Copolymer Gels Research Articles

Design, synthesis, and characterization of novel copolymer gel particles for water-plugging applications

Abstract Multi-stage plugging represents a promising strategy for enhancing production and injection rates in medium-and low-permeability oilfields. Despite its potential, the efficacy of current plugging agents, particularly hydrophobically bonded water-soluble polyacrylamide-based gel microspheres, is hindered by notable drawbacks such as low stability and inadequate compressive strength. Therefore, a comprehensive understanding of water plugging mechanisms coupled with the optimization of gel microsphere properties is essential for advancing the development of gel-based plugging agents with superior characteristics or intelligent regulatory capabilities. The P(AA-AM-[PrSO3]Vim) ionic liquid copolymerized gel particles were designed and synthesized by using microfluidic technique and titration gel method with AM, acrylic acid (AA), 1-vinylimidazole (Vim) and 1,3-propylsulfonyl lactone (PrSO3) as the raw materials. The morphology and structure of the copolymer gel particles were characterized, and the effects of [PrSO3]Vim and cross-linker content on the water-absorbing properties and strength of the gel particles were investigated. When the amount of [PrSO3]Vim was 12%, the concentration of crosslinker was 1.5%, and the temperature was 40°C, the water absorption capacity reached the maximum value of 163 g·g−1. The strength of the P(AA–AM–[PrSO3]Vim) spherical gel particles was maximized at a [PrSO3]Vim content of 4%. Furthermore, the chemical and physical roles of the P(AA–AM–[PrSO3]Vim) spherical gel particles were studied in a typical water-plugging environment. This study provides experimental data and a theoretical basis for the application of functional spherical gel-plugging particles in current oilfield environments.

Local, Sustained, and Targeted Co-Delivery of MEK Inhibitor and Doxorubicin Inhibits Tumor Progression in E-Cadherin-Positive Breast Cancer.

Effectively utilizing MEK inhibitors in the clinic remains challenging due to off-target toxicity and lack of predictive biomarkers. Recent findings propose E-cadherin, a breast cancer diagnostic indicator, as a predictor of MEK inhibitor success. To address MEK inhibitor toxicity, traditional methodologies have systemically delivered nanoparticles, which require frequent, high-dose injections. Here, we present a different approach, employing a thermosensitive, biodegradable hydrogel with functionalized liposomes for local, sustained release of MEK inhibitor PD0325901 and doxorubicin. The poly(δ-valerolactone-co-lactide)-b-poly(ethylene-glycol)-b-poly(δ-valerolactone-co-lactide) triblock co-polymer gels at physiological temperature and has an optimal degradation time in vivo. Liposomes were functionalized with PR_b, a biomimetic peptide targeting the α5β1 integrin receptor, which is overexpressed in E-cadherin-positive triple negative breast cancer (TNBC). In various TNBC models, the hydrogel-liposome system delivered via local injection reduced tumor progression and improved animal survival without toxic side effects. Our work presents the first demonstration of local, sustained delivery of MEK inhibitors to E-cadherin-positive tumors alongside traditional chemotherapeutics, offering a safe and promising therapeutic strategy.

Structure and thermal properties of acrylic copolymer gels: effect of composition and cross-linking method

Two approaches to the synthesis of hydrogels based on polyacrylamide (pAAm) with copolymers were compared in the paper—traditional chemical cross-linking and physical cross-linking with montmorillonite (MMT). The main aim of the work was to find an adequate replacement of the chemical toxic cross-linking agent MBAAm (N,N'-methylene-bis-acrylamide) by using non-toxic—natural clay MMT for synthesis of pAAm gels, which are planned to be used as soil conditioners. A series of hydrogels based on acrylic monomers (acrylamide (AAm), acrylonitrile (AN), acrylic acid (AA)) physically cross–linked by MMT and chemically cross-linked were synthesized. For the synthesized gels, the influence of the synthesis method on the formation of the structure and the mechanism of thermal destruction in the presence of air was analyzed using a set of physicochemical methods: FTIR, XRD, SEM, DSC and TG/DTG. According to FTIR and XRD data, pAAm-MMT and pAAm-AN-MMT samples formed an intercalated/exfoliated structure, whereas pAAm-AA-MMT had an intercalated structure. The endothermic reaction of decomposition of xerogels based on acrylic polymers with and without MMT was observed using DSC and derivative thermogravimetry analyses, coupled with measurement of FTIR spectra of volatile products of thermolysis. All studied composites were relatively thermoresistant, which had three distinct regions of phase transitions and their thermal decomposition occurred at a temperature range 310–465 °C.Graphical

Cytocompatible hydrogel derived from dextrin and Poly(N-Vinyl acetamide) toward controlled antimicrobial release

The work aims to develop a biopolymer-dextrin-based three-dimensional crosslinked hydrophilic material for antimicrobial delivery. The copolymer (Dxt-PNVA) has been prepared by in-situ grafting of poly(N-vinylacetamide), followed by cross-linking with N,N'-methylenebisacrylamide with dextrin. By varying the concentrations of the reactants, an optimized copolymer (Dxt-PNVA 5) with the lowest % of crosslinking has been chosen for biomedical applications. The copolymeric gel has been characterized in detail using various techniques, followed by its cytocompatibility study using HeLa Cell lines that confirm the cytocompatible nature of the material. Copolymeric gel is a suitable material for the effective release of two antimicrobials (amoxicillin trihydrate and ornidazole) from tablet formulation for a prolonged period of 24 h. The obtained data demonstrates that the cytocompatible hydrogel has the potential characteristics of a daily dose administration for amoxicillin trihydrate and ornidazole.

Influence of PEG-PPG-PEG Block Copolymer Concentration and Coagulation Bath Temperature on the Structure Formation of Polyphenylsulfone Membranes.

The effect of amphiphilic block copolymer polyethylene glycol (PEG)-polypropylene glycol (PPG)-PEG concentration in the polyphenylsulfone (PPSU) casting solution and coagulation bath temperature (CBT) on the structure, separation, and antifouling performance of PPSU ultrafiltration membranes was studied for the first time. According to the phase diagram obtained, PPSU/PEG-PPG-PEG/N-methyl-2-pyrrolidone (NMP) systems are characterized by a narrow miscibility gap. It was found that 20 wt.% PPSU solutions in NMP with the addition of 5-15 wt.% of PEG-PPG-PEG block copolymer feature upper critical solution temperature, gel point, and lower critical solution temperature. Membrane composition and structure were studied by Fourier-transform infrared spectroscopy, scanning electron and atomic force microscopies, and water contact angle measurements. The addition of PEG-PPG-PPG to the PPSU casting solution was found to increase the hydrophilicity of the membrane surface (water contact angle decreased from 78° for the reference PPSU membrane down to 50° for 20 wt.%PPSU/15 wt.% PEG-PPG-PEG membrane). It was revealed that the pure water flux increased with the rise of CBT from 18-20 L·m-2·h-1 for the reference PPSU membrane up to 38-140 L·m-2·h-1 for 20 wt.% PPSU/10-15 wt.% PEG-PPG-PEG membranes. However, the opposite trend was observed for 20 wt.% PPSU/5-7 wt.% PEG-PPG-PEG membranes: pure water flux decreased with an increase in CBT. This is due to the differences in the mechanism of phase separation (non-solvent-induced phase separation (NIPS) or a combination of NIPS and temperature-induced phase separation (TIPS)). It was shown that 20 wt.% PPSU/10 wt.% PEG-PPG-PEG membranes were characterized by significantly higher antifouling performance (FRR-81-89%, DRr-26-32%, DRir-10-20%, DT-33-45%) during the ultrafiltration of bovine serum albumin solutions compared to the reference PPSU membrane prepared at different CBTs (FRR-29-38%, DRr-6-14%, DRir-74-89%, DT-88-94%).

Multifunctional Self-Assembled Block Copolymer/Iron Oxide Nanocomposite Hydrogels Formed from Wormlike Micelles.

This article reports the preparation of multifunctional magnetic nanocomposite hydrogels formed from wormlike micelles. Specifically, iron oxide nanoparticles were incorporated into a temperature responsive block copolymer, poly(glycerol monomethacrylate)-b-poly(2-hydroxypropyl methacrylate) (PGMA-b-PHPMA), and graphene oxide (GO) dispersion at a low temperature (∼2 °C) through high-speed mixing and returning the mixture to room temperature, resulting in the formation of nanocomposite gels. The optimal concentrations of iron oxide and GO enhanced the gel strength of the nanocomposite gels, which exhibited a strong magnetic response when a magnetic field was applied. These materials retained the thermoresponsiveness of the PGMA-PHPMA wormlike micelles allowing for a solid-to-liquid transition to occur when the temperature was reduced. The mechanical and rheological properties and performance of the nanocomposite gels were demonstrated to be adjustable, making them suitable for a wide range of potential applications. These nanocomposite worm gels were demonstrated to be relatively adhesive and to act as strain and temperature sensors, with the measured electrical resistance of the nanocomposite gels changing with applied strain and temperature sweeps. The nanocomposite gels were found to recover efficiently after the application of high shear with approximately 100% healing efficiency within seconds. Additionally, these nanocomposite worm gels were injectable, and the addition of GO and iron oxide nanomaterials seemed to have no significant adverse impact on the biocompatibility of the copolymer gels, making them suitable not only for 3D printing in nanocomposite engineering but also for potential utilization in various biomedical applications as an injectable magnetic responsive hydrogel.

Hybrid Banana Pseudo Stem biochar- poly (N-hydroxyethylacrylamide) hydrogel and its magnetic nanocomposite for effective remediation of dye from wastewater

A hybrid hydrogel based on Banana Pseudo Stem, an agricultural waste material, has been developed as an adsorbent for use in wastewater treatment. The Biochar obtained from Banana Pseudo Stem was modified by graft copolymerization with N-hydroxyethylacrylamide (HEAAm). The graft copolymer was made by microwave irradiation of an aqueous mixture containing BPSBC, N-hydroxyethylacrylamide (HEAAm), N,N-methylenebisacrylamide (MBA), and potassium peroxodisulphate (KPS). The magnetite (Fe3O4) nanoparticles have been incorporated into the gel by in-situ diffusion of Fe2+ and Fe3+ followed by a reaction with ammonia solution. FTIR, SEM, EDS, TGA, VSM, BET, and XRD techniques were used to characterize the gel and its nanocomposite. The swelling process appeared to be a second-order kinetic process and the mechanism of water transport is found to be non-Fickian. The hybrid gel and nanocomposite were evaluated for the adsorptive removal of cationic dyes using Methylene Blue (MB) and Crystal Violet (CV) as model dyes. The adsorption capacities of the graft copolymer gel for MB and CV were 200 mg g−1 and 183 mg g−1 respectively. A considerable increase in adsorption capacities was observed in nanocomposite formation, with adsorption capacity values of 235 and 202 mg g−1 for MB and CV respectively. The pseudo-second-order kinetic model and Freundlich adsorption isotherm model provide the best fit of the dye sorption data. Thermodynamic studies revealed adsorption to be a spontaneous and endothermic process. Effective desorption under acidic conditions illustrated the possibility of reuse of the developed adsorbent materials in repeated cycles during the wastewater treatment process.

Gelation of copolymers of acrylamide and sodium acrylate upon coordination with Cu2+ ions in concentrated solutions

The phase state of Cu2+ complexes with acrylamide and sodium acrylate copolymers at different copolymer concentrations and components molar ratios was studied. The change in complex stoichiometry from 2 to 3 carboxylate groups per Cu2+ ion was detected with an increase of copolymer concentration. In the concentrated solutions of copolymers, gelation is observed upon addition of Cu2+ ions, with the lowest concentration of copper required for gelation decreasing with the increase in copolymer concentration. These hydrogels are attributed to the formation of meta-stable inter-polymer metal complexes, which are able to persist due to a low segment mobility. The phase separation of complexes is shown to be associated with the bidentate coordination of carboxylate groups to Cu2+ ions, while the hydrogels formed in concentrated solutions mostly consist of bridging structures. Gelation threshold corresponds to the second critical concentration of poly(acrylamide-co-sodium acrylate) and is lower for copolymers with the higher molecular weight. Low acrylate content in the copolymers prevents collapse of the hydrogels caused by the salting-out effect. A higher gel content can be reached by increasing the copolymer concentration or the molar ratio of copper ions to carboxylate groups, with the latter reducing the swelling degree.

Synthesis of thermo-responsive polymer gels composed of star-shaped block copolymers by copper-catalyzed living radical polymerization and click reaction

ABSTRACT In recent times, there has been a significant surge in research interest surrounding thermo-responsive water-soluble polyacrylamides, primarily due to their intriguing capability to undergo significant solubility changes in water. These polymers exhibit the remarkable ability to shift from a soluble to an insoluble state in response to temperature variations. The capacity of these polymers to dynamically respond to temperature changes opens up exciting avenues for designing smart materials with tunable properties, amplifying their utility across a spectrum of scientific and technological applications. Researchers have been particularly captivated by the potential applications of thermo-responsive water-soluble polyacrylamides in diverse fields such as drug delivery, gene carriers, tissue engineering, sensors, catalysis, and chromatography separation. This study reports the construction and functionalization of polymer gels consisting of a polymer network of polyacrylamide derivatives with nano-sized structural units. Specifically, thermo-responsive polymer gels were synthesized by combining well-defined star-shaped polymers composed of polyacrylamide derivatives with a multifunctional initiator and linking method through a self-accelerating click reaction. The polymerization system employed a highly living approach, resulting in polymer chains characterized by narrow molecular weight distributions. The method’s high functionality facilitated the synthesis of a temperature-responsive block copolymer gel composed of N-isopropyl acrylamide (NIPA) and N-ethyl acrylamide (NEAA). The resulting polymer gel, comprising star-shaped block copolymers of NIPA and NEAA, showcases smooth volume changes with temperature jumps.

Comparison of Structural, Water-Retaining and Sorption Properties of Acrylamide-Based Hydrogels Cross-Linked by Physical and Chemical Methods.

Two series of hydrogels based on acrylamide and its copolymers with acrylonitrile and acrylic acid were synthesized by two cross-linking methods - chemical (using N,N'-methylene bis-acrylamide) and physical (using montmorillonite (MMT)) ones. The structure of the gels was characterized by Fourier Transform Infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The swelling and sorption properties were analyzed as a function of both the monomer composition and the cross-linking method. The shift of the band corresponding to Si-O (995-1030 cm-1 ) confirmed the formation of intercalation structures for MMT-cross-linked gels. Moreover, physically cross-linked gels demonstrated a non-monotonic dependence of the swelling degree on the MMT concentration, and acrylamide-acrylic acid copolymer MMT-cross-linked gels showed pH sensitivity and the highest swelling degree of 150 g/g. The highest sorption capacity towards cadmium(II) ions was demonstrated by acrylamide-acrylic acid copolymer gels, both covalently cross-linked (30 mg/g) and MMT-cross-linked (8.9 mg/g).

Anionic starch-based hybrid cryogel-embedded ZnO nanoparticles: tuning the elasticity and pH-functionality of biocomposites with dicarboxylic acid units.

Weakly anionic semi-interpenetrating polymer network (semi-IPN) biocomposites based on starch (ST)-incorporated poly(acrylamide-co-itaconic acid)/ZnO (ST-PAI/ZnO) were synthesized by a simple one-pot method via free radical aqueous polymerization. Hybrid biocomposites exhibited lower equilibrium swelling compared with neat copolymer gel. For both hydrogels and cryogels, swelling followed a decreasing order as copolymer PAI > starch-free PAI/ZnO > ST-PAI/ZnO gels. With the addition of 9% ST and ZnO, the swelling ratio of gels decreased from 898 to 68.3, resulting in a significant increase in elastic modulus. Compared with a fixed amount of ST, biocomposite cryogels exhibited significantly higher modulus than hydrogels. With the addition of 9% ST, the elastic modulus of cryogels reached 22.2 kPa while it was 2.7 kPa for the hydrogels. An equation expressing the effective cross-linking density of semi-IPNs presented by a cubic polynomial as a function of starch was obtained. As pH increased with the presence of dicarboxylic acid units, a gradual increase in swelling occurred at two different pH values. A gradually reproducible swelling change of semi-IPNs was depicted with pH ranging from 2.1 to 11.2. Biocomposite cryogels showed rapid swelling in a buffer solution of pH 11.2 and rapid shrinking in pH 2.1. Salt-induced swelling testing showed that the ability to reduce the degree of swelling and solubility of starch was Br- > Cl- > NO3- > SO42- for anions consistent with the Hofmeister series. Adsorption efficiency for the removal of methyl violet (MV) dye was analyzed using Langmuir, Freundlich, Dubinin-Radushkevich and Temkin isotherm models. The results confirmed that the Langmuir isotherm and pseudo-second-order model are suitable for describing MV adsorption on semi-IPN biocomposites. The synthesized biocomposites with good swelling/deswelling kinetics in different pH-buffer solutions, high saline absorbency, desirable adsorption efficiency, and acceptable pH-dependent swelling reversibility can be considered as smart hybrid materials for the adsorption of the dye in water purification tasks.

Research Progress of Gel Foam Extinguishing Agent in Coal Mines

Gel foam extinguishing agent (gel foam) has promising applications in the prevention and management of mine coal spontaneous combustion. Based on the research on coal spontaneous combustion and prevention technology, this article discusses recent studies on using gel foam to extinguish coal mines. The structural properties and principles of gel foam are described briefly. The research developments of three significant varieties of gel foam are then presented in detail, including silicate gel foam, acrylamide copolymer gel foam, and natural polymer gel foam. Meanwhile, the research status of gel foam anti-fire technology’s rheological properties, stability property, plugging property, and inhibitory properties are introduced. Furthermore, in conjunction with the research state, the prospects of the research direction of gel foam are proposed, which serve as a reference for future research on gel foam.

Regulating the π–π interactions of copolymer gelators: Effective molecular design of highly stretchable and tough ionogels for wearable ionotronics

The emergence of stretchable ionic conductors has facilitated the development of wearable devices that can perceive changes in their surrounding environment and interpret external stimuli. An example of this is ionic skin, a form of artificial skin that is worn constantly for the real-time monitoring of temperature, pressure, and tension. However, ionic skins are vulnerable to physical damage and stress, which reduces their functionality, performance, and longevity. To obtain mechanically durable ionic skins, the toughness of their constituent ionogels must be improved by increasing their strength and/or stretchability. However, the molecular design and synthesis of these materials remain challenging due to the inherent trade-off between mechanical durability and ionic conductivity. In the present study, we introduced three styrene derivatives containing pendant groups of different sizes to copolymer gelators as ionic liquid (IL)-solvophobic components that form physically crosslinked domains and compared the mechanical and conductivity performance of the resulting ionogels. As the packing density of the styrene decreased, the IL-solvophobic domains became softer and more deformable due to the weaker physical crosslinking via π–π interactions. The optimal ionogel exhibited high stretchability (∼1200 %), excellent toughness (∼3.4 MJ·m−3), and high transparency (∼98 %). The successful use of the optimal ionogel in ionic skin sensors and deformable alternating-current electroluminescent displays demonstrated its broad range of practical applications.

Percutaneous Intratumoral Immunoadjuvant Gel Increases the Abscopal Effect of Cryoablation for Checkpoint Inhibitor Resistant Cancer.

Percutaneous cryoablation is a common clinical therapy for metastatic and primary cancer. There are rare clinical reports of cryoablation inducing regression of distant metastases, known as the "abscopal" effect. Intratumoral immunoadjuvants may be able to augment the abscopal rate of cryoablation, but existing intratumoral therapies suffer from the need for frequent injections and inability to confirm target delivery, leading to poor clinical trial outcomes. To address these shortcomings, an injectable thermoresponsive gel-based controlled release formulation is developed for the FDA-approved Toll-like-receptor 7 (TLR7) agonist imiquimod ("Imigel") that forms a tumor-resident depot upon injection and contains a contrast agent for visualization under computed tomography (CT). The poly-lactic-co-glycolic acid-polyethylene glycol-poly-lactic-co-glycolic acid (PLGA-PEG-PLGA)-based amphiphilic copolymer gel's underlying micellar nature enables high drug concentration and a logarithmic release profile that is additive with the neo-antigen release from cryoablation, requiring only a single injection. Rheological testing demonstrated the thermoresponsive increase in viscosity at body temperature and radio-opacity via microCT. Its ability to significantly augment the abscopal rate of cryoablation is demonstrated in otherwise immunotherapy resistant metastatic tumors in two aggressive colorectal and breast cancer dual tumor models with an all or nothing response, responders generally demonstrating complete regression of bilateral tumors in 90-day survival studies.

Construction and performance of PVDF-HFP-matrix comb-like gel copolymer electrolyte for high-performance quasi-solid-state lithium-metal batteries

Rechargeable lithium metal batteries (LMBs) have encountered bottlenecks in energy density, durability, and safety issues. Designing functional polymer electrolytes has been considered as an effective way to develop high-performance of LMBs. In this study, PVDF-HFP-matrix polymeric electrolytes blended with copolymer P(MMA-co-PEGMEMA) (PPxPy) via a simple one-pot free-radical polymerization are successfully designed and prepared. It has been found that the PPxPy electrolytes can construct different comb-like networks via systematically tuning monomer ratios. The tailored PP5P5 gel electrolyte exhibited high ionic conductivity of 0.74 × 10−3 S cm−1 at room temperature (RT), an enlarged electrochemical window up to 4.77 V, high lithium-ion transference number tLi+ of 0.65, and good mechanical property with Yang's modulus up to 131 MPa. Benefited from these good properties, the Li||LiFePO4 batteries assembled with PP5P5 gel electrolyte achieved an exceptional discharge capacity of 152 mAh g−1 with nearly 100 % Coulombic efficiency after 150 cycles at 1C. Furthermore, the Li|PP5P5|NCM811 cell exhibits excellent reversible specific capacity of 188 mAh g−1 at 0.1C. Consequently, it can be anticipated the as-prepared functional polymer structure to provide a reliable method for the preparation of polymer electrolytes in quasi-solid-state batteries with high-energy-density.

Removal o f Congo red by copoly (DMAEMA-AMPS) hydrogels for water treatment

Ten copolymer gels were prepared from dimethylaminomethacrylate and 2-acrylamido-methylpropane-1-sulfonic acid with crosslinking agent methylene-bisacrylamide by redox polymerization. Hydrogels were characterized by studying their swelling ratios, the surface morphology by SEM, and studying the porosity and specific surface area by BET technique. The hydrogel copolymers were used to remove Congo red dye from aqueous solutions. It was found that there are two copolymers (C20 and E20) gave the best results for removing this dye from aqueous solutions at pH 7. The adsorption behavior was in agreement with Freundlich's model for C20, while E20 matched with Langmuir's model. It was also found that adsorption of Congo red dye on the two copolymeric hydrogels followed a pseudo-second-order kinetics. The results of the activation energy showed that the adsorption of the dye with the hydrogel C20 is chemisorption in nature, while it is physisorption with the hydrogel E20. Finally, desorption studies carried out in 0.1 M of NaOH and hydrochloric acid, distilled water, and 95% ethanol indicated that the best eluent for dye recovery was NaOH.

Dynamic Metal-Ligand Coordination-Assisted Ionogels for Deformable Alternating Current Electroluminescent Devices.

Overcoming the trade-off between the mechanical robustness and conductivity of ionic conductors is a crucial challenge for deformable ionotronics. In this work, we propose a simple but effective gelation strategy for selectively improving the mechanical robustness of ionogels without compromising their ionic conductivity. To achieve this, we introduce dynamic metal-ligand coordination chemistry into the ionic liquid (IL)-insoluble domains of a physically crosslinked ionogel network structure. As a result, the overall mechanical property is remarkably improved with the aid of additional chemical crosslinking. This strategy does not require any additional heat/light (UV) treatments to induce chemical crosslinking. The homogeneous physically/chemically dual crosslinked ionogel films can be readily obtained by simply casting a solution containing Ni2+ sources, copolymer gelators, and ILs. The effects of adjusting fundamental parameters on the ionogel properties are investigated systematically. The optimized mechanically robust and highly conductive ionogels are successfully employed as deformable ionic electrodes in alternating-current electroluminescent displays, indicating their high practicality. Overall, these results validate that exploiting metal-ligand coordination dynamic bonding is an extremely straightforward strategy for selectively improving the mechanical characteristics of conductive ionogels, which are promising platforms for deformable ionotronics.

Nanostructure Scaling in Semi‐Dilute Triblock Copolymer Gels

AbstractThere is a considerable body of work that describes the scaling of diblock copolymer micelle dimensions in dilute and semi‐dilute solution based upon block degrees of polymerization and copolymer concentration. However, there is a lack of analogous information for semi‐dilute ABA triblock copolymer gels, which consist of ABA triblock copolymer dissolved in midblock‐selective (B‐selective) solvent. The present study uses small angle X‐ray scattering to extract micelle dimensions for numerous triblock copolymer gels that vary in copolymer identity (and hence block lengths) and copolymer concentration, as well as gels that contain various ratios of two unique triblock copolymers. Analysis of micelle structural data subsequently translates to universal scaling expressions for the micelle core radius – rA ≈ NA0.53NB−0.14ϕABA0.16 where NA and NB are the endblock and midblock degrees of polymerization, respectively, and ϕABA is the volume fraction of triblock copolymer in the gel – and for the intermicelle spacing – lAA ≈ NA0.09NB0.29ϕABA−0.35. Each scaling expression describes the full collection of experimental data very well. Additionally, these scaling expressions are partially in line with expectations from semi‐dilute diblock copolymer solution theory.

Phosphate-based gel polymer electrolyte enabling remarkably long cycling stable sodium storage in a wide-operating-temperature

Gel polymer electrolytes are regarded as one of the efficient strategies to substitute traditional liquid electrolytes for achieving safer high energy density sodium ion batteries. However, operating under wide temperature range especially at low temperature under zero is still a great challenge for most gel polymer electrolytes and becomes a hindrance to sodium ion batteries further development. Herein, a multifunctional phosphate gel copolymer electrolyte with larger crosslinking degree and encapsulation over a broader operation temperature range (−20 to 70 °C) is designed and synthesized via in situ free radical copolymerization. This gel polymer electrolyte displays a wide electrochemical stability window up to 5.1 V (vs. Na+/Na) and high ionic conductivity even at low temperature of − 20 °C (>1.0 × 10−3 S cm−1). Moreover, its outstanding interfacial stability is confirmed via alternating-current impedance and Na plating/stripping experiments. The morphology and X-ray photoelectron spectroscopy data of separators after long cycling suggest the gel electrolyte has ability to inhibit the decomposition of liquid electrolyte and suppress the growth of sodium dendrite, hence enhance the cycling stability of battery efficiently at wide temperature range. As a result, the assembled gel Na||Na3V2(PO4)3 battery delivers outstanding ultralong cycling stability with superior discharge capacity retention over wide temperature range, including at room temperature (0.002% capacity decay per cycle for 3000 cycles), 60 °C (0.005% fade per cycle for 1500 cycles) and −10 °C (0.002% fade per cycle for 1200 cycles).

An Acrylonitrile-Based Copolymer Gel as an NMR Alignment Medium for Extraction of Residual Dipolar Couplings of Small Molecules in Aqueous Solution.

An NMR weakly-aligning polymer gel has been prepared by copolymerization of acrylonitrile and 2-acrylamide-2-methyl-1-propanesulfonic acid in the presence of 1,4-butanediol diacrylate as a cross-linker. The polymer readily swells in water in a large range of temperatures, although the swelling ratio is decreased in saline solutions. The swollen gel can be mechanically compressed, in a reversible way, generating anisotropy, as easily shown in 2 H NMR experiments, and allowing measurement of 1 DCH residual dipolar couplings (RDCs) through F1-coupled HSQC experiments. The performance of this gel as a NMR alignment medium was evaluated in several water-soluble organic molecules and, while it provided RDCs of proper size for sucrose and even such as small molecule as 5-norbornen-2-ol, in the case of azidothymidine and cefuroxime sodium salt the strong interaction of these molecules with the gel prevented successful extraction of the RDCs.