductivity and freeze tolerance, which could be cooled to −20 °C without freezing. The DPC strategy opens an avenue to fabricate hydrogels with outstanding mechanical properties.