semi-IPN Hydrogels Research Articles

Green synthesis of multifunctional responsive hydrogel embedded with silver, based on xanthan gum, N-isopropylacrylamide, vinyl imidazole, and Luffa cylindrica for wound healing

In this study, a pH- and temperature-responsive smart hydrogel was developed by utilizing Xanthan Gum (XG), N-Isopropylacrylamide (NIPAM), Vinyl Imidazole (VI), and Luffa cylindrical (LC). Semi-interpenetrating polymer networks (semi-IPNs) were created using free radical polymerization with N,N′-methylenebisacrylamide (MBA) as the cross-linker and ammonium persulfate (APS) as the initiator. Silver nanoparticles (AgNPs) were synthesized within semi-IPN hydrogel network structures to impart antibacterial properties. Malva sylvestris (MS) aqueous leaf extract was used as a reducing and stabilizing agent for the green synthesis of the AgNPs. The semi-IPN hydrogels exhibited pH- and temperature-responsive swelling behavior, which also enabled the controlled release of the drug. After 11 h, the cumulative release reached approximately 73% at pH 7.2 and 87% at pH 8.3. Additionally, the sustained release mechanism of the Trimethoprim drug was described using the Korsmeyer-Peppas model and was governed by Fickian diffusion. The drug-loaded semi-IPN@Ag nanocomposite hydrogel has demonstrated effective antibacterial activity against various Gram-negative and Gram-positive bacteria, indicating its promising potential as a wound dressing material for reducing infection risk.

Adsorption technique using new semi-IPN hydrogels for high removal of methylene blue dye from aqueous solutions

ABSTRACT Six new semi-IPN hydrogels using 2-acrylamido-methylpropane-1-sulfonic acid (AMPS) and Gelatin at different ratios through redox polymerization were prepared. Methylene-bisacrylamide and glutaraldehyde were used as the crosslinking agents for AMPS and Gelatin, respectively. The hydrogels’ swelling ratios and surface morphologies were analyzed using SEM for characterization. Porosity and specific surface area using the Brunauer–Emmett–Teller technique. DSC and Tg were also used for the thermal analysis of the prepared hydrogels, which show trans-glass temperature (Tg) higher than their raw materials AMPS and Gelatin. The prepared hydrogels were used to eliminate the cationic dye MB from the water-based solutions with an initial concentration of 600 ppm. The study discovered that the N9 and N10 hydrogels were extremely effective at removing a certain dye from aqueous solutions with an optimum pH level of 11 and an optimum temperature of 65°C. Both N9 and N10 achieved high removal efficiencies, reaching equilibrium at 90 min, whereas the other hydrogels required 120 min. N9 performed slightly better at 1078.919 mg/g and N10 at 1057.404 mg/g. The adsorption behavior of the two hydrogels followed the Langmuir model. The hydrogels exhibited pseudo-second-order kinetics. The thermodynamic study cleared that the adsorption of MB dye was endothermic and spontaneous. Results also showed that the adsorption of dyes with hydrogels N9 and N10 is chemisorption in nature. Desorption studies were conducted using 0.1 M HCl and NaOH. HCl was found to be the best eluent for dye recovery.

Semi-IPN polysaccharide-based hydrogels for effective removal of heavy metal ions and dyes from wastewater: a comprehensive investigation of performance and adsorption mechanism.

The escalating issue of environmental pollutants necessitates efficient, sustainable, and innovative wastewater treatment technologies. This review comprehensively analyzes the mechanisms and isotherms underlying the adsorption processes of semi-interpenetrating polymer network (semi-IPN) polysaccharide-based hydrogels to remove heavy metal ions and dyes from wastewater. Polysaccharides are extensively utilized in hydrogel synthesis due to their biocompatibility, cost-effectiveness, and non-toxic nature. The synthesis of these hydrogels as semi-IPNs enhances their mechanical and structural robustness and adsorption capacity. This review explores the key parameters affecting adsorption performance, including pH, temperature, contact time, and adsorbent dosage. Findings highlight that semi-IPN polysaccharide-based hydrogels exhibit remarkable adsorption capabilities through electrostatic interactions, ion exchange, and surface complexation. Furthermore, this review highlights the distinct advantages of semi-IPNs over other polymer networks. Semi-IPNs offer improved mechanical stability, higher adsorption efficiencies, and better reusability, making them a promising solution for wastewater treatment. Detailed isotherm models, including Langmuir and Freundlich isotherms, were studied to understand these hydrogels' adsorption behavior and capacity for different pollutants. This study highlights the potential of semi-IPN polysaccharide-based hydrogels as effective adsorbents forheavy metals and dyes and as a promising solution for mitigating environmental pollution. The insights provided herein contribute to developing advanced materials forenvironmental remediation, aligning with global sustainability goals, and advancing wastewater treatment technology.

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

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

A carboxymethyl-resistant starch/polyacrylic acid semi-IPN hydrogel with excellent adhesive and antibacterial properties for peri-implantitis prevention

Hydrogels possess inherent characteristics that render them promising for the prevention of peri-implantitis. Nonetheless, hydrogels with singular network structures are incapable of concurrently achieving the desired adhesion and mechanical properties. In this work, a carboxymethyl resistant starch/polyacrylic acid semi-interpenetrating (CMRS/PAA semi-IPN) hydrogel was successfully prepared in one step. Its morphology, structure, mechanical properties, and adhesion properties were systematically assessed, which revealed a homogeneously porous structure with a commendable mechanical strength of 67.317 kPa and an adhesion strength of 63 kPa. Ciprofloxacin (Cip) was loaded in the CMRS/PAA hydrogel via in situ compounding. The in vitro kinetic study of drug release shows that the slow drug release efficiency exceeds 90 % in the weakly acidic microenvironment at the infection site after 72 h, indicating enhanced antimicrobial properties. The Cip-loaded hydrogel also exhibits a remarkable bacterial inhibition rate exceeding 99 % against the pathogenic bacterium P. gingivalis and good cytocompatibility and hemocompatibility in vitro. In summary, the current work explored a novel solution and direction for the development of anti-infective medical materials applicable to dental implants.

Collagen-β-cyclodextrin hydrogels for advanced wound dressings: super-swelling, antibacterial action, inflammation modulation, and controlled drug release

A key strategy in enhancing the efficacy of collagen-based hydrogels involves incorporating polysaccharides, which have shown great promise for wound healing. In this study, semi-interpenetrating polymeric network (semi-IPN) hydrogels comprised of collagen (Col) with the macrocyclic oligosaccharide β-cyclodextrin (β-CD) (20–80 wt.%) were synthesised. Fourier-transform infrared (FTIR) spectroscopy confirmed the successful fabrication of these Col/β-CD hydrogels, evidenced by the presence of characteristic absorption bands, including the urea bond band at ∼1740 cm−1, related with collagen crosslinking. Higher β-CD content was associated with increased crosslinking, higher swelling, and faster gelation. The β-CD content directly influenced the morphology and semi-crystallinity. All Col/β-CD hydrogels displayed superabsorbent properties, enhanced thermal stability, and exhibited slow degradation rates. Mechanical properties were significantly improved with contents higher than β-CD 40 wt.%. These hydrogels inhibited the growth of Escherichia coli bacteria and facilitated the controlled release of agents, such as malachite green, methylene blue, and ketorolac. The chemical composition of the Col/β-CD hydrogels did not induce cytotoxic effects on monocytes and fibroblast cells. Instead, they actively promoted cellular metabolic activity, encouraging cell growth and proliferation. Moreover, cell signalling modulation was observed, leading to changes in the expression of TNF-α and IL-10 cytokines. In summary, the results of this research indicate that these novel hydrogels possess multifunctional characteristics, including biocompatibility, super-swelling capacity, good thermal, hydrolytic, and enzymatic degradation resistance, antibacterial activity, inflammation modulation, and the ability to be used for controlled delivery of therapeutic agents, indicating high potential for application in advanced wound dressings.

Development of a Controlled Released System Based on IPN Types Hydrogel for Cartilage Repair

The purpose of this study is to develop a controlled Fluconazole and Naproxen releasing system for cartilage repair. Interpenetrating polymer network (IPN) type of hydrogels were prepared by using different ratios of 2-Hydroxyethyl methacrylate (HEMA) and gelatin. The hydrogels were synthesized by using ammonium persulfate (APS) and sodium metabisulfite (SBS) as initiator pair and ethylene glycol dimethacrylate (EGDMA) and glutaraldehyde (GA) as cross linkers. The prepared hydrogels were characterized via hydrogel formation and swelling/degradation measurements, Fourier Transform Infrared Spectroscopy (FT-IR) and Scanning Electron Microscope (SEM) analysis. From swelling tests, it is observed that semi-IPN hydrogels swell much more than full-IPNs which crosslinked by two agents, EGDMA and GA. The higher ratios of HEMA/gelatin negatively affect swelling values. In general, the IPN hydrogel discs were not affected by the variation of temperature. The release studies of Fluconazole and Naproxen were performed at 37 ⁰C and it is found that the swelling and releasing profiles were similar to each other. The releases of drugs increase rapidly at first and then complies nearly 36 h-48 h. Because of the looser and porous structure, semi-IPN hydrogels have higher release values than full-IPNs.

Facile synthesis of an acrylic acid-co-2-acrylamide-2-methylpropanesulfonic acid copolymer / polyvinylpyrrolidone semi-IPN hydrogel with excellent swelling and anti-leakage properties

Water scarcity becomes an increasingly serious problem for humankind due to climate change and population growth, especially the water leakage in arid and semi-arid areas. Hydrogel polymers show increasingly important roles on water resources utilization. A novel hydrogel copolymer, acrylic acid-co-2-acrylamide-2-methylpropanesulfonic acid copolymer / polyvinylpyrrolidone (P(AA-co-AMPS)/PVP) semi-interpenetrating network (semi-IPN) hydrogel, was designed and successfully synthesized via a facile one-pot free radical copolymerization method. The main parameters during the synthesis process were optimized, including relative contents of polymer monomers, cross-linking agent, initiator and neutralization agent. Physical characterizations demonstrate that, P(AA-co-AMPS)/PVP hydrogel shows porous three-dimensional network structure, including a crosslinked network structure in P(AA-co-AMPS) copolymers and their intermolecular hydrogen bonding interactions with linear PVP. The as-synthesized P(AA-co-AMPS)/PVP hydrogel not only can deliver superior water absorbing capability (up to 1689.95 g g−1) and good reswelling performance, but also shows excellent water anti-leakage performance when being composed with red clay, demonstrating its multi-role applications in future sustainable agriculture.

Impact of Modifications from Potassium Hydroxide on Porous Semi-IPN Hydrogel Properties and Its Application in Cultivation.

This study synthesized and modified a semi-interpenetrating polymer network hydrogel from polyacrylamide, N,N'-dimethylacrylamide, and maleic acid in a potassium hydroxide solution. The chemical composition, interior morphology, thermal properties, mechanical characteristics, and swelling behaviors of the initial hydrogel (SH) and modified hydrogel (SB) in water, salt solutions, and buffer solutions were investigated. Hydrogels were used as phosphate fertilizer (PF) carriers and applied in farming techniques by evaluating their impact on soil properties and the growth of mustard greens. Fourier-transform infrared spectra confirmed the chemical composition of SH, SB, and PF-adsorbed hydrogels. Scanning electron microscopy images revealed that modification increased the largest pore size from 817 to 1513 µm for SH and SB hydrogels, respectively. After modification, the hydrogels had positive changes in the swelling ratio, swelling kinetics, thermal properties, mechanical and rheological properties, PF absorption, and PF release. The modification also increased the maximum amount of PF loaded into the hydrogel from 710.8 mg/g to 770.9 mg/g, while the maximum % release of PF slightly increased from 84.42% to 85.80%. In addition, to evaluate the PF release mechanism and the factors that influence this process, four kinetic models were applied to confirm the best-fit model, which included zero-order, first-order, Higuchi, and Korsmeyer-Peppas. In addition, after six cycles of absorption and release in the soil, the hydrogels retained their original shapes, causing no alkalinization or acidification. At the same time, the moisture content was higher as SB was used. Finally, modifying the hydrogel increased the mustard greens' lifespan from 20 to 32 days. These results showed the potential applications of modified semi-IPN hydrogel materials in cultivation.

Tuning physicomechanical properties of PEG-interpenetrated anionically modified semi-IPN cryogels functionalized with carboxylate groups

Anionically modified interpenetrated polymer network (semi-IPN) cryogels containing linear polyethylene glycol chains (PEG) were prepared via in situ synthesis and directed assembly of the negatively charged copolymer poly(acrylamide-co-sodium acrylate) (PAN) network template. The influence of reaction conditions; the concentration of linear PEG chains, and polymerization temperature on the elasticity and swelling of these IPNs was analyzed in detail. The interpenetrating structure of PEG chains and PAN host network have been confirmed by FTIR, TGA and XRD analysis. The equilibrium water content, oscillatory swelling/deswelling kinetics, and water transport mechanism were analyzed as a function of PEG content. The results showed that semi-IPN gels exhibited different swelling behavior as the reaction conditions varied. Addition of 13.9% (w/v) PEG resulted in a 25-fold increase in the swelling ratio of semi-IPN hydrogels. By performing compression tests on semi-IPN gels to determine the change of compression properties, the effective cross-linking density of semi-IPN PAN/PEG was expressed as a second-order polynomial depending on the amount of PEG. The swollen modulus of semi-IPN cryogels was much higher than that of semi-IPN hydrogels for all PEG concentrations. Semi-IPNs showed reversible on-off switching with remarkable sensitivity to external pH stimulus. Structural parameters, degree of swelling, volume fraction of cross-linked polymer in the swollen state, and diffusion coefficients due to pH-induced swelling of semi-IPN gels were determined. The presence of linear PEG chains in the structure promoted swelling by both increasing the swelling rate and significantly reducing the time required to reach the equilibrium-state. The swelling process was Fickian diffusion, and the diffusion coefficients for swelling of PEG-interpenetrated semi-IPNs increased with PEG content. The effectiveness of removing methylene blue (MB) dye from aqueous solutions by semi-IPNs was evaluated. Batch adsorption experiments were performed as a function of the gelation temperature, amount of PEG, contact time, and initial dye concentration. The adsorption isotherm and kinetics were described well by Langmuir isotherm model and pseudo-second-order model, respectively. Adsorption of MB was a multi-step process involving surface adsorption followed by intra-particle diffusion. Semi-IPN PAN/PEG cryogels prepared under cryocondition with high adsorption capacities and fast adsorption rates have been developed as new adsorbents effective in removing dyes and other toxic substances with higher mechanical strength in water and wastewater treatment.

Facile fabrication of temperature/pH dual sensitive hydrogels based on cellulose and polysuccinimide through aqueous amino-succinimide reaction

A temperature/pH dual sensitive hydrogel with a semi-interpenetrating network (semi-IPN) structure was synthesized through an aqueous amino-succinimide reaction between water-soluble polysuccinimide and polyethyleneimine in the presence of thermosensitive cellulose derivatives. Single-factor experiments were carried out to optimize the preparation conditions of the semi-IPN hydrogel. The swelling behavior and cytotoxicity assay of the hydrogel were tested. Finally, taking 5- fluorouracil (5-Fu) as a model drug, the release performance of the 5-Fu-loaded hydrogel was investigated. The results indicated that the swelling ratio (SR) first decreased and then increased when the pH of the solutions ascended from 2 to 10. The SR decreased with the increase in temperature. In addition, the swelling behavior of the hydrogel was reversible and reproducible under different pH values and temperatures. The prepared hydrogels had good cytocompatibility. The release behavior of 5-Fu was most consistent with the Korsmeyer-Peppas model and followed the case II diffusion. The acidic environment was beneficial for the release of 5-Fu. The preparation process of the semi-IPN hydrogel is simple and the reaction can proceed quickly in water. The strategy introduced here has great potential for application in the preparation of drug carriers.

Enhanced dye removal using montmorillonite modified with graphene quantum dots in sustainable salep nanocomposite hydrogel

This research investigated the utilization of graphene quantum dot/montmorillonite (GQD/MMT) as an effective nanofiller in a hydrogel composed of salep biopolymer. The semi-IPN hydrogel was synthesized using salep as the substrate, acrylamide (AAm) as the monomer, ammonium persulfate (APS) as an initiator in free radical polymerization, and N,N'-methylenebisacrylamide (MBA) as a cross-linking agent. The hydrogels were applied to remove safranin (SA), methylene blue (MB), crystal violet (CV), methyl green (MG), congo red (CR), and malachite green (MG) dyes from the water. The diverse properties were analyzed using a scanning electron microscope, fourier infrared spectroscopy, mapping, energy dispersive spectroscopy, weighing analysis, X-ray diffraction, and thermal stability analyses. The optimism of the prepared adsorbent in dye absorption was evaluated by measuring the swelling amount, pH impact, adsorbent dosage, and contact time. The adsorption calculations were described using kinetics and isotherm models. The results indicated that the Langmuir isotherm model (R2 = 99.6) and the pseudo-second-order kinetic model (R2 = 99.9) provided the best fit for the absorption process of MB. The presence of additional amounts of GQD/MMT had a reciprocal effect on the adsorption efficiency due to the accumulation of GQD/MMT in the semi-interpenetrating polymer network (semi-IPN (structure. The findings revealed that the samples exhibited high thermal stability, and the absorption process was primarily chemical. Furthermore, the nanocomposite hydrogels demonstrated distinct mechanisms for absorbing anionic dye (CR) and cationic dye (MB). Under optimal conditions, using 7 wt% GQD/MMT at a concentration of 5 ppm, pH = 7, an adsorbent dosage of 50 mg, at room temperature, and a contact time of 90 min, the maximum removal efficiencies were achieved: MB (96.2%), SA (98.2%), MG (86%), CV (99.8%), MG (95.8%), and CR (63.4%). These results highlight the adsorbent's high absorption capacity, rapid removal rate, and reusability, demonstrating its potential as an eco-friendly and cost-effective solution for removing dyes from water.

Simultaneous Formation of Polyhydroxyurethanes and Multicomponent Semi-IPN Hydrogels.

This study introduces an efficient strategy for synthesizing polyhydroxyurethane-based multicomponent hydrogels with enhanced rheological properties. In a single-step process, 3D materials composed of Polymer 1 (PHU) and Polymer 2 (PVA or gelatin) were produced. Polymer 1, a crosslinked polyhydroxyurethane (PHU), grew within a colloidal solution of Polymer 2, forming an interconnected network. The synthesis of Polymer 1 utilized a Non-Isocyanate Polyurethane (NIPU) methodology based on the aminolysis of bis(cyclic carbonate) (bisCC) monomers derived from 1-thioglycerol and 1,2-dithioglycerol (monomers A and E, respectively). This method, applied for the first time in Semi-Interpenetrating Network (SIPN) formation, demonstrated exceptional orthogonality since the functional groups in Polymer 2 do not interfere with Polymer 1 formation. Optimizing PHU formation involved a 20-trial methodology, identifying influential variables such as polymer concentration, temperature, solvent (an aprotic and a protic solvent), and the organo-catalyst used [a thiourea derivative (TU) and 1,8-diazabicyclo [5.4.0]undec-7-ene (DBU)]. The highest molecular weights were achieved under near-bulk polymerization conditions using TU-protic and DBU-aprotic as catalyst-solvent combinations. Monomer E-based PHU exhibited higher Mw¯ than monomer A-based PHU (34.1 kDa and 16.4 kDa, respectively). Applying the enhanced methodology to prepare 10 multicomponent hydrogels using PVA or gelatin as the polymer scaffold revealed superior rheological properties in PVA-based hydrogels, exhibiting solid-like gel behavior. Incorporating monomer E enhanced mechanical properties and elasticity (with loss tangent values of 0.09 and 0.14). SEM images unveiled distinct microstructures, including a sponge-like pattern in certain PVA-based hydrogels when monomer A was chosen, indicating the formation of highly superporous interpenetrated materials. In summary, this innovative approach presents a versatile methodology for obtaining advanced hydrogel-based systems with potential applications in various biomedical fields.

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.

Modulation of the biocompatibility of collagen/polyelectrolyte semi-IPN hydrogels with Zn-bioMOFs.

In this study, we examined the impact of Zn-bioMOF structures on the physical and chemical characteristics as well as the in vitro biocompatibility of a matrix composed of semi-interpenetrating polymeric networks (semi-IPN) made from collagen and L-tyrosine-based polyelectrolytes. We hydrothermally synthesized L-1, ZIF-8H Zn-bioMOFs, and the Zn-(L-His)2 complex, utilizing L-histidine, a bioactive amino acid, as a ligand. These metal-organic compounds primarily enhance the mechanical properties of the novel composite hydrogels through physical interactions such as hydrogen bonds and dipolar interactions. They also accelerate the gelation process. Composites containing Zn-bioMOFs exhibited greater biocompatibility than the collagen/polyelectrolyte matrix alone, as evidenced by cytotoxicity assays conducted with porcine fibroblasts, human monocytes, and RAW 264.7 cells. Furthermore, the evaluated materials did not exhibit hemolysis. We investigated the influence of Zn-bioMOFs on cell signaling by measuring the levels of crucial cytokines involved in the healing process, such as MCP-1, TGF-β, IL-10, and TNF-α secreted by human monocytes. The composite with Zn(L-His)2 promoted the secretion of MCP-1, TGF-β, and IL-10, while a decrease in TNF-α secretion was observed with the composite containing ZIF-8H. Zn-bioMOFs enhanced certain aspects of the biomedical and physicochemical properties of the composite hydrogels. Although the overall performance of the tested materials did not differ significantly, it is worth noting that the presence of Zn-bioMOFs in biopolymeric hydrogels modulated the metabolic activity of cells important for healing and their cytokine signaling, leading to improved biomedical performance.

Development of a polyethyleneimine/poly(N-isopropylacrylamide) semi-IPN hydrogel for use in the temperature-swing adsorption and selective desorption of hydrophobic organic compounds

BackgroundA novel polyethyleneimine/poly(N-isopropylacrylamide) semi-interpenetrating polymer network (PEI/poly(NIPA) semi-IPN) hydrogel was developed as a high-performance adsorbent for use in purifying wastewater containing multiple organic compounds and recovering each organic compound. Thermosensitive poly(NIPA) with a lower critical solution temperature (LCST) of ∼33 °C in water can perform the temperature-swing adsorption, i.e., reversibly adsorb/desorb adsorbates as the temperature varies across the LCST owing to its hydrophilic/hydrophobic transition. In addition, PEI, which is a branched polymer with primary, secondary, and tertiary amine groups, can adsorb acidic adsorbates via acid-base interactions. Thus, the developed hydrogel can adsorb adsorbates via hydrophobic and/or acid-base interactions. MethodsThe PEI/poly(NIPA) semi-IPN hydrogel was prepared by free radical polymerization of NIPA and a cross-linking monomer in an aqueous solution dissolving PEI, and characterized as an adsorbent for hydrophobic organic compounds in aqueous media. FindingsThe removal (water purification) and mutual separation (recovery) of binary components (p-nitrophenol and 4-iodoaniline as model adsorbates) were demonstrated via adsorption at 50°C, followed by two-step desorption at 20°C in water and an aqueous HCl solution. This process was based on the presence or absence of hydrophobic and acid-base interactions.

Effect of Linear Polyacrylamide on the Properties of semi–IPN Hydrogels Based on N, N’–Dimethylacrylamide, and Maleic Acid

In this work, the semi–interpenetrating polymer network hydrogels based on Polyacrylamide; N, N’–Dimethylacrylamide, and Maleic acid were synthesized and investigated by changing the content of linear polyacrylamide in the obtained materials. The chemical properties, morphology, swelling behaviors in distilled water, and mechanical properties of the hydrogels were investigated. Fourier transform infrared spectra confirmed the polymerization ability of monomers, scanning electronic microscopy images showed that the pore size could be controlled by the added volume of linear polyacrylamide was in the range of 252.8 ± 5.0 ~ 888.5 ± 3.5 µm. The swelling ratio and the mechanical properties of the hydrogels increased with increasing linear polyacrylamide content. All of the results in this work showed that semi–interpenetrating polymer network hydrogels based on Polyacrylamide; N, N’–Dimethylacrylamide, and Maleic acid had a high swelling ratio, good water retention, thermal properties, and mechanical properties. Potential applications of the obtained hydrogels are in progress.

Preparation and application of the thermo-/pH−/ ion-sensitive semi-IPN hydrogel based on chitosan

Chitosan based hydrogels with multiple stimulus responses have broad application prospects in many fields. Considering the advantages of semi interpenetrating network (IPN) technology and the special temperature and ion responsiveness of polymers containing zwitterionic groups, a semi-IPN hydrogel was prepared through in situ free radical polymerization of N,N-dimethyl acrylamide and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium hydroxide with polyethylene glycol dimethacrylate as a crosslinker and carboxymethyl chitosan as filler. The gel mass fraction and swelling ratio were measured, and the preparation conditions were optimized. The result indicated that the hydrogel possessed a unique thermo-/pH−/ ion-sensitive behavior. The swelling ratio increased with the increase of temperature and ion concentration, and showed a decreasing trend with the increase in pH. In addition, the hydrogel was stable when the stimuli changed. Adsorption behavior of the hydrogel to Eosin Y (EY) was systematically investigated. The adsorption process can be described well by the pseudo-second-order kinetic model and Langmuir isotherm model, indicating that it was a chemical adsorption. The experiments indicated that the hydrogel exhibited good antifouling and reusability features. Therefore, the semi-IPN hydrogel with antifouling properties and thermo-/pH−/ion-sensitivity can be easily manufactured is expected to find applications in water treatment fields.

Solar driven thermal responsive polyionic liquid/PDDA semi-IPN hydrogel for near-room temperature membrane-free osmotic desalination

The designed thermally responsive polyionic liquid (TPIL)/ poly (diallyl dimethylammonium chloride) (PDDA) hydrogel with a semi-interpenetrating (semi-IPN) structure, containing highly charged chloride anions, was fabricated to explore the comprehensive capabilities of solar driven membrane-free osmotic desalination. Introducing linear PDDA polyelectrolyte with higher charge density has effectively excluded salt ions from entering the TPIL hydrogel matrix due to the strong charge concentration gradient established between the hydrogel and the saline reservoir. Meanwhile, the thermo-sensitivity of the polyionic liquid/PDDA semi-IPN (PNCl) hydrogel enabled the release of absorbed salt-depleted water at a temperature above the Lower Critical Solution Temperature (LCST). The multiple purification process established by partial submersion of PNCl hydrogel in saline enabled continual reduction of the salt ion concentration during the upwards transportation of water along the polyelectrolyte network. Moreover, a mushroom-shaped hydrogel demonstrated enhanced the effectiveness in long-term cyclic desalination. The “mushroom cap” was loaded with photo-thermal conversion fillers (Ti3C2Tx MXene) to achieve higher photo-thermal conversion efficiency for water recovery. A record high salt rejection rate of more than 93% was obtained for membrane-free osmotic desalination. More importantly the whole desalination/water absorption/release process was solely supported by gently heating the PNCl hydrogel under the illumination of renewable solar energy.

Asymmetric Crosslinked Polyacrylamide/Natural Rubber Semi-IPN Hydrogel for Application of Methyl Orange Dye Removal: Combined Experimental and DFT Study

Asymmetric Crosslinked Polyacrylamide/Natural Rubber Semi-IPN Hydrogel for Application of Methyl Orange Dye Removal: Combined Experimental and DFT Study