Ionic Crosslinking Research Articles

Human Muscle Inspired Anisotropic and Dynamic Metal Ion-Coordinated Mechanically Robust, Stretchable and Swelling-Resistant Hydrogels for Underwater Motion Sensing and Flexible Supercapacitor Application.

Mechanically robust and anisotropic conductive hydrogels have emerged as crucial components in the field of flexible electronic devices, since they possess high mechanical properties and intelligent sensing capabilities. However, the hydrogels often swell on exposure to aqueous medium because of their hydrophilicity, which compromises their mechanical properties. Additionally, the hydrogels' isotropic polymeric networks demonstrate isotropic ion transport, which significantly diminishes the sensing capabilities of electrical devices based on hydrogels. These factors greatly limit their use in flexible and wearable sensors. In this study, we have developed poly(acrylamide-co-maleic acid-co-butyl acrylate) based anisotropic hydrogels by prestretching and drying, followed by ionic cross-linking to fix the alignment. The anisotropic arrangement of the polymer network resulted in significant improvements in mechanical performance and electrical conductivity along the prestretching direction. This anisotropic hydrogel combines hydrophobic and metal ion-ligand interactions, enhancing the maximum tensile strength up to 11 MPa along the prestretching direction, about 3 times higher than in the perpendicular direction. The optimized 200% prestretched hydrogel exhibited high tensile strength (7 MPa), flexibility (fracture strain 370%), high toughness (16 MJ m-3) and antiswelling behavior in water (equilibrium swelling ratio 2% after 15 days). alongside higher conductivity (3 times higher) and strain sensing ability (4 times higher gauge factor) along the prestretching direction. The hydrogel demonstrated efficient and stable underwater sensing for underwater communication and to monitor human limb position and movement. The anisotropic hydrogel electrolyte-based flexible supercapacitor exhibited 117 Fg-1 specific capacitance at 0.5 Ag-1, and maximum energy density 5.85 Whkg-1, significantly higher than the corresponding values for the isotropic hydrogel-based device (88 F g-1 and 4.4 Whkg-1, respectively). This hydrogel mimics the structural design of unidirectionally oriented muscle fibers, showing better direction dependent functional properties than the corresponding isotropic hydrogel. The anti-swelling ability and retention of mechanical and conductive properties of these hydrogels in aqueous environment suggest long-term usage capability of these functional materials.

Ultrasensitive Flexible Organic Synaptic Transistors Modulated by a Chemically Cross-Linked Solvent-Resistive Ion Composite.

We demonstrate a flexible organic synaptic transistor (FOST) with an ion-composite electrolyte film resistant to chemical reagents, which uses a three-dimensionally cross-linked polyimide matrix to accommodate a high-concentration ionic liquid. FOST shows versatile synaptic plasticity for classical conditioning, high-pass filtering, and the learning-forgetting process. The device achieves low-energy consumption down to 1.02 femtojoule per synaptic event with an ultrasensitive impulse to presynaptic spike down to 0.5 mV. Moreover, the electrical performance of the device is still stable after 1000 mechanical bending cycles. These results demonstrate that the device can be applied to future flexible neuromorphic electronics.

A strategy for improving the mechanical properties of silk fibers through the combination of genetic manipulation and zinc ion crosslinking.

Silk fiber is generally considered an excellent biological material due to its good biocompatibility, morphological plasticity and biodegradability. Previously, the construction of silkworm silk gland bioreactors based on the piggyBac transposon has been optimized. However, the inserted exogenous genes have problems such as position uncertainty, and expression is not strictly controlled. Here, we applied transcription activator-like effector nuclease (TALEN)-mediated homology-directed repair (HDR) to precisely insert histidine-rich cuticular protein (CP) into silkworm Sericin1 (Ser1) gene. The Ser1-CP fusion protein was successfully secreted into cocoon shell. Subsequently, based on the metal coordination ability of the histidine imidazole group, we crosslinked cocoon with metal ions in vitro. In this strategy, the mechanical properties of the fused silk fibers with crosslinked Zn2+ improved, and the maximum breaking stress of the crosslinked Zn2+-fused silk fibers was 23.5 % greater than that of the wild-type fibers. Analysis of the secondary structure of the silk protein showed that the fused silk fibers crosslinked with Zn2+ had more β-sheet structures. This study pioneered a method of improving the mechanical properties of silk fibers by crosslinking metal ions with fused exogenous proteins and expanded the application value of silk gland bioreactors in the development of novel biomaterials.

In vitro bioprinted 3D model enhancing osteoblast-to-osteocyte differentiation

Abstract In vitro bone models are pivotal for understanding tissue behavior and cellular responses, particularly in unravelling certain pathologies' mechanisms and assessing the impact of new therapeutic interventions. A desirable in vitro bone model should incorporate primary human cells within a 3D environment that mimics the mechanical properties characteristics of osteoid and faithfully replicate all stages of osteogenic differentiation from osteoblasts to osteocytes. However, to date, no bio-printed model using primary osteoblasts has demonstrated the expression of osteocytic protein markers. This study aimed to develop bio-printed in vitro model that accurately captures the differentiation process of human primary osteoblasts into osteocytes. Given the considerable impact of hydrogel stiffness and relaxation behavior on osteoblast activity, we employed three distinct cross-linking solutions to fabricate hydrogels. These hydrogels were designed to exhibit either similar elastic behavior with different elastic moduli, or similar elastic moduli with varying relaxation behavior. These hydrogels, composed of gelatin (5% w/v), alginate (1%w/v) and fibrinogen (2%w/v), were designed to be compatible with micro-extrusion bioprinting and proliferative. The modulation of their biomechanical properties, including stiffness and viscoelastic behavior, was achieved by applying various concentrations of cross-linkers targeting both gelatin covalent bonding (transglutaminase) and alginate chains’ ionic cross-linking (calcium). Among the conditions tested, the hydrogel with a low elastic modulus of 8 kPa and a viscoelastic behavior over time exhibited promising outcomes regarding osteoblast-to-osteocyte differentiation. The cessation of cell proliferation coincided with a significant increase in alkaline phosphatase (ALP) activity, the development of dendrites, and the expression of the osteocyte marker PHEX. Within this hydrogel, cells actively influenced their environment, as evidenced by hydrogel contraction and the secretion of collagen I. This bio-printed model, demonstrating primary human osteoblasts expressing an osteocyte-specific protein, marks a significant achievement. We envision its substantial utility in advancing research on bone pathologies, including osteoporosis and bone tumors.

Alginate-chitosan hydrogel formulations for VEGFA expressed baculovirus delivery promoting angiogenesis for wound healing and revascularization

Abstract Background Baculoviruses, engineered to express growth factors, offer a promising avenue for short-term gene therapy, such as wound dressings, due to their safety and specificity. Encapsulation in natural polymers like alginate and chitosan addresses limitations like serum inactivation and fragility, while promoting sustained delivery and shielding from immune inactivation. Wound healing involves complex processes that can be enhanced by maintaining an antimicrobial, moist environment, which promotes cell migration and angiogenesis. Vascular endothelial cell growth factor A (VEGFA) is known to be one of the most potent pro-angiogenic factors and plays a key role in wound healing. Purpose This investigation seeks to enhance wound healing and angiogenesis, support the revascularization process, and provide anti-inflammatory and anti-microbial effects. Additionally, it aims to assess the preclinical efficacy and safety of the approach. Methods Ionic cross-linking was used for virus encapsulation under aseptic conditions. The capsules were assessed for their surface morphology, particle size, zeta potential, and in vitro release profile. Additionally, their therapeutic potential was studied using cell lines. The efficacy of hydrogel delivery of VEGFA-expressing baculoviruses in promoting cell migration and angiogenesis for wound healing applications was investigated on Human Umbilical Vein Endothelial Cells (HUVECs). Hydrogel morphology, swelling, and encapsulation efficiency were evaluated, along with endothelial tube formation assays and hemocompatibility studies on HUVECs. Results Encapsulation of baculovirus expressing the VEGFA gene in alginate and chitosan–alginate hydrogels achieve a high encapsulation efficiency of 99.9%. This allows for prolonged virus delivery and an increased therapeutic window. The encapsulated baculovirus maintains activity and is released over eight days, with a transduction efficiency of over 40%. This promotes tube formation, cell proliferation, and cell migration for angiogenesis, particularly beneficial for chronic wound-healing applications. The hydrogels also prevented E. coli and C. albicans growth directly below and inhibited C. albicans growth surrounding the alginate–chitosan hydrogels. The hydrogels demonstrated no cytotoxicity and good blood compatibility. Conclusion This proof of concept underscores the potential of encapsulated baculovirus delivery systems for various gene therapy applications including cardiovascular tissue regeneration and revascularization.

Low Fouling Molecular Selective Channels through Self-assembly of Cross-linked Block Copolymer Micelles for Selective Separation of Dye and Salt.

We report the solvent-evaporation and ionic cross-linking mediated self-assembly of the shell cross-linked micelles of the amphiphilic triblock copolymer containing middle poly(methyl methacrylate) block (hydrophobic) and poly(2-dimethylamino)ethyl methacrylate end blocks (hydrophilic) on the membrane substrate to create molecular selective channels. The formation of selective channels on the substrate is attributed to the local increase of micelle concentration upon solvent evaporation, which leads to the core-core hydrophobic interaction. The post-ionic cross-linking of the shell part further reduces the intermicelle distance, thereby creating interstices for selective separation. The TUF-1:1 membrane prepared by the self-assembly of the cross-linked micelles (triblock copolymer:halide-terminated PEG-based = 1:1 w w-1) and by the post-ionic cross-linking shows molecular weight cutoff of 3000 g mol-1 and pure water permeance of 52 L m-2 h-1 bar-1. The membrane shows 99.5-99.9% rejection of Congo red and Direct red-80 in the presence or absence of salts and Na2SO4 to dye separation factor of about 900. The added functionality (PEG) in the micelle structure provides good fouling-resistant properties toward dye and bovine serum albumin. This work provides the membrane formation mechanism and the advantages of the membrane for fractionation and resource recovery applications.

Ionically assembled hemostatic powders with rapid self-gelation, strong acid resistance, and on-demand removability for upper gastrointestinal bleeding.

Upper gastrointestinal bleeding (UGIB) is bleeding in the upper part of the gastrointestinal tract with an acidic and dynamic environment that limits the application of conventional hemostatic materials. This study focuses on the development of N-[(2-hydroxy-3-trimethylammonium) propyl] chitosan chloride/phytic acid (HTCC/PA, HP) powders with fast hemostatic capability and strong acid resistance, for potential applications in managing UGIB. Upon contact with liquids within 5 seconds, HP powders rapidly transform into hydrogels, forming ionic networks through electrostatic interactions. The ionic crosslinking process facilitates the HP powders with high blood absorption (3.4 times of self-weight), sufficient tissue adhesion (5.2 and 6.1 kPa on porcine skin and stomach, respectively), and hemostasis (within 15 seconds for in vitro clotting). Interestingly, the PA imparts the HP powders with strong acid resistance (69.8% mass remaining after 10 days of incubation at pH 1) and on-demand removable sealing while HTCC contributes to fast hemostasis and good wet adhesion. Moreover, the HP powders show good biocompatibility and promote wound healing. Therefore, these characteristics highlight the promising clinical potential of HP powders for effectively managing UGIB.

Efficient and sustainable recovery of Au(I) from thiosulfate solution by tri-n-butylphosphine functionalized chitosan microspheres with abundant pores

Thiosulfate as a green and environmentally friendly lixiviant has received great attention in the field of gold extraction. However, the problem of gold ion recovery in thiosulfate gold leaching solution has hindered the large-scale application of this technology. Here, tri-n-butylphosphine (TBUP) was used as a functional monomer to prepare an adsorbent (CTS-TBUP) with abundant pores through the ion crosslinking reaction of chitosan, which was used to recover Au(I) from Au[(S2O3)2]3− solution with high efficiency and large capacity. CTS-TBUP exhibited good potential for industrial applications with a gold loading capacity of 46.34 mg/g. CTS-TBUP exhibited a similar gold recovery performance for all pH ranges from 6 to 11, and the adsorption process of Au(I) on CTS-TBUP was well described by pseudo-second-order kinetics and Langmuir isothermal model. The mechanism by which CTS-TBUP adsorbs gold ions involves ligand exchange between TBUP and Au[(S2O3)2]3−. In addition, Au(I) on CTS-TBUP will be reduced to elemental gold by TBUP in CTS-TBUP. The mechanism of Au(I) adsorption by CTS-TBUP was also confirmed by density functional theory calculations, and confirmed the rationality of forming a complex with a coordination ratio of 2:1 between TBUP and Au(I) at the theoretical level. CTS-TBUP has a good affinity for gold ions in thiosulfate solution, which provides a new idea for the preparation of gold adsorbent.

POM-Based Hydrogels for Efficient Synergistic Chemodynamic/Low-Temperature Photothermal Antibacterial Therapy.

Bacterial infection of wound surfaces has posed a significant threat to human health and represents a formidable challenge in the clinical treatment. In this study, a novel antimicrobial hydrogel utilizing POM is synthesized as the primary component, with gelatin and sodium alginate as the structural framework. The resultant hydrogel demonstrates exceptional mechanical properties and viscoelasticity attributed to the hydrogen-bonded cross-linking between POM and gelatin, as well as the ionic cross-linking between sodium alginate and Ca2+. In addition, the integration of CuS nanoparticles conferred photothermal properties to the hydrogel system. To address the concerns regarding the potential thermal damage to the surrounding normal cells, this study employs a LT-PTT combined with CDT approach to achieve the enhanced antimicrobial efficacy while minimizing the inadvertent harm to the healthy cells. The findings suggested that POM-based hydrogels, serving as an inorganic-organic hybrid material, will represent a promising antimicrobial solution and offer valuable insights for the development of the non-antibiotic materials.

Structural, physicochemical, and in vitro digestion properties of microgel-reinforced synbiotic hydrogel beads filled with pectic oligosaccharides as a delivery system for Limosilactobacillus reuteri

Pea protein microgel (MG)-reinforced synbiotic low methoxyl pectin (LMP) hydrogel beads filled with different concentrations (0 %, 0.2 %, and 0.4 %) of pectic oligosaccharides (POS) were developed as delivery system for Limosilactobacillus reuteri (L. reuteri). SEM results revealed that incorporating POS into the hydrogel beads made the gel matrix smoother and more compact, reducing probiotic leakage and higher encapsulation efficiency. FT-IR analysis observed new ionic crosslinking between LMP and calcium ions. In vitro digestion results suggested that MG-reinforced synbiotic hydrogel beads showed higher survival rates throughout upper gastrointestinal tract than MG, and the highest values were observed in the hydrogel beads with 0.4 % of POS. Most L. reuteri was released from the developed system after exposure to simulated colonic conditions for 48 h. MG-reinforced synbiotic hydrogel beads showed higher thermal and storage stability than MG alone, indicating that adding hydrogel bead layer to MG can efficiently protect L. reuteri from environmental stresses.

Low cost Non freeze-drying construction strategy of cellulose aerogels for efficient solar desalination

Aerogel-like materials with three-dimensional pore structures show great potential in the field of efficient solar-driven interfacial evaporation by virtue of their fast water transport as well as efficient energy confinement properties. However, the preparation of aerogels is currently limited by high-cost strategies such as freeze drying or supercritical drying. Here, we present a foam template-assisted (FTA) strategy for atmospheric pressure drying of cellulose nanofiber (CNF) aerogels. Building a robust CNF network is the key to resisting surface tension during water evaporation and achieving drying in ambient environments, which is achieved through cleverly designed ionic cross-linking with the help of FTA. Cellulose aerogel (CA) constructed using the FTA strategy exhibit lightweight (9 mg cm−3) and porous properties (porosity: > 99 %). The tannic-coated CA (TCA) was achieved by further polymerizing tannic acid on the CA surface, which has excellent photothermal conversion capability. Meanwhile, TCA achieved an impressive evaporation rate of 3.58 kg m-2h−1 and an energy efficiency of 97.2 % at 1sun radiation by virtue of its excellent energy confinement and water management capabilities. This strategy provides a promising solution for the low-cost construction of aerogels as well as for the realization of efficient solar-driven interfacial evaporators.

Influence of copper ion cross-linked CMC-PVA film on cell viability and cell proliferation study

In this study, films composed of carboxymethyl cellulose and polyvinyl alcohol were fabricated using the solution casting method. Citric acid (4 %) was employed as a cross-linking agent, while glycerol (3 %) as a plasticizer. Cupric chloride (CuCl2·2H2O) was used for cross-linking at concentrations 0.5 %, 1 %, and 3 % over different times. The cross-linking with copper ions led to a noticeable reduction in elasticity, with the breaking strain ranging from 17.9 %–52.9 %. The ion hydration phenomenon increased the contact angle and swelling ratio. Fourier-transform infrared (FTIR) spectroscopy confirmed esterification reactions and copper ion cross-linking with sodium carboxymethyl cellulose (Na-CMC). The films showed antibacterial activity against Staphylococcus aureus and Escherichia coli. The ion-released mechanism followed was the non-Fickian super case-II type. The concentration and duration of cross-linking significantly influenced cell viability and proliferation. FE-SEM analysis revealed that effective concentrations of CuCl2.2H2O were 0.5 % and 1 %, and cross-linking times were 5–15 min, facilitating cell attachment and proliferation. Films are non-adhesive with water vapor permeation 800–900 g/m2/day. These results indicate the potential use of the films in treating second-degree burn wounds with low to medium exudate levels. This study provides valuable insights into the development of copper-infused materials for advanced wound healing applications.

Tragacanth gum hydrogels with cellulose nanocrystals: A study on optimizing properties and printability

This study investigates a novel all-polysaccharide hydrogel composed of tragacanth gum (TG) and cellulose nanocrystals (CNCs), eliminating the need for toxic crosslinkers. Designed for potential tissue engineering applications, these hydrogels were fabricated using 3D printing and freeze-drying techniques to create scaffolds with interconnected macropores, facilitating nutrient transport. SEM images revealed that the hydrogels contained macropores with a diameter of 100–115 μm. Notably, increasing the CNC content within the TG matrix (30–50 %) resulted in a decrease in porosity from 83 % to 76 %, attributed to enhanced polymer-nanocrystal interactions that produced denser networks. Despite the reduced porosity, the hydrogels demonstrated high swelling ratios (890–1090 %) due to the high water binding capacity of the hydrogel. Mechanical testing showed that higher CNC concentrations significantly improved compressive strength (27.7–49.5 kPa) and toughness (362–707 kJ/m3), highlighting the enhanced mechanical properties of the hydrogels. Thermal analysis confirmed stability up to 400 °C and verified ionic crosslinking with CaCl₂. Additionally, hemolysis tests indicated minimal hemolytic activity, affirming the biocompatibility of the TG/CNC hydrogels. These findings highlight the potential of these hydrogels as advanced materials for 3D-printed scaffolds and injectable hydrogels, offering customizable porosity, superior mechanical strength, thermal stability, and biocompatibility.

Effects of Coaxial Nozzle's Inner Nozzle Diameter on Filament Strength and Gelation in Extrusion-Based 3D Printing with In Situ Ionic Crosslinking.

This study systematically investigates the effects of the coaxial nozzle's inner nozzle diameter on the strength and gelation of filaments produced via extrusion-based 3D printing with in situ ionic crosslinking. In this system, bioink (sodium alginate solution) was extruded through the outer nozzle, and the ionic crosslinking solution (calcium chloride solution) was extruded through the inner nozzle. The outer nozzle diameter was fixed at 2.16 mm, and the inner nozzle diameter was varied among 1.19, 0.84, and 0.584 mm. The results indicate that, as the inner nozzle diameter decreased, filament strength decreased, and filament gelation became poorer. These findings highlight the importance of optimizing inner nozzle diameter for improved filament strength and gelation in extrusion-based 3D printing with in situ ionic crosslinking.

Mechanical and Biological Characterization of Ionic and Photo-Crosslinking Effects on Gelatin-Based Hydrogel for Cartilage Tissue Engineering Applications.

Articular cartilage degeneration poses a significant public health challenge; techniques such as 3D bioprinting are being explored for its regeneration in vitro. Gelatin-based hydrogels represent one of the most promising biopolymers used in cartilage tissue engineering, especially for its collagen composition and tunable mechanical properties. However, there are no standard protocols that define process parameters such as the crosslinking method to apply. To this aim, a reproducible study was conducted for exploring the influence of different crosslinking methods on 3D bioprinted gelatin structures. This study assessed mechanical properties and cell viability in relation to various crosslinking techniques, revealing promising results particularly for dual (photo + ionic) crosslinking methods, which achieved high cell viability and tunable stiffness. These findings offer new insights into the effects of crosslinking methods on 3D bioprinted gelatin for cartilage applications. For example, ionic and photo-crosslinking methods provide softer materials, with photo-crosslinking supporting cell stretching and diffusion, while ionic crosslinking preserves a spherical stem cell morphology. On the other hand, dual crosslinking provides a stiffer, optimized solution for creating stable cartilage-like constructs. The results of this study offer a new perspective on the standardization of gelatin for cartilage bioprinting, bridging the gap between research and clinical applications.

Mechanism underlying anion-sieving in poly(ionic liquid)-based membrane: Effective acid recovery from engineering waste

Anion exchange membranes (AEMs) are promising for recovering acid from different engineering effluent due to their lower energy consumption, positive environmental impact, and potential for providing clean water resources. Utilizing the diffusion dialysis (DD) process, AEMs effectively retain metal ions while selectively allowing fast proton permeation. Achieving high hydrophilicity, proton conductivity, and ion exchange capacity through exact control of polymeric structure and chemical composition is crucial for enhancing the efficiency of the acid recovery process. This study presents the findings on the impact of novel Poly(ionic liquid) on cellulose acetate-based AEMs for acid recovery through DD application. In this study, interconnected nanochannel AEMs with high acid permeability are engineered using a straightforward blending technique. Poly(3-butyl-1-vinylimidazolium bromide-co-methyl methacrylate-co-styrene) (poly([BVIM]-[Br]–co–MMA-co-Styrene, PIL) is blended with cellulose acetate to achieve ionic crosslinking, resulting in a mechanically stable membrane. The dosage of PIL within the membrane matrix plays a vital role in determining the prepared membranes' physicochemical properties and ion exchange capabilities, which exhibit excellent thermal stability. Remarkably, the optimal AEM (7.5 % PILM) exhibits a high acid dialysis coefficient (UH+) of 1.05 m/h and a separation factor (S) of 802, outperforming previously reported state-of-the-art AEMs and commercial membranes. These findings indicate that the prepared AEMs are highly effective for acid recovery through DD. Notably, our work stands out by introducing new AEMs with superior acid dialysis performance and selectivity.

A novel chitosan-based hydrogel microspheres for efficient heavy metal-ion adsorption

Pb (II) and Cu (II) are the most critical metal ion pollutants commonly found in wastewater, and prolonged exposure to these metal ions can pose serious risks to human health. Therefore, the removal of these pollutants from wastewater is of particular importance. In this study, soy hull nanocellulose/sodium alginate/chitosan (SHNC/SA/CS) hydrogel microspheres were prepared using the ion crosslinking method, and they were used to adsorb Pb (II) and Cu (II) present in wastewater. The SHNC/SA/CS hydrogel microspheres exhibited excellent toughness (18.67 MPa) and hydrophilicity (21.43° ± 0.65°), which improved their reuse rate. Furthermore, hydroxyl, carboxyl and amino groups served as excellent chelating groups and considerably improved the adsorption efficiency of the SHNC/SA/CS hydrogel microspheres. The SHNC/SA/CS hydrogel microspheres exhibited an ultrahigh adsorption rate and an outstanding adsorption capacity for Pb (II) and Cu (II), with an equilibrium adsorption period of 50 min. The equilibrium adsorption capacities for Pb (II) and Cu (II) reached 116.62 and 94.32 mg/g, respectively. Furthermore, the SHNC/SA/CS hydrogel microspheres maintained a removal rate of up to 80 % for Pb (II) and Cu (II) after 10 adsorption–desorption cycles, demonstrating their potential for reuse. The SHNC/SA/CS hydrogel microspheres demonstrated an adsorption performance superior to that reported for CS-based adsorption materials. Moreover, X-ray photoelectron spectroscopy revealed that the adsorption mechanisms of SHNC/SA/CS hydrogel microspheres for Pb (II) and Cu (II) included ion exchange, pore filling, complexation and electrostatic attraction. Moreover, a synergistic coordination effect existed between carboxyl and amino groups.

Multilayered alginate–hydrogel-functionalized zeolite based on ionic cross-linking composed with a certain Ca2+ and Mg2+ ratio for ammonium adsorption

To enhance ammonium removal in wastewater treatment, a novel adsorbent, multilayered ionic cross–linked alginate–hydrogel–metal-coated zeolite (Al-H-M-Z), was synthesized. Essential divalent cations, 2.60 mmol of Ca2+ and Mg2+, were incorporated into Al-H-M-Z (10 g) in a Ca2+:Mg2+ ratio of 0.73:1.85, facilitating strong alginate–polymer interactions and significantly enhancing the adsorption efficiency. Langmuir and Freundlich isotherm analyses revealed that Al-H-M-Z had a maximum adsorption capacity of 56.5 ± 8.78 mg g−1 and an adsorption intensity of 0.703 ± 0.122, which were 7.24-fold and 1.59-fold higher than those of natural zeolite (7.80 ± 1.09 mg g−1 and 0.444 ± 0.254), respectively. These enhanced properties are attributed to the modified structural and surface chemistry. The Al-H-M-Z coating exhibited a 4.76-fold increase in surface area (3.91 m2 g−1), an 8.94-fold increase in micropore volume (17.8 × 10−3 cm3 g−1), and a 4.22-fold increase in pore diameter (4.14 nm) when compared to the traditional Al-only coating. For applicability, Al-H-M-Z and Z achieved ammonium removal rates of 7.94% and 5.61%, respectively, in actual fish farm wastewater, representing a 1.41-fold improvement in adsorption efficiency after the coating process.

Homogeneous CaAlg/PES hybrid ultrafiltration membranes prepared with in situ ionic crosslinking and phase inversion method

Calcium alginate hydrogel/polyethersulfone (CaAlg/PES) hybrid membranes were synthesized via combining in situ ion crosslinking with phase conversion method. Once the Sodium alginate (NaAlg) uniformly dispersed in the casting solution contacted with Ca2+ dissolved in coagulation bath solution in the phase conversion membrane formation process, nanoscale CaAlg hydrogel was in situ formed through ion exchange and evenly dispersed in the membrane matrix. FT-IR and XPS were adopted to confirm the formation of CaAlg hydrogel distributed in PES membrane matrix. SEM, AFM, BET analysis and contact Angle analyzer were all used to characterize the surface changes of morphology, roughness and hydrophilicity in detail. Specific separation performance was also evaluated and compared by cross-flow ultrafiltration tests. Comprehensive analysis of the measured properties of all obtained membranes, when the content of NaAlg was 1.5 wt%, the CaAlg/PES hydrogel membrane M32 had the most excellent performance. The pure water flux increased from 1967 to 2193 L/m2hMPa, rejection rate of BSA was up to 99.87 %, and RFR value was almost 76.83 % after 4 cycles BSA filtration. XPS characterization of the membrane after filtration for 72 hours showed that the retention rate of Ca (2 P) reached 95 %, which further proved the stability of the membrane operation.

Biomimetic anisotropic hydrogel as a smart self-healing agent of sustainable cement-based infrastructure

The durability improvement of cement-based infrastructure is an effective strategy to achieve sustainable development and reduce the carbon footprint. In this work, a biomimetic anisotropic hydrogel, alginate/polyacrylamide/halloysite nanotubes hybrid hydrogel (SA/AM/HNTs-RDC), was fabricated as a self-healing agent to enhance the self-healing ability and extend the service life of cement-based infrastructure. The effects of SA/AM/HNTs-RDC hydrogel on the formation and deposition of healing products and the self-healing behavior of cement in the different conditions (water condition and CO2-rich condition) were investigated. Compared with the matrix hydrogel (alginate/polyacrylamide, SA/AM), the crosslinking ions and anisotropic microstructure of SA/AM/HNTs-RDC hydrogel can stimulate the massive formation and dense deposition of healing products (ettringite (AFt) and monosulfo aluminate (AFm) in the simulated water condition, calcite and AFt in CO2-rich condition) to accelerate the performance recovery of the damaged construction. The self-healing measurements exhibited that the cracks around 200 μm in the cement paste with 1 % anisotropic hydrogel (RDC1) can be sealed completely after 14-day-curing in water, and its recovery ratio of the compressive strength increased by about 10 % compared with control samples. In CO2-rich condition, the closure rate of cracks was accelerated and the complete healing of cracks with similar width only needed 7 days. The compressive strength recovery increased by 13.7 % over control samples.