Search Results (67)

Developing functional agricultural materials that synchronize nutrient release, water retention, and soil amendment is crucial to advancing resource-efficient, sustainable farming systems. However, integrating these multifunctional properties within a single material remains a significant challenge. In this work, we fabricated a multifunctional hydrogel (CPAUH) via a one-pot synthesis strategy, which was composed of carboxylated cellulose nanofibers as a rigid network combined with poly(AA-co-KAA), forming a semi-interpenetrating network (semi-IPN) for loading urea and humic acid. The structure and properties of hydrogels were characterized by FTIR, TGA, SEM, and XPS. The CPAUH exhibited outstanding mechanical strength (0.169 MPa), water absorption capacity (121.65 g g⁻¹), and retained 118 g g⁻¹ after three absorption–desorption cycles, demonstrating remarkable structural stability. Nutrient release kinetics revealed sustained-release behavior, with cumulative elution of only 66.91% for urea and 92.45% for humic acid over 15 days. Under salt stress, the 1.5% CPAUH amendment (P2) markedly enhanced wheat growth compared with the non-amended control (P0), as reflected by significant increases in plant height, chlorophyll content, fresh weight, dry weight, and nitrogen uptake. Concurrently, CPAUH application effectively improved soil conditions by reducing electrical conductivity by 39.16% (to 4.38 mS·cm⁻¹). These collective findings of CPAUH hydrogel offer substantial potential as a multifunctional soil amendment for enhancing water-fertilizer efficiency, reclaiming saline–alkali soils, and improving crop productivity under resource-limited conditions. Full article

In this study, semi-interpenetrating polymer network (semi-IPN) hydrogels based on methacrylated dextran and native inulin were designed as biodegradable carriers for the colon-specific delivery of uracil as a model antitumor compound. The hydrogels were synthesized via free-radical polymerization, using diethylene glycol diacrylate (DEGDA) as a crosslinking agent at varying concentrations (5, 7.5, and 10 wt%), and their structural, thermal, and biological properties were systematically evaluated. Fourier transform infrared spectroscopy (FTIR) confirmed successful crosslinking and physical incorporation of uracil through hydrogen bonding. Concurrently, differential scanning calorimetry (DSC) revealed an increase in glass transition temperature (T_g) with increasing crosslinking density (149, 153, and 156 °C, respectively). Swelling studies demonstrated relaxation-controlled, first-order swelling kinetics under physiological conditions (pH 7.4, 37 °C) and high gel fraction values (84.75, 91.34, and 94.90%, respectively), indicating stable network formation. SEM analysis revealed that the hydrogel morphology strongly depended on crosslinking density and drug incorporation, with increasing crosslinker content leading to a more compact and wrinkled structure. Uracil loading further modified the microstructure, promoting the formation of discrete crystalline domains within the semi-IPN hydrogels, indicative of physical drug entrapment. All formulations exhibited high encapsulation efficiencies (>86%), which increased with increasing crosslinker content, consistent with the observed gel fraction values. Simulated in vitro gastrointestinal digestion showed negligible drug release under gastric conditions and controlled release in the intestinal phase, primarily governed by crosslinking density. Antimicrobial assessment against Escherichia coli and Staphylococcus epidermidis, used as an initial or indirect indicator of cytotoxic potential, revealed no inhibitory activity, suggesting low biological reactivity at the screening level. Overall, the results indicate that DEGDA-crosslinked dextran/inulin semi-interpenetrating (semi-IPN) hydrogels represent promising carriers for colon-targeted antitumor drug delivery. Full article

The anthrone-based dummy molecularly imprinted membrane (DIM) was successfully synthesized using a semi-interpenetrating polymer network (semi-IPN) approach for the selective recognition and adsorption of fluorene and phenanthrene in aqueous systems. Fourier-transform infrared spectroscopy (FTIR) confirmed the successful incorporation of functional groups, while scanning electron microscopy (SEM) revealed a uniform porous morphology favorable for analyte diffusion. Thermogravimetric analysis (TGA) demonstrated good thermal stability, and Brunauer–Emmett–Teller (BET) and Barrett–Joyner–Halenda (BJH) analyses indicated an enhanced surface area and mesoporous structure that supported improved adsorption performance. Adsorption isotherm studies revealed favorable adsorption behavior, with the maximum adsorption capacities of the DIM calculated to be 130.857 mg/g for fluorene and 453.030 mg/g for phenanthrene. The imprinting factors (IFs) were approximately 2.01 for fluorene and 2.17 for phenanthrene, confirming the successful imprinting effect. The recovery values achieved were 86.61% for fluorene and 92.40% for phenanthrene, demonstrating the efficiency and selectivity of the fabricated membrane. These results highlight the potential application of the anthrone-based DIM in the environmental monitoring of polycyclic aromatic hydrocarbons (PAHs). Full article

Deep coalbed methane (CBM) reservoirs are characterized by high hydrocarbon content and are considered an important strategic resource. Due to their inherently low permeability and porosity, horizontal well drilling is commonly employed to enhance production, with the length of the horizontal section playing a critical role in determining CBM output. However, during extended horizontal drilling, wellbore instability frequently occurs as a result of drilling fluid invasion into the coal formation, posing significant safety challenges. This instability is primarily caused by the physical intrusion of drilling fluids and their interactions with the coal seam, which alter the mechanical integrity of the formation. To address these challenges, interpenetrating and semi-interpenetrating network (IPN/s-IPN) hydrogels have gained attention due to their superior physicochemical properties. This material offers enhanced sealing and support performance across fracture widths ranging from micrometers to millimeters, making it especially suited for plugging applications in deep CBM reservoirs. A self-degradable interpenetrating double-network hydrogel particle plugging agent (SSG) was developed in this study, using polyacrylamide (PAM) as the primary network and an ionic polymer as the secondary network. The SSG demonstrated excellent thermal stability, remaining intact for at least 40 h in simulated formation water at 120 °C with a degradation rate as high as 90.8%, thereby minimizing potential damage to the reservoir. After thermal aging at 120 °C, the SSG maintained strong plugging performance and favorable viscoelastic properties. A drilling fluid containing 2% SSG achieved an invasion depth of only 2.85 cm in an 80–100 mesh sand bed. The linear viscoelastic region (LVR) ranged from 0.1% to 0.98%, and the elastic modulus reached 2100 Pa, indicating robust mechanical support and deformation resistance. Full article

One of the emergent regenerative treatments for the restoration of the articular cartilage is tissue engineering (TE), in which hydrogels can functionally imitate the extracellular matrix (ECM) of the native tissue and create an optimal microenvironment for the restoration of the defective tissue. Hyaluronic acid (HA) is known for its potential in the field of TE as a regenerative material for many tissues. It is one of the major components of the articular cartilage ECM contributing to cell proliferation and migration. HA is the only non-sulphated glycosaminoglycan (GAG). However, herein, we use a HA presenting a high amount of sulphated glycosaminoglycans (sGAGs), altering the intrinsic properties of the material particularly in terms of biological response. Alginate (Alg) is another polysaccharide widely used in TE that allows stiff and stable hydrogels to be obtained when crosslinked with CaCl₂. Taking the benefit of the favourable characteristics of each biomaterial, semi-interpenetrating (semi-IPN) hydrogels had been developed by the combination of both materials, in which alginate is gelled, and HA remains uncrosslinked within the hydrogel. Varying the concentration of alginate and HA, the final rheological, viscoelastic, and mechanical properties of the hydrogel can be tailored, always seeking a trade-off between biological and physico-mechanical properties. All developed semi-IPN hydrogels have great potential for biomedical applications. Full article

The need for new biomaterials to meet the needs of advanced healthcare therapies is constantly increasing. Polysaccharide-based matrices are considered extremely promising because of their biocompatibility and soft structure; however, their use is limited by their poor mechanical properties. In this light, a strategy for the reinforcement of dextran-based hydrogels and interpenetrated polymer networks (semi-IPNs and IPNs) is proposed, which will introduce multifunctional crosslinkers that can modify the network crosslinking density. Hydrogels were prepared via dextran methacrylation (DexMa), followed by UV photocrosslinking in the presence of diacrylate (NPGDA), triacrylate (TMPTA), and tetraacrylate (PETA) crosslinkers at different concentrations. The effect of these molecules was also tested on DexMa-gellan semi-IPN (DexMa/Ge) and, later, on IPN (DexMa/CaGe), obtained after solvent exchange with CaCl₂ in HEPES and the resulting Ge gelation. Mechanical properties were investigated via rheological and dynamic mechanical analyses to assess the rigidity, resistance, and strength of the systems. Our findings support the use of crosslinkers with different functionality to modulate the properties of polysaccharide-based scaffolds, making them suitable for various biomedical applications. While no significative difference is observed on enriched semi-IPN, a clear improvement is visible on DexMa and DexMa/CaGe systems when TMPTA and NPGDA crosslinker are introduced at higher concentrations, respectively. Full article

An alternative synthetic pathway was proposed for the optimization of synthesis to find a better correlation between the swelling and elasticity of hyaluronic acid-interpenetrated gels via temperature regulation. An experimental design methodology was presented for the synthesis of polyacrylamide/poly(acrylic acid sodium salt)/hyaluronic acid, PAAm/PSA/HyA, gels by modifying the one-pot procedure using free radical crosslinking copolymerization of AAm with the addition of anionic linear PSA chains in the presence of various amount of HyA, ranging between 0.05% and 0.20% (w/v). Semi-interpenetrated polymer network (IPN)-structured gels were designed with tunable elasticity, in which the extent of covalent crosslinking interactions is controlled by polymerization temperature ranging between −18 and 45 °C. Depending on the HyA content added in the synthesis and the polymerization temperature, the swelling ratio could be controlled. The addition of 0.05% (w/v) HyA increased the swelling of semi-IPNs, while the elastic modulus increased with increasing HyA content and decreased with the polymerization temperature. PAAm/PSA/HyA semi-IPNs showed the typical pH-sensitive swelling of anionic gels, and the swelling reached a maximum at a pH of 11.2. PAAm/PSA/HyA gels were tested for the removal of methyl violet from wastewater. Adsorption kinetics were shown to be well-fitted with the pseudo-second-order model using linear and nonlinear regression analysis. With the clear relationship between increased modulus and composition, this study enabled the fine-tuning of semi-IPN interactions by varying the polymerization temperature. Full article

Cellulose nanofibrils/poly(N-Isopropylacrylamide) semi-interpenetrating networks (MMCNF-PNAs) were synthesized using an in situ fabrication (semi-IPN). The polymerization of N-isopropylacrylamide (NIPAM) (free radical) was conducted in the presence of magnetic modified cellulose nanofibrils (MMCNFs). The adsorption behaviors and surface morphology of the synthesized adsorbents were investigated systematically. The adsorption behaviors of the as-prepared MMCNF-PNA towards methylene blue (MB, as the model contaminant) dye was studied, and the optimal adsorption conditions were also studied. The adsorption processes could be well fitted using pseudo-second-order and Elovich kinetic models. Meanwhile, Langmuir and Freundlich isotherm models were used to fit the adsorption which occurred at 25, 37 and 65 °C. The corresponding results showed that the Freundlich isotherm model fitted the adsorption process better, indicating that the dye’s adsorption happened via heterogeneous adsorptive energies on the prepared MMCNF-PNAs. Their desorption and reusability were also studied to verify magnetic responsivity. To sum up, MMCNF-PNAs are promising magnetic and thermal stimuli-responsive adsorbents, showing a controlled adsorption/desorption process. Full article

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. Full article

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 $\overline{M_w}$ 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. Full article

Hydrogels made of cross-linked polyacrlyamides (cPAM) and conducting materials made of polyanilines (PANIs) are both the most widely used materials in each category. This is due to their accessible monomers, easy synthesis and excellent properties. Therefore, the combination of these materials produces composites which show enhanced properties and also synergy between the cPAM properties (e.g., elasticity) and those of PANIs (e.g., conductivity). The most common way to produce the composites is to form the gel by radical polymerization (usually by redox initiators) then incorporate the PANIs into the network by oxidative polymerization of anilines. It is often claimed that the product is a semi-interpenetrated network (s-IPN) made of linear PANIs penetrating the cPAM network. However, there is evidence that the nanopores of the hydrogel become filled with PANIs nanoparticles, producing a composite. On the other hand, swelling the cPAM in true solutions of PANIs macromolecules renders s-IPN with different properties. Technological applications of the composites have been developed, such as photothermal (PTA)/electromechanical actuators, supercapacitors, movement/pressure sensors, etc. PTA devices rely on the absorption of electromagnetic radiation (light, microwaves, radiofrequency) by PANIs, which heats up the composite, triggering the phase transition of a thermosensitive cPAM. Therefore, the synergy of properties of both polymers is beneficial. Full article

New biobased hydrogels were prepared via a semi-interpenetrating polymer network (semi-IPN) using polyacrylamide/chitosan (PAAM/chitosan) hydrogel for the adsorption of As(V) or poly acrylic acid/alginate (PAA/alginate) hydrogel for the adsorption of Cu(II). Both systems were crosslinked using N,N′-methylenebisacrylamide as the crosslinker and ammonium persulfate as the initiating agent. The hydrogels were characterized by SEM, Z-potential, and FTIR. Their performance was studied under different variables, such as the biopolymer effect, adsorbent dose, pH, contact time, and concentration of metal ions. The characterization of hydrogels revealed the morphology of the material, with and without biopolymers. In both cases, the added biopolymer provided porosity and cavities’ formation, which improved the removal capacity. The Z-potential informed the surface charge of hydrogels, and the addition of biopolymers modified it, which explains the further metal removal ability. The FTIR spectra showed the functional groups of the hydrogels, confirming its chemical structure. In addition, the adsorption results showed that PAAM/chitosan can efficiently remove arsenic, reaching a capacity of 17.8 mg/g at pH 5.0, and it can also be regenerated by HNO₃ for six cycles. On the other hand, copper-ion absorption was studied on PAA/alginate, which can remove with an adsorption capacity of 63.59 mg/g at pH 4.0, and the results indicate that it can also be regenerated by HNO₃ for five cycles. Full article

Electroactive composite materials are very promising for musculoskeletal tissue engineering because they can be applied in combination with electrostimulation. In this context, novel graphene-based poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/polyvinyl alcohol (PHBV/PVA) semi-interpenetrated networks (semi-IPN) hydrogels were engineered with low amounts of graphene (G) nanosheets dispersed within the polymer matrix to endow them with electroactive properties. The nanohybrid hydrogels, obtained by applying a hybrid solvent casting–freeze-drying method, show an interconnected porous structure and a high water-absorption capacity (swelling degree > 1200%). The thermal characterization indicates that the structure presents microphase separation, with PHBV microdomains located between the PVA network. The PHBV chains located in the microdomains are able to crystallize; even more after the addition of G nanosheets, which act as a nucleating agent. Thermogravimetric analysis indicates that the degradation profile of the semi-IPN is located between those of the neat components, with an improved thermal stability at high temperatures (>450 °C) after the addition of G nanosheets. The mechanical (complex modulus) and electrical properties (surface conductivity) significantly increase in the nanohybrid hydrogels with 0.2% of G nanosheets. Nevertheless, when the amount of G nanoparticles increases fourfold (0.8%), the mechanical properties diminish and the electrical conductivity does not increase proportionally, suggesting the presence of G aggregates. The biological assessment (C2C12 murine myoblasts) indicates a good biocompatibility and proliferative behavior. These results reveal a new conductive and biocompatible semi-IPN with remarkable values of electrical conductivity and ability to induce myoblast proliferation, indicating its great potential for musculoskeletal tissue engineering. Full article

This study analyzes the physico-chemical properties of interpenetrated polymer networks (IPNs) and semi-IPN resulting from cross-linking chitosan with glutaraldehyde and alginate with Ca²⁺ cations, as a function of the order in which the cross-linking agents are added to the polymer mixture. Three physico-chemical methods were used to assess the differences between systems: rheology, IR spectroscopy, and electron paramagnetic resonance (EPR) spectroscopy. While rheology and IR spectroscopy are commonly used to characterize gel materials, EPR spectroscopy is rarely used, but has the advantage of providing local information about the dynamics of a system. The rheological parameters, which describe the global behavior of the samples, show that semi-IPN systems have a weaker gel behavior and the order of introducing the cross-linker in the polymer systems plays a role. The IR spectra of samples resulting by adding only Ca²⁺ or Ca²⁺ as the first cross-linker are similar to that of the alginate gel, while the spectra of samples in which glutaraldehyde is firstly added resemble the chitosan gel spectrum. Using spin-labeled alginate and spin-labeled chitosan, we monitored the changes occurring in the dynamic of the spin labels due to the formation of IPN and semi-IPN. The results show that the order of adding the cross-linking agents influences the dynamic of the IPN network, and that the formation of the alginate network determines the characteristics of the entire IPN system. The EPR data were correlated with the rheological parameters and IR spectra of the analyzed samples. Full article

In this research, the porous polymer structures (IPN) were made from natural isoprene rubber (NR) and poly(methyl methacrylate) (PMMA). The effects of molecular weight and crosslink density of polyisoprene on the morphology and miscibility with PMMA were determined. Sequential semi-IPNs were prepared. Viscoelastic, thermal and mechanical properties of semi-IPN were studied. The results showed that the key factor influencing the miscibility in semi-IPN was the crosslinking density of the natural rubber. The degree of compatibility was increased by doubling the crosslinking level. The degree of miscibility at two different compositions was compared by simulations of the electron spin resonance spectra. Compatibility of semi-IPNs was found to be more efficient when the PMMA content was less than 40 wt.%. A nanometer-sized morphology was obtained for a NR/PMMA ratio of 50/50. Highly crosslinked elastic semi-IPN followed the storage modulus of PMMA after the glass transition as a result of certain degree of phase mixing and interlocked structure. It was shown that the morphology of the porous polymer network could be easily controlled by the proper choice of concentration and composition of crosslinking agent. A dual phase morphology resulted from the higher concentration and the lower crosslinking level. This was used for developing porous structures from the elastic semi-IPN. The mechanical performance was correlated with morphology, and the thermal stability was comparable with respect to pure NR. Investigated materials might be interesting for use as potential carriers of bioactive molecules aimed for innovative applications such as in food packaging. Full article