Three-dimensional Polymeric Network Research Articles

Understanding the role of host-guest interactions in enhancing oil recovery through β‑cyclodextrin and adamantane modified copolymer

Adamantane (ADA) and β-Cyclodextrin (β-CD) modified hydrolyzed polyacrylamide (MHPAM) polymers have been confirmed to have excellent performance in enhanced oil recovery (EOR). However, the molecular mechanism of the formation of three-dimensional polymer network structure has been not yet fully understood. In this work, the cross-linked mode of MHPAM polymers and their interaction information was investigated by molecular dynamics (MD) simulations and quantum chemical (QC) calculations. Results suggest that the ADA and β-CD molecules play a pivotal molecular recognition and binding role (like hormones and receptors, antigens and antibodies) in the process of host-guest interaction. The proposed mechanism of MHPAM cross-linking in the experiments was supplemented by our MD simulations. In addition, the strong electrostatic and van der Walls (vdW) component can be explained by the overlap of positive and negative ESP/vdW side. The viscosity of hydrolyzed polyacrylamide (HPAM) was increased via the modification of ADA and β-CD, which can be attributed to the hydrophobic associations of MHPAM. Based on our results, it will allow a more informed selection of these as polymers for use in enhanced oil recovery, enabling the properties of these polymers to be tailored to a particular application.

A pH-Sensitive, Stretchable, Antibacterial Artificial Tongue Based on MXene Cross-Linked Ionogel.

Dehydration has always been a confusing problem for a hydrogel exposed to air, which restricts its application in practical detection. While an ionogel with unique properties can lock water molecules efficiently due to its low vapor pressure, the design and development of an ionogel with excellent water-locking properties and stability to achieve satisfactory detection are thus highly desirable. In this work, a pH-sensitive, stretchable, antibacterial, and stable ionogel artificial tongue was fabricated through dual cross-linking. The artificial tongue consisted of MXene as a cross-linking agent, phenol red as an indicator, gelatin, N-(2-hydroxyethyl) acrylamide, and 1-butyl-3-methylimidazolium chloride as the three-dimensional polymer network. A small quantity of MXene was used as a cross-linker the first time to promote the initiator in the system to generate free radicals, accelerating the reaction process and the multilevel linkage among the polymers. Meanwhile, the indicator phenol red was introduced into the ionogel successfully for the first time, showing great stability in 5 weeks. After evaluation by the Brand-Altman analysis, it was found that the method of pH measurement using ionogels had good consistency with the pH meter measurement method. Additionally, the prepared ionogel presented excellent water retention, mechanical stretchability, antibacterial property, and stability, as well as good test results in the test of artificial simulated saliva, demonstrating great potential in clinical applications.

Ultrasonic-Induced Synthesis of Underwater Adhesive and Antiswelling Hydrogel for Strain Sensor.

To perceive the human body's multienvironmental mobility, intelligent flexible electronic equipment with an underwater motion monitoring function has potential research value in the field of intelligent detection. Hydrogels are widely used in the field of flexible electronics for their unique three-dimensional polymer networks. Due to the instinctive hydrophilicity of hydrogels, the swelling of hydrogels underwater and the formation of hydration coating on the surface become the primary obstacles to underwater applications. Herein, a hydrogel sensor that can achieve underwater utilization was prepared through copolymerization between hydrophobic and hydrophilic polymer monomers. The synergistic impact of electrostatic interaction, metal coordination, and hydrogen bonding ensured the hydrogel's remarkable underwater adhesive ability to a variety of substrates. The hydrophobic micelles and self-hydrophobization process induced from ultrasonic dispersion in the polymer matrix gave an outstanding hydrophobic performance (water contact angle of 130.4°) and antiswelling property (swelling ratio of 26% after 72 h of immersion), presenting unprecedented underwater adaptability. The above-mentioned hydrogel could be assembled into a flexible hydrogel sensor with satisfactory sensitivity (gauge factor of 0.44), ultrafast response rate (106 ms), and excellent cyclic stability, demonstrating accurate monitoring of complex human motions in water and air.

Construction and evaluation of a graphite oxide Nanoparticle-Reinforced polymer flooding system for enhanced oil recovery

Insufficient mobility control capability and limited swept volume are the primary challenges faced by polymer flooding technology. In this work, a graphite oxide nanoparticle-reinforced polymer (GORP) flooding system was constructed. Compared with the conventional polymer (CP) flooding system, the GORP flooding system with 0.15% graphite oxide nanoparticles has a better viscosity increasing effect, shearing resistance and aging stability. In terms of mobility control capability, due to the reinforcing effect of graphite oxide nanoparticles on the three-dimensional polymer network structure, the GORP flooding system has a higher resistance factor and residual resistance factor than the CP flooding system in different permeability cores. In addition, the NMR online displacement experiment results further prove that the enhanced oil recovery performance of the GORP flooding system is more prominent, with a total recovery of 72.87%, which is 5.04% higher than that of the CP flooding system. The GORP flooding system may have the potential to become a long-term effective technology to control the water cut of oil wells.

Preparation of CTS/PAMAM/SA/Ca2+ hydrogel and its adsorption performance for heavy metal ions

As a new functional polymer material with three-dimensional polymer network structure, hydrogel is widely used in the removel of heavy metal ions pollutants in sewage. In this work, semi-dissolution acidification sol–gel transition method was used to prepare the hydrogel with chitosan/sodium alginate/calcium ion (CTS/SA/Ca2+) physical cross-linked double network structure without adding chemical cross-linking agent. Meanwhile, hyperbranched polyamide-amine with different generations which was rich in amino groups were introduced to improve the adsorption capacity of hydrogel, and the CTS/PAMAM/SA/Ca2+ hydrogel adsorbent with no secondary pollution, environmental protection and high adsorption capacity was obtained. Experimental results show that the hydrogel with third-generation hyperbranched polyamide-amine have the best comprehensive performance. Its maximum adsorption capacities for copper ions and cadmium ions could reach 174.82 mg/g and 157.72 mg/g respectively. Furthermore, it was found that the adsorption behaviors of copper ions and cadmium ions on the hydrogel conformed to the pseudo-second-order kinetic model and Langmuir adsorption isotherm model by studying the factors affecting the adsorption process. The CTS/PAMAM/SA/Ca2+ hydrogel has the advantages of high heavy metal ion adsorption capacity, uniform structure, and recyclability. As a functional material with simple preparation and excellent performance, it has good application potential and research value.

Hydrogels as promising carriers for the delivery of food bioactive ingredients.

The burden of public health challenges associated with the western dietary and living style is growing. Nutraceuticals have been paid increasing attentions due to their effects in promotion of health. However, in the gastrointestinal (GI) tract, the nutraceuticals suffer from not only the harsh acidic environment of the stomach and a variety of digestive enzymes, but also the antibacterial activity of intestinal bile salts and the action of protease from the gut microbiota. The amount of the nutraceuticals arriving at the sites in GI tract for absorption or exerting the bioactivities is always unfortunately limited, which puts forward high requirements for protection of nutraceuticals in a certain high contents during oral consumption. Hydrogels are three-dimensional polymeric porous networks formed by the cross-linking of polymer chains, which can hold huge amounts of water. Compared with other carries with the size in microscopic scale such as nanoparticle and microcapsules, hydrogels could be considered to be more suitable delivery systems in food due to their macroscopic bulk properties, adjustable viscoelasticity and large spatial structure for embedding nutraceuticals. Regarding to the applications in food, natural polymer-based hydrogels are commonly safe and popular due to their source with the appealing characteristics of affordability, biodegradability and biocompatibility. Although chemical crosslinking has been widely utilized in preparation of hydrogels, it prefers the physical crosslinking in the researches in food. The reasonable design for the structure of natural polymeric hydrogels is essential for seeking the favorable functionalities to apply in the delivery system, and it could be possible to obtain the enhanced adhesive property, acid stability, resistant to bile salt, and the controlled release behavior. The hydrogels prepared with proteins, polysaccharides or the mix of them to deliver the functional ingredients, mainly the phenolic components, vitamins, probiotics are discussed to obtain inspiration for the wide applications in delivery systems. Further efforts might be made in the in situ formation of hydrogels in GI tract through the interaction among food polymers and small-molecular ingredients, elevation of the loading contents of nutraceuticals in hydrogels, development of stomach adhesive hydrogels as well as targeting modification of gut microbiota by the hydrogels.

Construction and Ion Transport-Related Applications of the Hydrogel-Based Membrane with 3D Nanochannels.

Hydrogel is a type of crosslinked three-dimensional polymer network structure gel. It can swell and hold a large amount of water but does not dissolve. It is an excellent membrane material for ion transportation. As transport channels, the chemical structure of hydrogel can be regulated by molecular design, and its three-dimensional structure can be controlled according to the degree of crosslinking. In this review, our prime focus has been on ion transport-related applications based on hydrogel materials. We have briefly elaborated the origin and source of hydrogel materials and summarized the crosslinking mechanisms involved in matrix network construction and the different spatial network structures. Hydrogel structure and the remarkable performance features such as microporosity, ion carrying capability, water holding capacity, and responsiveness to stimuli such as pH, light, temperature, electricity, and magnetic field are discussed. Moreover, emphasis has been made on the application of hydrogels in water purification, energy storage, sensing, and salinity gradient energy conversion. Finally, the prospects and challenges related to hydrogel fabrication and applications are summarized.

Nanoparticle–Hydrogel Based Sensors: Synthesis and Applications

Hydrogels are hydrophilic three-dimensional (3D) porous polymer networks that can easily stabilize various nanoparticles. Loading noble metal nanoparticles into a 3D network of hydrogels can enhance the synergy of the components. It can also be modified to prepare intelligent materials that can recognize external stimuli. The combination of noble metal nanoparticles and hydrogels to produce modified or new composite materials has attracted considerable attention as to the use of these materials in sensors. However, there is limited review literature on nanoparticle–hydrogel-based sensors. This paper presents the detailed strategies of synthesis and design of the composites, and the latest applications of nanoparticle–hydrogel materials in the sensing field. Finally, the current challenges and future development directions of nanoparticle–hydrogel-based sensors are proposed.

Structural diversity and luminescence properties of M(II) complexes based on 4-carboxyphenoxybutanoic acid and N-containing ligands

4-Carboxyphenoxybutanoic acid (H2cpob) and its monosodium salt (NaHcpob) are synthesized and characterized. The crystal structure of NaHcpob shows that the sodium atoms are connected by the carboxyl group of Hcpob−, forming a three-dimensional coordination polymer network. NaHcpob reacts with metal salts and N-containing ligands produced following complexes: [Co(cpob)(H2O)2]n1, [Zn(cpob)(phen)(H2O)]22, [Cd(cpob)(phen)]n3, [Mn(cpob)(phen)·4H2O]n4, and [Cd2(cpob)2(bimb)]n5 (phen ​= ​1,10-phenanthroline, bimb ​= ​1,4-bis(imidazole-1-ylmethyl)benzene). Single-crystal X-ray diffraction analysis showed that these complexes have different metal-organic frameworks, ranging from binuclear (2) to one-dimensional (3 and 4), two-dimensional (1), and three-dimensional (5) arrangements. When only H2cpob forms a complex with metal ions, the ligand connects the metal ions into a higher-dimensional structure. In contrast, the terminal ligand (phen) added as an auxiliary ligand forms a low-dimensional complex. And when the bridging auxiliary ligand (bimb) is added, the high-dimensional complex can still be formed. The flexible conformation of H2cpob and the different N-containing ligands may be responsible for the structural diversity of binary H2cpob metal complexes. These metal complexes also displayed many differences in their fluorescence properties in the solid state.

Advanced Materials for High Biocompatible Hydrogel System

Hydrogels are gels with water as the dispersion medium and three-dimensional porous polymer networks cross-linked chemically or physically [...]

Design strategies for adhesive hydrogels with natural antibacterial agents as wound dressings: Status and trends.

The wound healing process is usually susceptible to different bacterial infections due to the complex physiological environment, which significantly impairs wound healing. The topical application of antibiotics is not desirable for wound healing because the excessive use of antibiotics might cause bacteria to develop resistance and even the production of super bacteria, posing significant harm to human well-being. Wound dressings based on adhesive, biocompatible, and multi-functional hydrogels with natural antibacterial agents have been widely recognized as effective wound treatments. Hydrogels, which are three-dimensional (3D) polymer networks cross-linked through physical interactions or covalent bonds, are promising for topical antibacterial applications because of their excellent adhesion, antibacterial properties, and biocompatibility. To further improve the healing performance of hydrogels, various modification methods have been developed with superior biocompatibility, antibacterial activity, mechanical properties, and wound repair capabilities. This review summarizes hundreds of typical studies on various ingredients, preparation methods, antibacterial mechanisms, and internal antibacterial factors to understand adhesive hydrogels with natural antibacterial agents for wound dressings. Additionally, we provide prospects for adhesive and antibacterial hydrogels in biomedical applications and clinical research.

Activation Mechanism of Coal Gangue and Its Impact on the Properties of Geopolymers: A Review.

Coal gangue is one of the industrial solid wastes that may harm the human body through the ecosystem for a long time. Using coal gangue in geopolymer preparation can effectively reduce cement output and meet the sustainability requirements. In this paper, the physical and chemical characteristics, including the heavy metal content, of coal gangue from different producing areas are described. Then, the mechanism of physical activation (mechanical and thermal activation), chemical activation, and compound activation of coal gangue are illustrated. The machinability, as well as the mechanical, microscopic, and toxicity consolidation properties of geopolymers prepared from coal gangue, are summarized and analyzed. The results indicate that the coal gangue geopolymers can have higher mobility and mechanical strength than cement-based composites by adjusting high calcium element material, alkali activator content, Na2SiO3 modulus, and curing condition. After physical activation, coal gangue is used in geopolymer preparation with a chemical activator (alkali excitation agent), which effectively forms a three-dimensional silicon aluminate polymer network. The pore structure is dense, the physical fixation and chemical bonding are strengthened, and the solidification and adsorption of heavy metal ions are improved. Further, it can also be applied to solidifying radioactive waste, which is following the future development direction.

Molecular insights into impacts of EDTMPA on membrane fouling caused by transparent exopolymer particles (TEP)

While ethylenediamine tetramethylenephosphonic acid (EDTMPA) has been emerged as a stronger chelating agent than ethylene diamine tetraacetic acid (EDTA) for fouling mitigation, and transparent exopolymer particles (TEP) is a major foulant in membrane-based water treatment process, effects of EDTMPA on TEP fouling and the underlying mechanism have been not yet studied. In this study, Flory-Huggins lattice theory was combined with density functional theory (DFT) technology to explore this subject at molecular level. Filtration experiments showed a unimodal pattern of specific filtration resistance (SFR) of TEP sample with Ca2+ concentration in range of 0–3 mM. For the TEP sample with the peak SFR value at 1.5 mM Ca2+, continuous addition of EDTMPA (from 0 to 100 mg·L−1) resulted in a sustained decrease in SFR. Energy dispersive spectroscopy (EDS) mapping characterization showed the continuing decline of calcium content in the TEP layer with increase of EDTMPA addition, indicating that EDTMPA successfully captured Ca2+ from alginate‑calcium ligation (TEP), and then disintegrated the TEP structure. DFT simulation showed that Ca2+ preferentially coordinated with the terminal carboxyl groups of alginate chains to form a coordination configuration that is conducive to stretch the three-dimensional polymer network. Such a network corresponded to an extremely high SFR according to Flory-Huggins theory. EDTMPA addition caused disintegration of the coordination configuration of Ca2+ binding to terminal carboxyl groups, which further resulted in collapse and flocculation of TEP gel network structure, thus leading to a continuous SFR decrease. This work provided deep thermodynamic insights into effects of EDTMPA on TEP-associated fouling at molecular level, facilitating to better understanding and mitigation of membrane fouling.

Synthesis and Applications of Carboxymethyl Cellulose Hydrogels.

Hydrogels are basic materials widely used in various fields, especially in biological engineering and medical imaging. Hydrogels consist of a hydrophilic three-dimensional polymer network that rapidly expands in water and can hold a large volume of water in its swelling state without dissolving. These characteristics have rendered hydrogels the material of choice in drug delivery applications. In particular, carboxymethyl cellulose (CMC) hydrogels have attracted considerable research attention for the development of safe drug delivery carriers because of their non-toxicity, good biodegradability, good biocompatibility and low immunogenicity. Aiming to inspire future research in this field, this review focuses on the current preparation methods and applications of CMC gels and highlights future lines of research for the further development of diverse applications.

Mixed diffusion and relaxation kinetics model for hydrogels swelling

Hydrogels have a unique ability to retain moisture due to the three-dimensional (3D) polymeric network. Both swelling capacity and swelling rate of hydrogels depend on the various parameters such as solution concentration, temperature, degree of cross-linking in the gel structure, type of hydrophilic groups, pH, etc. Various kinetics models were presented for swelling rate, however, most of them only describe diffusion or polymer relaxation as the predominant process on the swelling rate. In the present work, a new mixed diffusion and relaxation kinetics model is presented by simultaneously considering both diffusion and polymer relaxation. The mixed model is able to cover the whole of swelling and provides insight into the gelling mechanism. By the presented kinetics model, it is possible to indicate the contribution of solvent molecules diffusion and polymer relaxation on the swelling rate and also determine the predominant process at different extent of swelling. It is shown that this new mixed kinetics model is a general equation and covers most of the previously reported equations. The presented mixed kinetics equation was used for modeling experimental swelling kinetics data at different conditions very well.

Free-Radical Photopolymerization for Curing Products for Refinish Coatings Market.

Even though there are many photocurable compositions that are cured by cationic photopolymerization mechanisms, UV curing generally consists of the formation of cross-linking covalent bonds between a resin and monomers via a photoinitiated free radical polymerization reaction, obtaining a three-dimensional polymer network. One of its many applications is in the refinish coatings market, where putties, primers and clear coats can be cured faster and more efficiently than with traditional curing. All these products contain the same essential components, which are resin, monomers and photoinitiators, the latter being the source of free radicals. They may also include additives used to achieve a certain consistency, but always taking into account the avoidance of damage to the UV curing—for example, by removing light from the innermost layers. Surface curing also has its challenges since it can be easily inhibited by oxygen, although this can be solved by adding scavengers such as amines or thiols, able to react with the otherwise inactive peroxy radicals and continue the propagation of the polymerization reaction. In this review article, we cover a broad analysis from the organic point of view to the industrial applications of this line of research, with a wide current and future range of uses.

Antimony Nanoparticles Encapsulated in Self-Supported Organic Carbon with a Polymer Network for High-Performance Lithium-Ion Batteries Anode.

Antimony (Sb) demonstrates ascendant reactive activation with lithium ions thanks to its distinctive puckered layer structure. Compared with graphite, Sb can reach a considerable theoretical specific capacity of 660 mAh g−1 by constituting Li3Sb safer reaction potential. Hereupon, with a self-supported organic carbon as a three-dimensional polymer network structure, Sb/carbon (3DPNS-Sb/C) composites were produced through a hydrothermal reaction channel followed by a heat disposal operation. The unique structure shows uniformitarian Sb nanoparticles wrapped in a self-supported organic carbon, alleviating the volume extension of innermost Sb alloying, and conducive to the integrality of the construction. When used as anodes for lithium-ion batteries (LIBs), 3DPNS-Sb/C exhibits a high invertible specific capacity of 511.5 mAh g−1 at a current density of 0.5 A g−1 after 100 cycles and a remarkable rate property of 289.5 mAh g−1 at a current density of 10 A g−1. As anodes, LIBs demonstrate exceptional electrochemical performance.

Biomechanical origins of inherent tension in fibrin networks

Blood clots form at the site of vascular injury to seal the wound and prevent bleeding. Clots are in tension as they perform their biological functions and withstand hydrodynamic forces of blood flow, vessel wall fluctuations, extravascular muscle contraction and other forces. There are several mechanisms that generate tension in a blood clot, of which the most well-known is the contraction/retraction caused by activated platelets. Here we show through experiments and modeling that clot tension is generated by the polymerization of fibrin. Our mathematical model is built on the hypothesis that the shape of fibrin monomers having two-fold symmetry and off-axis binding sites is ultimately the source of inherent tension in individual fibers and the clot. As the diameter of a fiber grows during polymerization the fibrin monomers must suffer axial twisting deformation so that they remain in register to form the half-staggered arrangement characteristic of fibrin protofibrils. This deformation results in a pre-strain that causes fiber and network tension. Our results for the pre-strain in single fibrin fibers is in agreement with experiments that measured it by cutting fibers and measuring their relaxed length. We connect the mechanics of a fiber to that of the network using the 8-chain model of polymer elasticity. By combining this with a continuum model of swellable elastomers we can compute the evolution of tension in a constrained fibrin gel. The temporal evolution and tensile stresses predicted by this model are in qualitative agreement with experimental measurements of the inherent tension of fibrin clots polymerized between two fixed rheometer plates. These experiments also revealed that increasing thrombin concentration leads to increasing internal tension in the fibrin network. Our model may be extended to account for other mechanisms that generate pre-strains in individual fibers and cause tension in three-dimensional proteinaceous polymeric networks.

Formation of Perpendicular Three-Dimensional Network Nanostructures in ABC-Star Copolymers.

Perpendicular arrangements in hierarchical nanostructures show superior mechanical properties and provide great opportunities for the development of advanced membranes because different channels are connected by the perpendicular blocks. To obtain these perpendicular hierarchical nanostructures, we use a simple ABC-star terpolymer because of the existence of a conjunction point by using the A block as a polymer network template, which guides the BC phase separation accordingly. When χBC is 10, the formed phase and the corresponding phase diagram of ABC-star are similar to those of the AB2 triblock because of the mixture between the B and C blocks. Interestingly, at increased χBC, the B and C blocks phase separate, leading to the formation of a series of perpendicular nanostructures, including perpendicular lamellae-in-lamellae (L⊥), perpendicular lamellae-in-cylinder (C⊥), and even perpendicular three-dimensional polymer networks (G⊥). The corresponding stability regime of each phase is identified through the dedicated comparison of free energy, which can well explain the missing phases in Monte Carlo simulations. Our proposed design route according to the target structures and the calculated phase diagram can provide useful guidance for the experimental observation of these perpendicular nanostructures.

Xyloglucan-cellulose nanocrystal-chitosan double network hydrogels for soft actuators

Hydrogels are materials consisting in a three-dimensional hydrophilic polymer network swollen by a large amount of water. An efficient strategy to elaborate hydrogels consists in establishing double polymer networks in order to achieve high strengthening effect associated with other properties such as transparency or tailored swelling capacities. In this work, we prepared cellulose nanocrystals (CNC)-based hydrogels with double network architecture. The first network, formed by CNC and xyloglucan (XG), takes advantage of entropic adsorption of XG on the CNC surface while the second network relies on electrostatic interactions between cationic Chitosan (Chi) and anionic CNC. Hydrogels with different compositions were successfully prepared. Their rheological properties, stability and swelling capacities in acidic and alkaline solutions were evaluated. Internal organizations of hydrogels were investigated by fluorescence microscopy after polymer labelling and polarized optical microscopy (POM). Finally, hydrogels demonstrated excellent mechanical properties and tuneable swelling capacities that can be leveraged for the implementation of bilayer actuators. Therefore, we further prepared films composed of two hydrogels layers, each one containing a different XG/CNC ratio. Bilayered films bended in water due to the asymmetric swelling of layers and the extent of bending can be modulated by the XG/CNC ratio.