Interpenetrating Polymer Networks Research Articles

Formulation and Evaluation of Novel Interpenetrating Polymer Network Microspheres for Controlled Release of Zaleplon

Formulation and Evaluation of Novel Interpenetrating Polymer Network Microspheres for Controlled Release of Zaleplon

3D printed thermo-responsive electroconductive hydrogel and its application for motion sensor

Stimulus-responsive hydrogels with excellent conductivity have been widely used in electrical, electrochemical, biomedical, and other fields. It is still a challenge to prepare gels with high conductivity. In this paper, poly (N-isopropyl acrylamide) is 3D printed by changing the rheological properties of the printing solution with clay. By forming phytic acid cross-linked polyaniline conductive polymer network in situ on the poly (N-isopropyl acrylamide) matrix, 3D printing of thermally responsive conductive hybrid hydrogels was realized. The interpenetrating polymer network structure provides an electron transport path for hydrogels. The hydrogels have high porosity, strong interaction, high electrical conductivity, high thermal response sensitivity, and significant mechanical enhancement. The results show that the swelling and mechanical properties of the gel are influenced by soaking in different concentrations. The application scenario of the hydrogel was confirmed by a temperature-sensitive switch and finger motion detection.

Photoinitiation Mechanisms of Novel Phenothiazine‐Based Oxime and Oxime Esters Acting as Visible Light Sensitive Type I and Multicomponent Photoinitiators

AbstractIn this work, three new photoinitiators, based on the phenothiazine scaffold as a chromophore and potentially bearing the oxime ester functionality as an initiating group are designed and synthesized for the free radical polymerization of acrylates, the cationic polymerization of epoxides, and the formation of interpenetrated polymer networks upon irradiation with a light emitting diode emitting at 405 nm. These phenothiazine‐based oxime and oxime esters revealed impressive photoinitiation ability manifested by excellent polymerization rates and high final reactive function conversions. Significantly, they can be used as both; one‐component (Type I) and two‐component photoinitiating systems. Photoinitiation mechanisms through which reactive species are produced are investigated by means of different complementary techniques including real‐time Fourier transform infrared spectroscopy, UV–visible absorption spectroscopy, electron spin resonance spectroscopy, fluorescence (steady state and time resolved), cyclic voltammetry, and molecular modeling calculations. Thermal initiation behavior of the different oxime esters is also studied by using differential scanning calorimetry, highlighting their dual thermal/photochemical initiation ability. Finally, 3D printed objects are successfully fabricated by conducting both direct laser writing and 3D printing experiments.

Nanocellulose, The Origin of Natural Reinforcement in Advanced Biocomposites


 The study on nanocellulose was early reported in 1956 by Battista et al., for the term of level-off degree of polymerization of cellulose which nowadays the crystal is maintained with high aspect ratio (length/diameter) as named as cellulose nanocrystal and further, in 1983 by Turbak et al., for the term of microfibrillated cellulose which has gel-like structure and thixotropic viscosity properties, afterwards, the extraction study of nanocellulose has gaining sky rocketly in the number of publications, yet it is not commercially available in the market readily in the general bioproducts. Cellulose is the most abundant and ubiquitous linier biopolymer on earth and is found in the cell walls of plants as the origin, where it provides structural support for plants consist of glucose monomer with 1-4-β glycosidic linkage. While nanocellulose is a type of cellulose material that has been broken down into nanoscale dimensions which contain aggregation of cellulose biopolymer due to inter- and intra-molecular hydrogen bonding within cellulose. Those nanoscales provide zero-defect, nir-dislocation, which caused high modulus strength and high tensile strength material, up to 150 GPa and 2 GPa, respectively. The remarkable properties of cellulose provide the wood as a strong, tough and smart living organism. Therefore, with nanotechnology, many scholars have seeking knowledge to mimic the biocomposite of wood to make lightweight, strong, tough, and functionalized advanced materials. The behavior of nanocellulose as reinforcing agents has been elaborated for their high surface area, surface charge for better dispersion, surface functionality, dimension and morphology, thermal expansion, crystallinity, and amphiphilicity. Beside nanocellulose properties, the key-technology to develop advanced bio-nanocomposite is the ability to handle the interface and interphase between reinforcing agent and its matrix and the choice of matrices is also important. The hierarchical structure of cellulose in wood could be the inspiration to modify the interaction of nanocellulose within composite such as hybrid, tertiary bio nanocomposite, honey-comb designed composite, or interpenetrated polymer networks composite.

CNCs extraction from single‐use cups: effects of grafting it onto MMA monomer

AbstractBACKGROUNDThe difficulty of separating fiber from polyolefin coatings of single‐use plastic (SUP) cups for cold (carbonated) or hot (coffee) drinks, has led us to investigate a recycling method to obtain new high‐performance materials. The present work relates to valorization of ICEE S.A. de C.V. cups into crystalline nanocellulose (CNC), while studying the effects on the structural, thermal, morphological and particle size properties in dependence of the acid hydrolysis concentration (40 and 64% v/v) employing sulfuric acid to remove amorphous cellulose.RESULTSOn the basis of results, optimal CNC was found at 64% v/v concentration obtaining ribbon‐like morphologies rich in cellulose types Iα (27%) and II (45.1%) of triclinic and monoclinic structures, respectively, high crystallinity percentage (91%) and nanosize scale (26.70 nm). CNC was successfully grafted through the C2 in cellulose onto the methyl methacrylate (MMA) monomer to obtain PMMA‐g‐CNC, considering different concentrations (5, 10, 20 and 30 wt%) of CNC. A reduction of crystallinity % was found when CNC is grafted onto MMA owing to the amorphous nature of the poly(methyl methacrylate) (PMMA). However, this is not a limitation.CONCLUSIONSPMMA‐g‐CNC samples displayed high thermal stability (345 °C) and nanometric scale (165–260 nm), which have potential to be studied as reinforcement agents for incompatible polymers such as PMMA and poly(urethane) (PU) through Interpenetrating Polymer Networks. Preliminary mechanical studies indicated that PMMA‐g‐CNC systems are able to reinforce the tensile properties becoming the PMMA/PU into ductile materials. Specially, the MMA90CNC10 system improved the strain four‐fold compared to the pure PMMA/PU IPN. © 2023 Society of Chemical Industry (SCI).

Double Cross‐Linked Biomimetic Hyaluronic Acid‐Based Hydrogels with Thermo‐Stimulated Self‐Contraction and Tissue Adhesiveness for Accelerating Post‐Wound Closure and Wound Healing

AbstractWhen skin trauma occurs, rapid achievement of the post‐wound closure is required to prevent microbial invasion, inhibit scar formation and promote wound healing. To develop a wound dressing for accelerating post‐wound‐closure and wound healing, a thermo‐responsive and tissue‐adhesive hydrogel with interpenetrating polymer networks (IPN) is fabricated based on N‐dimethylbisacrylamide (NIPAM) and glutaraldehyde (GTA) cross‐linked hyaluronic acid (HA). Results not only confirm the thermo‐stimulated self‐contraction and tissue adhesiveness of the HA‐based IPN (PNI‐HA), which effectively aids wound closure via mechanical stretch, but also verify the hemocompatibility and cytocompatibility of PNI‐HA that tend to accelerate wound healing. In vivo, a mouse model of total skin defect demonstrates that PNI‐HA acting as hydrogel sealant significantly achieves the sutureless post‐wound‐closure at the early stage of wound healing, and then promotes wound healing by reducing inflammatory cells infiltration, promoting angiogenesis as well as reducing collagen deposition. These results indicate that the developed thermo‐responsive and tissue‐adhesive hydrogel dressing offers a candidate to serve as a tissue sealant for wound healing.

Mussel‐inspired double cross‐linked interpenetrating network with unique mechanical properties using di‐diol complexation

AbstractPolymer nanocomposites with exceptionally high mechanical properties owing to strong interfacial attraction have garnered tremendous interest in the research community. In general, tough and robust polymer nanocomposites are usually obtained via dispersing a nano‐flaky filler in the polymer matrix, although the strategy is only sometimes practically viable. To this end, in this work, a facile strategy has been adopted to achieve a strong and tough polymer nanocomposite. A novel mussel‐inspired full interpenetrating polymeric network (IPN) consisting of polyvinylalcohol and polydopamine was prepared. This technique helped integrate the advantages of dopamine chemistry with forming a full IPN using Borax as a common crosslinker. The infusion of 1 wt% acid‐modified carbon nanotubes (ACNT) in the IPN matrix helped greatly improve the current state‐of‐the‐art. The synergistic effect of nano‐reinforcement and formation of ester linkage through a substantial amount of di‐diol complexation dominated and accounted for the significant enhancement of mechanical properties. This is further supported by decreased intensity of free OH groups in the FTIR investigations, viscosity enhancement from rheological behavior, and temperature‐dependent dynamic mechanical property analysis. Such an IPN structure is a promising way to enhance mechanical properties.

Exosomal Lnc NEAT1 from endothelial cells promote bone regeneration by regulating macrophage polarization via DDX3X/NLRP3 axis

BackgroundBone regeneration is a complex procedure that involves an interaction between osteogenesis and inflammation. Macrophages in the microenvironment are instrumental in bone metabolism. Amount evidence have revealed that exosomes transmitting lncRNA is crucial nanocarriers for cellular interactions in various biotic procedures, especially, osteogenesis. However, the underlying mechanisms of the regulatory relationship between the exosomes and macrophages are awaiting clarification. In the present time study, we aimed to explore the roles of human umbilical vein endothelial cells (HUVECs)-derived exosomes carrying nuclear enrichment enriched transcript 1 (NEAT1) in the osteogenesis mediated by M2 polarized macrophages and elucidate the underlying mechanisms.ResultsWe demonstrated HUVECs-derived exosomes expressing NEAT1 significantly enhanced M2 polarization and attenuated LPS-induced inflammation in vitro. Besides, the conditioned medium from macrophages induced by the exosomes indirectly facilitated the migration and osteogenic differentiation of bone marrow-derived mesenchymal stem cells (BMSCs). Mechanically, Exos carrying NEAT1 decreased remarkably both expression of dead-box helicase 3X-linked (DDX3X) and nod-like receptor protein 3 (NLRP3). The level of NLRP3 protein increased significantly after RAW264.7 cells transfected with DDX3X overexpression plasmid. Additionally, the knockdown of NEAT1 in exosomes partially counteracted the aforementioned effect of Exos. The results of air pouch rat model demonstrated that HUVECs-derived exosomes increased anti-inflammatory cytokines (IL-10) and decreased pro-inflammatory cytokines (IL-1β and IL-6) significantly in vivo, contributing to amelioration of LPS-induced inflammation. Afterwards, we further confirmed that the HUVECs-derived exosomes encapsulated in alginate/gelatin methacrylate (GelMA) interpenetrating polymer network (IPN) hydrogels could promote the bone regeneration, facilitate the angiogenesis, increase the infiltration of M2 polarized macrophages as well as decrease NLRP3 expression in the rat calvarial defect model.ConclusionsHUVECs-derived exosomes enable transmitting NEAT1 to alleviate inflammation by inducing M2 polarization of macrophages through DDX3X/NLRP3 regulatory axis, which finally contributes to osteogenesis with the aid of alginate/GelMA IPN hydrogels in vivo. Thus, our study provides insights in bone healing with the aid of HUVECs-derived exosomes-encapsulated composite hydrogels, which exhibited potential towards the use of bone tissue engineering in the foreseeable future.

Formation of Alginate/Chitosan Interpenetrated Networks Revealed by EPR Spectroscopy.

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.

Preparation and Application of Double Network Interpenetrating Colon Targeting Hydrogel Based on Konjac Glucomannan and N-Isopropylacrylamide.

Konjac glucomannan (KGM) can be degraded by colon-specific enzymes in the colonic environment, making it one of the materials for treating colonic diseases, which has attracted more and more attention. However, during drug administration, especially in the gastric environment and due to its easy swelling, the structure of KGM is usually destroyed and the drug is released, thereby reducing the bioavailability of the drug. To solve this problem, the easy swelling and drug release properties of KGM hydrogels are avoided by creating interpenetrating polymer network hydrogels. In this study, N-isopropylacrylamide (NIPAM) is first formed into a hydrogel framework under the action of a cross-linking agent to stabilize the gel shape before the gel is heated under alkaline conditions to make KGM molecules wrap around the NIPAM framework. The structure of the IPN(KGM/NIPAM) gel was confirmed using Fourier transform infrared spectroscopy (FT-IR) and x-ray diffractometer (XRD). In the stomach and small intestine, it was found that the release rate and swelling rate of the gel were 30% and 100%, which were lower than 60% and 180% of KGM gel. The experimental results showed that this double network hydrogel has a good colon-directed release profile and fine drug carrier ability. This provides a new idea for the development of konjac glucomannan colon-targeting hydrogel.

Preparation and Performance Evaluation of a Plugging Agent with an Interpenetrating Polymer Network.

In view of the problems of polymer cross-linked elastic particle plugging agents commonly used in oilfields, including easy shear, poor temperature resistance, and weak plugging strength for large pores, the introduction of particles with certain rigidity and network structure, and cross-linking with a polymer monomer can improve the structural stability, temperature resistance, and plugging effect, and the preparation method is simple and low-cost. An interpenetrating polymer network (IPN) gel was prepared in a stepwise manner. The conditions of IPN synthesis were optimized. The IPN gel micromorphology was analyzed by SEM and the viscoelasticity, temperature resistance, and plugging performance were also evaluated. The optimal polymerization conditions included a temperature of 60 °C, a monomer concentration of 10.0-15.0%, a cross-linker concentration of 1.0-2.0% of monomer content, and a first network concentration of 20%. The IPN showed good fusion degree with no phase separation, which was the prerequisite for the formation of high-strength IPN, whereas particle aggregates reduced the strength. The IPN had better cross-linking strength and structural stability, with a 20-70% increase in the elastic modulus and a 25% increase in temperature resistance. It showed better plugging ability and erosion resistance, with the plugging rate reaching 98.9%. The stability of the plugging pressure after erosion was 3.8 times that of a conventional PAM-gel plugging agent. The IPN plugging agent improved the structural stability, temperature resistance, and plugging effect of the plugging agent. This paper provides a new method for improving the performance of a plugging agent in an oilfield.

Photoinitiator or photosensitizer? Dual behaviour of m-terphenyls in photopolymerization processes

A series of eight m-terphenyl-based compounds functionalized with amino, diethylamino, piperidine, and pyrrolidine moieties were synthesized and investigated for the first time as one-component free-radical photoinitiators for acrylate and methacrylate monomers. Developed compounds were also applied as photosensitizers of iodonium salt in two-component initiating systems for free radical and cationic photopolymerization. That is why they are excellent for hybrid polymerization e.g. synthesis of interpenetrating polymer networks (IPN). The mechanical properties of produced IPN samples were measured. We investigated the effect of the amine group modification and the presence of one or two bromine atoms on the photophysical and electrochemical properties of the m-terphenyls and their consequent efficiency in polymerization processes. Two bromine substituents in the molecule slightly shift the absorption spectrum towards longer wavelengths in comparison to a compound with one bromine atom. Functionalization of amine group by the introduction of alkyl moieties strongly affects absorption properties, the wavelength corresponding with the maximum absorption values increases in the following order: amine group > diethylamine group > piperidine group > pyrrolidine group. Investigated compounds were found to be efficient in photoinitiating systems for free-radical, cationic, and hybrid photopolymerization, kinetic of polymerization processes with the use of different monomers were followed using real-time FT IR methodology. Moreover, the chemical mechanism was investigated using photolysis and ESR experiments. Developed photoinitiators were also applied for laser writing experiments. In the next step, the key printing parameters were settled, the critical energy necessary to initiate polymerization (Ec) and penetration depth of curing light (Dp), and studied systems were applied for resin used for LCD-based 3d printing.

Removal of Fermentation Inhibitors from Sugarcane Bagasse Hydrolysate via Post-cross-linked Hydrophilic-Hydrophobic Interpenetrating Polymer Networks.

The efficient and economical removal of fermentation inhibitors from the complex system of biomass hydrolysate was one of the basics and keys in bio-chemical transformation. In this work, post-cross-linked hydrophilic-hydrophobic interpenetrating polymer networks (PMA/PS_pc IPNs and PAM/PS_pc IPNs) were proposed to remove fermentation inhibitors from sugarcane bagasse hydrolysate for the first time. PMA/PS_pc and PAM/PS_pc IPNs can obviously enhance the adsorption performance towards fermentation inhibitors due to their higher surface area and hydrophilic-hydrophobic synergetic surface properties, especially PMA/PS_pc IPNs has higher selectivity coefficients of 4.57, 4.63, 4.85, 16.0, 49.43, and 22.69, and higher adsorption capacity of 24.7 mg/g, 39.2 mg/g, 52.4 mg/g, 9.1 mg/g, 13.2 mg/g, and 144.9 mg/g towards formic acid, acetic acid, levulinic acid (LA), 5-hydroxymethylfurfural (HMF), furfural, and acid-soluble lignin (ASL), respectively, in a lower total sugar loss of 2.03%. The adsorption kinetics and isotherm of PMA/PS_pc IPNs were studied to elucidate its adsorption behavior towards fermentation inhibitors. In addition, the cyclic utilization property of PMA/PS_pc IPNs was stable. Synthesizing PMA/PS_pc IPNs is a new strategy to provide an efficient adsorbent for the removal of fermentation inhibitors from lignocellulosic hydrolysate.

Development of Carbon Nanotube/Graphene- Based Alginate Interpenetrating Hydrogels for Removal of Antibiotic Pollutants.

The extensive use of pharmaceutical antibiotics in treatment of human and animal infections has resulted in growing concerns about antibiotic pollution worldwide. In this work a novel interpenetrating polymer network (IPN) hydrogel has been developed to function as an effective and non-selective adsorbent for various antibiotic pollutants in aqueous solution. This IPN hydrogel is made of multiple active components, including carbon nanotube (CNTs), graphene oxide (GO), and urea-modified sodium alginate (SA). It can be readily prepared through efficient carbodiimide-mediated amide coupling reaction followed by calcium chloride-induced alginate cross-linking. The structural properties, swellability, and thermal stability of this hydrogel have been investigated, while its adsorption properties towards an important antibiotic pollutant, tetracycline, was thoroughly characterized based on adsorption kinetic and isotherm analyses. With a BET surface area of 38.7 m2/g, the IPN hydrogel shows an excellent adsorption capacity of 84.28 ± 4.2 mg/g towards tetracycline in water, while the adsorption capacity is decreased by only 18% after four cycles of use, demonstrating very good reusability. Adsorptive performance in removing two other antibiotics, neomycin and erythromycin, has also been examined and compared. Overall, our studies disclose that this newly designed hybrid hydrogel is an effective and reusable adsorbent material for treating antibiotic pollution in the environment.

Facile Li+ Transport in Interpenetrating O‐ and F‐Containing Polymer Networks for Solid‐State Lithium Batteries (Adv. Funct. Mater. 12/2023)

Interpenetrating Polymer Network Electrolyte In article number 2213469, Hsisheng Teng and co-workers demonstrate a robust solid-state lithium battery with synergy between O-based and F-based polymer networks, which overpowers liquid electrolyte batteries in terms of safety and performance. This synergistic relationship, combined with the creation of an anion-aggregate domain, expedites Li+ transport in the battery.

Electrostatically Complexed Natural Polysaccharides as Aqueous Barrier Coatings for Sustainable and Recyclable Fiber-Based Packaging.

Driven by the ever-growing awareness of sustainability and circular economy, renewable, biodegradable, and recyclable fiber-based packaging materials are emerging as alternatives to fossil-derived, nonbiodegradable single-use plastics for the packaging industry. However, without functional barrier coatings, the water/moisture vulnerability and high permeability of fiber-based packaging significantly restrain its broader application as primary packaging for food, beverages, and drugs. Herein, we develop waterborne complex dispersion barrier coatings consisting of natural, biodegradable polysaccharides (i.e., chitosan and carboxymethyl cellulose) through a scalable, one-pot mechanochemical pathway. By tailoring the electrostatic complexation, the key element to form a highly crosslinked and interpenetrated polymer network structure, we formulate complex dispersion barrier coatings with excellent film-forming property and adaptable solid-viscosity profiles suitable for paperboard and molded pulp substrates. Our complex dispersions enable the formation of a uniform, defect-free, and integrated coating layer, leading to a remarkable oil and grease barrier and efficient water/moisture sensitivity reduction while still exhibiting excellent recyclability profile of the resulting fiber-based substrates. This natural, biorenewable, and repulpable barrier coating is a promising candidate to serve as a sustainable option for fiber-based packaging intended for the food and food service packaging industry.

A study on physical and morphological properties of novel bio-cotton/E-glass fiber–reinforced vinyl ester/epoxy resin hybrid interpenetrating polymer networks composites

A study on physical and morphological properties of novel bio-cotton/E-glass fiber–reinforced vinyl ester/epoxy resin hybrid interpenetrating polymer networks composites

Miscibility, Hierarchical Structures, and Enhanced Mechanical Properties of Acrylic Rubber by the Formation of a Chemically and Physically Crosslinked Partially Miscible Interpenetrating Polymer Network with Poly(vinylidene fluoride)

Miscibility, Hierarchical Structures, and Enhanced Mechanical Properties of Acrylic Rubber by the Formation of a Chemically and Physically Crosslinked Partially Miscible Interpenetrating Polymer Network with Poly(vinylidene fluoride)

A thermal management strategy for electronic devices based on copper double skin inspired hydrogel

A passive cooling material was proposed by combining the advantages of an interpenetrating polymer network and copper powder. The experimental thermal conductivity of copper based composite hydrogel was enhanced to 0.71 W/(m·K). At the same time, MD simulations showed a thermal conductivity of approximately 0.84 W/(m·K), which primarily caused by the increased overlap between hydrogel components. Due to the improvement of the thermal conductivity, the heat flux of copper based composite hydrogel increased to 977 W/m2 at a constant heat source temperature of 65 °C and the total heat dissipation increased by 104.4%. The thermal management tests showed copper based composite hydrogel could reach 35 °C, while the copper based composite hydrogel could reach 50 °C. The obtained copper based PNIPAM/Alginate-Ca2+ hydrogel exhibited a synergistic property enhancement of high thermal conductivity, stability in shape and decreased aggregation of the copper nanoparticles, which should provide a new strategy for thermal management.

Interpenetrating Polymer Networks of Polyacrylamide with Polyacrylic and Polymethacrylic Acids and Their Application for Modified Drug Delivery - a Flash Review.

Polyacrylic and polymethacrylic acids, in combination with polymers such as polyacrylamide, provide the ability for controlled and sustained drug delivery since they represent pHand temperature responsiveness. In addition, the synthesis techniques can be used to develop a higher level of supramolecular structures as the interpenetrating polymer networks - as bulk hydrogels or micro-/nanogels. They can provide the opportunity to organize and build up state-ofthe- art carriers for different types of drugs, thus providing the ability to control their loading capacity and drug release performance. This flash review aims to summarize the efforts for synthesizing such interpenetrating polymer networks and their properties and to demonstrate the authors' contributions to this field.