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Magnetic gels with embedded micro-/nano-sized magnetic particles in cross-linked polymer networks can be actuated by external magnetic fields, with changes in their internal microscopic structures and macroscopic mechanical properties. We investigate the responses of such magnetic gels to an external magnetic field, by means of coarse-grained molecular dynamics simulations. We find that the dynamics of magnetic particles are determined by the interplay of magnetic dipole–dipole interactions, polymer elasticity, and thermal fluctuations. The corresponding microscopic structures formed by the magnetic particles, such as elongated chains, can be controlled by the external magnetic field. Furthermore, the magnetic gels can exhibit reinforced macroscopic mechanical properties, where the elastic modulus increases algebraically with the magnetic moments of the particles in the form of ∝ (m − m c ) 2 when magnetic chains are formed. This simulation work can not only serve as a tool for studying the microscopic and the macroscopic responses of the magnetic gels, but also facilitate future fabrications and practical controls of magnetic composites with desired physical properties. [ABSTRACT FROM AUTHOR]

The elasticity of polymer networks, formed by cross-linking high molecular mass polymers in the melt state and then swollen by a solvent, involves contributions from both the presence of cross-link network junctions and the interchain interactions associated with the combined effect of excluded volume interactions and topological constraints that become modified when the network is swollen. We test the capacity of the previously developed localization model of rubber elasticity, a mean field "tube model," to describe changes in elasticity observed in classical experimental studies of the mechanical properties of this type of network. In order to obtain a satisfactory comparison to the experiments, it was found to be necessary to account for the independently observed tendency of the network junctions to become localized in the network with appreciable swelling, as well as the interchain interactions emphasized in previous discussions of the localization model. [ABSTRACT FROM AUTHOR]

Materials incorporating covalent adaptive networks (CAN), e.g., vitrimers, have received significant scientific attention due to their distinctive attributes of self-healing and stimuli-responsive properties. Different from direct crosslinked systems, bivalent and multivalent systems require a bond swap algorithm that respects detailed balance, considering the multiple equilibria in the system. Here, we propose a simple and robust algorithm to handle bond swap in multivalent and multi-species CAN systems. By including a bias term in the acceptance of Monte Carlo moves, we eliminate the imbalance from the bond swap site selection and multivalency effects, ensuring the detailed balance for all species in the system. [ABSTRACT FROM AUTHOR]

The network structure within polymers significantly influences their mechanical properties, including their strength, toughness, and fatigue resistance. All-atom molecular dynamics (AAMD) simulations offer a method to investigate the energy dissipation mechanism within polymers during deformation and fracture; Such an approach is, however, computationally inefficient when used to analyze polymers with complex network structures, such as the common chemically double-networked hydrogels. Alternatively, coarse-grained molecular dynamics (CGMD) models, which reduce the computational degrees of freedom by concentrating a set of adjacent atoms into a coarse-grained bead, can be employed. In CGMD simulations, a coarse-grained force field (CGFF) is a critical factor affecting the simulation accuracy. In this paper, we proposed a data-based method for predicting the CGFF parameters to improve the simulation efficiency of complex cross-linked network in polymers. Here, we utilized a typical chemically double-networked hydrogel as an example. An artificial neural network was selected, and it was trained with the tensile stress–strain data from the CGMD simulations using different CGFF parameters. The CGMD simulations using the predicted CGFF parameters show good agreement with the AAMD simulations and are almost fifty times faster. The data-inspired CGMD model presented here broadens the applicability of molecular dynamics simulations to cross-linked polymers and has the potential to provide insights that will aid the design of polymers with desirable mechanical properties. [ABSTRACT FROM AUTHOR]

The diffusion of small molecular penetrants through polymeric materials represents an important fundamental problem, relevant to the design of materials for applications such as coatings and membranes. Polymer networks hold promise in these applications because dramatic differences in molecular diffusion can result from subtle changes in the network structure. In this paper, we use molecular simulation to understand the role that cross-linked network polymers have in governing the molecular motion of penetrants. By considering the local, activated alpha relaxation time of the penetrant and its long-time diffusive dynamics, we can determine the relative importance of activated glassy dynamics on penetrants at the segmental scale vs entropic mesh confinement on penetrant diffusion. We vary several parameters, such as the cross-linking density, temperature, and penetrant size, to show that cross-links primarily affect molecular diffusion through the modification of the matrix glass transition, with local penetrant hopping at least partially coupled to the segmental relaxation of the polymer network. This coupling is very sensitive to the local activated segmental dynamics of the surrounding matrix, and we also show that penetrant transport is affected by dynamic heterogeneity at low temperatures. To contrast, only at high temperatures and for large penetrants or when the dynamic heterogeneity effect is weak, does the effect of mesh confinement become significant, even though penetrant diffusion more broadly empirically follows similar trends as established models of mesh confinement-based transport. [ABSTRACT FROM AUTHOR]

In situ formed poly(1,3‐dioxolane) (PDOL) electrolytes are of great interest due to the facile process and the improved interface contact. However, the practical application of in situ PDOL electrolytes is still plagued by fast solidification time (liquid state) and poor high‐voltage stability (solid state). Herein, the slow‐release carriers triglycidyl isocyanurate (TGIC), which play dual roles as initiator sustained‐release and network confinement, can tune DOL curing time and cathode/electrolyte interface chemistry is demonstrated. Specifically, the electronegative C≐O and epoxy groups in TGIC have an affinity with BF3, the decomposition product of lithium bis(oxalate)borate (LiDFOB), delaying BF3 protonation reaction and thus extending DOL solidification time. In addition, the epoxy groups in TGIC serve as crosslinking sites to form in situ crosslinked polymer electrolytes (TPDOL@FEC). The corresponding network structure suppresses the contact reaction between high‐fluidity organic components and cathodes, generating a uniform and thin cathode electrolyte interface layer. As a result, the TPDOL@FEC precursor solution can remain its liquid state even after resting 24 h at room temperature. The assembled LiNi0.6Co0.2Mn0.2O2||TPDOL@FEC||Li cells display an impressive capacity retention of 91.5% after 100 cycles at 4.4 V (0.5 C). This study is expected to be a leap in the pursuit of practically feasible in situ formed PDOL electrolytes. [ABSTRACT FROM AUTHOR]

Glucose has been extensively studied as a targeting ligand on nanoparticles for biomedical nanoparticles. A promising nanocarrier platform are single-chain polymer nanoparticles (SCNPs). SCNPs are well-defined 5–20 nm semi-flexible nano-objects, formed by intramolecularly crosslinked linear polymers. Functionality can be incorporated by introducing labile pentafluorophenyl (PFP) esters in the polymer backbone, which can be readily substituted by functional amine-ligands. However, not all ligands are compatible with PFP-chemistry, requiring different ligation strategies for increasing versatility of surface functionalization. Here, we combine active PFP-ester chemistry with copper(I)-catalyzed azide alkyne cycloaddition (CuAAC) click chemistry to yield dual-reactive SCNPs. First, the SCNPs are functionalized with increasing amounts of 1-amino-3-butyne groups through PFP-chemistry, leading to a range of butyne-SCNPs with increasing terminal alkyne-density. Subsequently, 3-azido-propylglucose is conjugated through the glucose C1- or C6-position by CuAAC click chemistry, yielding two sets of glyco-SCNPs. Cellular uptake is evaluated in HeLa cancer cells, revealing increased uptake upon higher glucose-surface density, with no apparent positional dependance. The general conjugation strategy proposed here can be readily extended to incorporate a wide variety of functional molecules to create vast libraries of multifunctional SCNPs. [Display omitted] [ABSTRACT FROM AUTHOR]

We report the first-ever complete measurement of MAOStress material functions, which reveal that stress can be more fundamental than strain or strain rate for understanding linearity limits as a function of Deborah number. The material used is a canonical viscoelastic liquid with a single dominant relaxation time: polyvinyl alcohol (PVA) polymer solution cross-linked with tetrahydroborate (Borax) solution. We outline experimental limit lines and their dependence on geometry and test conditions. These MAOStress measurements enable us to observe the frequency dependence of the weakly nonlinear deviation as a function of stress amplitude. The observed features of MAOStress material functions are distinctly simpler than MAOStrain, where the frequency dependence is much more dramatic. The strain-stiffening transient network model was used to derive a model-informed normalization of the nonlinear material functions that accounts for their scaling with linear material properties. Moreover, we compare the frequency dependence of the critical stress, strain, and strain-rate for the linearity limit, which are rigorously computed from the MAOStress and MAOStrain material functions. While critical strain and strain-rate change by orders of magnitude throughout the Deborah number range, critical stress changes by a factor of about 2, showing that stress is a more fundamental measure of nonlinearity strength. This work extends the experimental accessibility of the weakly nonlinear regime to stress-controlled instruments and deformations, which reveal material physics beyond linear viscoelasticity but at conditions that are accessible to theory and detailed simulation. [ABSTRACT FROM AUTHOR]

This study addresses the critical challenge of excessive water production in mature oil and gas reservoirs. It focuses on the effectiveness of polymer gel injection into porous media as a solution, with an emphasis on understanding its impact at the pore scale. A step-wise Lattice Boltzmann Method (LBM) is employed to simulate polymer gel injection into a 2D Berea sample, representing a realistic porous media. The non-Newtonian, time-dependent characteristics of polymer gel fluid necessitate this detailed pore-scale analysis. Validation of the simulation results is conducted at each procedural step. The study reveals that the methodology is successful in predicting the effect of polymer gel on reducing permeability as the gel was mainly formed in relatively larger pores, as it is desirable for controlling water cut. Mathematical model presented in this study accurately predicts permeability reductions up to 100% (complete blockage). In addition, simulations conducted over a wide range of gelation parameters, TD_factor from 1 to 1.14 and Threshold between 0.55 and 0.95, revealed a quadratic relationship between permeability reduction and these parameters. The result of this research indicates LBM can be considered as promising tool for investigating time-dependant fluids on porous media. [ABSTRACT FROM AUTHOR]

Dynamic optical modulation in response to stimuli provides exciting opportunities for designing novel sensing, actuating, and authentication devices. Here, we demonstrate that the reversible swelling and deswelling of crosslinked polymer colloidal spheres in response to pH and temperature changes can be utilized to drive the assembly and disassembly of the embedded gold nanoparticles (AuNPs), inducing their plasmonic coupling and decoupling and, correspondingly, color changes. The multi‐responsive colloids are created by depositing a monolayer of AuNPs on the surface of resorcinol‐formaldehyde (RF) nanospheres, then overcoating them with an additional RF layer, followed by a seeded growth process to enlarge the AuNPs and reduce their interparticle separation to induce significant plasmonic coupling. This configuration facilitates dynamic modulation of plasmonic coupling through the reversible swelling/deswelling of the polymer spheres in response to pH and temperature changes. The rapid and repeatable transitions between coupled and decoupled plasmonic states of AuNPs enable reversible color switching when the polymer spheres are in colloidal form or embedded in hydrogel substrates. Furthermore, leveraging the photothermal effect and stimuli‐responsive plasmonic coupling of the embedded AuNPs enables the construction of hybrid hydrogel films featuring switchable anticounterfeiting patterns, showcasing the versatility and potential of this multi‐stimuli‐responsive plasmonic system. [ABSTRACT FROM AUTHOR]

The high‐performance development of advanced resin matrix composites has resulted in higher requirements for the mechanical strength and toughness of epoxy resin matrices. However, enhancing the toughness of the epoxy resin while maintaining its mechanical strength remains a considerable challenge. In this study, we utilized triazine rings as the skeleton, and introduced flexible chain segments and other forces into the polymer cross‐linked network to fabricate a star‐shaped epoxy resin (CNE) with exceptional mechanical properties. Benefiting from its meticulously designed rigid‐flexible integrated structure, after curing by 4,4′‐diaminodiphenylmethane (DDM), it demonstrated outstanding mechanical properties. The storage modulus of CNE/DDM was measured at up to 5.48 GPa; moreover, its tensile modulus and strength went as high as 5.04 GPa and 134.72 MPa respectively, and it also exhibited an elongation at break of up to 3.35%. The mechanical properties of CNE/DDM are far superior to those of AFG‐90 (N,N‐diglycidyl‐4‐glycidyloxyaniline)/DDM. Over all, the findings of this study thus provide an effective synthesis pathway toward achieving epoxy resins with high modulus, strength, and toughness. [ABSTRACT FROM AUTHOR]

Visualizing the network of a solvent‐swollen polymer gel remains problematic. To address this challenge, open transmission electron microscopy (TEM) was applied to thin gel films permeated by a nonvolatile ionic liquid. The targeted physical gels were prepared by cooling concentrated solutions of poly(ethylene glycol) in 1‐ethyl‐3‐methyl imidazolium ethyl sulfate [EMIM][EtSO4]. During the cooling, gelation occurred by a frustrated crystallization of the dissolved polymer, leading to a percolated, solvent‐permeated semicrystalline network in which nanoscale polymer crystals acted as crosslinks. Crystalline features ranging from ~5 to ~200 nm were observed, with the visible network strands dominantly consisting of long curvilinear crystallites of ~15–20 nm diameter. Nascent spherulites irregularly decorated the network, creating a complex structural hierarchy that complicated analyses. Lacking diffraction contrast, TEM did not visualize the many disordered, fully solvated PEG chains present in the voids between crystals. Recognizing that a network's three dimensionality is ambiguous when assessed through two‐dimensional microscopy projections, a small gel region was studied by TEM tomography, revealing a nearly isotropic three‐dimensional arrangement of the curvilinear crystallites, which displayed remarkably uniform cylindrical cross sections. [ABSTRACT FROM AUTHOR]

The worldwide prevalence of musculoskeletal disorders is expected to rise due to an accelerating aging population and increasing associated factors. Despite the high rate of disability induction, clinical options for the treatment of musculoskeletal disorders remain limited. Hydrogel microspheres (HMSs), which are colloidal particles with crosslinked polymer networks at the nanometer scale, are characterized by excellent biocompatibility, easy‐to‐tune structures (e.g., stiffness, porosity, and composition), and high encapsulation efficiency of therapeutic agents (e.g., drugs and cells). At present, multiple techniques are utilized for the fabrication of HMSs and encapsulation of therapeutic agents. The HMSs can be produced and used in different states to match specific utilizations. These desirable properties, along with their injectability, bestow HMSs with mutifunctionalities that can be utilized for a variety of biomedical applications (e.g., delivery of biologics, tissue regeneration, and bio‐lubrication), and thus enable them to be promising tools for tackling a variety of clinical diseases. Herein, the focus is the fabrication and application of therapeutic HMSs for i) bone disorders, ii) cartilage and osteochondral disorders, iii) intervertebral disc (IVD) disorders, and iv) neurovascular disorders, with the aim of overviewing the recent progress to summarize key contributions and findings and highlight the limitations and opportunities in this field. [ABSTRACT FROM AUTHOR]

Porous polymer beads with grafted poly(tertiary amine) were prepared by grafting triethylenetetramine to porous crosslinked poly(methyl acrylate) beads via ester amidation reaction, followed by Eschweiler–Clarke methylation reaction using formaldehyde and formic acid to converting the primary and secondary amine groups to tertiary amines in the beads. The tertiary amine groups in the beads were protonated with hydrochloric acid, hydrobromic acid or hydriodic acid, and the protonated tertiary amine group-containing beads showed high catalytic activity and high selectivity for the formation of propylene carbonate through cycloaddition of propylene oxide with CO2, while free tertiary amine group-containing beads exhibited almost no catalytic activity. The recyclability of the catalyst was studied, and slight loss of the activity was observed after five runs. [ABSTRACT FROM AUTHOR]

A ternary composite (KB/BMO-GO) consisting of graphene oxide, Bi 2 MoO 6 and crosslinked benzene polymer was prepared by solvothermal and in-situ deposition methods, which were used to promote the synergistic adsorption-photocatalytic degradation of the refractory pollutant oxytetracycline (OTC). A cycle involving the simultaneous adsorption and photocatalytic enhances the degradation performance of oxytetracycline. The 15% KB/BMO-GO sample exhibited the best synergistic adsorption-photocatalytic degradation performance, which has great potential in practical applications for low concentration refractory pollutants removal of water. [Display omitted] Antibiotics are refractory degradable organic pollutants that present a significant hazard to water environments. In this work, a ternary composite (KB/BMO-GO) comprising of graphene oxide (GO), Bi 2 MoO 6 (BMO), and a cross-linked benzene polymer (KB) was synthesized and applied to promote the synergistic adsorption-photocatalytic degradation of the refractory pollutant, oxytetracycline (OTC). The inclusion of GO and KB in the composite enhanced the OTC adsorption performance of the catalysts, and the construction of Z-scheme heterojunction promoted the photogenerated charge separation efficiency and broadened the range of light absorption, thereby enhancing the photocatalytic performance. Moreover, we compared the performance of catalysts loaded with different mass ratios of KB (x% KB/BMO-GO). Among them, the 15 % KB/BMO-GO catalyst sample had the best OTC degradation performance. Specifically, 15 % KB/BMO-GO could adsorb 69.7 % of OTC in 30 min, reaching an OTC degradation rate of 93.3 % under visible light irradiation. h+ and 1O 2 are the main active substances in the photocatalytic process. In addition, the catalysts are acid-alkali and salt-resistant, as well as good reusability. This study provides a valuable reference for the preparation of highly efficient photocatalysts for synergistic adsorption-photodegradation processes. [ABSTRACT FROM AUTHOR]

The construction of amorphous‐crystalline interfaces of heterogeneous metal oxide systems is an effective approach to modulate the interfacial adsorption behavior and carrier transfer pathways for the photocatalytic process. In this work, the amorphous‐crystalline interface is constructed by covalently linking a flexible crosslinked polymer (FCP) layer to a Pt0.25%/TO(B) substrate. Adsorption‐photodegradation experiments show that Pt0.25%/TO(B)‐FCP can ultimately enrich bisphenol A molecules to the interface within 5 min and in situ‐photodegrade >97.0% of bisphenol A within 10 min (50 ppm), which is 6.21 times than pure TO(B). In addition to the efficient accumulation of BPA molecules, the rapid hole transfer pathway at the amorphous‐crystalline interface is revealed by theoretical calculations, Kelvin probe force microscopy, and photoelectrochemical characterization. The coexistence of Pt single atoms (SAs) and nanoclusters (NCs) optimizes the transfer kinetics and reduces the energy barrier of photogenerated holes of TO(B). Meanwhile, the covalent hole transfer channels between the FCP layer and Pt0.25%/TO(B) significantly accelerate the separation and transfer of photogenerated carrier, promoting the photodegradation of adsorbed BPA molecules. [ABSTRACT FROM AUTHOR]

Cross-linked polymers with covalent adaptable networks (CANs) can be reprocessed under external stimuli owing to the exchangeability of dynamic covalent bonds. Optimization of reprocessing conditions is critical since increasing the reprocessing temperature costs more energy and even deteriorates the materials, while reducing the reprocessing temperature via molecular design usually narrows the service temperature range. Exploiting CO2 gas as an external trigger for lowering the reprocessing barrier shows great promise in low sample contamination and environmental friendliness. Herein, we develop a type of CANs incorporated with ionic clusters that achieve CO2-facilitated recyclability without sacrificing performance. The presence of CO2 can facilitate the rearrangement of ionic clusters, thus promoting the exchange of dynamic bonds. The effective stress relaxation and network rearrangement enable the system with rapid recycling under CO2 while retaining excellent mechanical performance in working conditions. This work opens avenues to design recyclable polymer materials with tunable dynamics and responsive recyclability. Cross-linked polymers with covalent adaptable networks are reprocessed under external stimuli at high temperatures which might deteriorate their performance. Here, the authors introduce carbon dioxide responsive ionic clusters into covalent adaptable polymer networks to facilitate the exchange of dynamic bonds providing materials with a rapid recycling and good mechanical performance. [ABSTRACT FROM AUTHOR]

Hydraulic conductivity tests were conducted on six bentonite-polymer (B–P) geosynthetic clay liners (GCLs) to investigate the effect of the slow cation exchange process and polymer elution on the long-term hydraulic conductivity of B–P GCLs. Tests were conducted up to 1458 days and as many as 443 pore volumes of flows (PVFs). Three B–P GCLs consist of linear polymer whereas the other three have crosslinked polymer. One sodium geosynthetic clay liner (Na–B GCL) was used as a control. Hydraulic conductivities (K 6766) of B–P GCLs (5.4 × 10−12 m/s to 3.7 × 10−11 m/s) per ASTM D6766 were approximately 2-3 orders of magnitude lower than that of Na–B GCL (2.3 × 10−9 m/s to 3.5 × 10−9 m/s). Tests were continued after hydraulic and chemical equilibrium to investigate the long-term hydraulic conductivity of GCLs. Hydraulic conductivities of GCLs had an increasing trend after hydraulic and chemical equilibrium. The ratio of K L /K 6766 for B–P GCLs was 3.5–14.7, whereas ratio of K L /K 6766 for Na–B GCLs was 1.0–1.7. Total organic carbon (TOC) tests results confirmed that polymer elution occurred during the entire permeation process. The higher ratio of K L /K 6766 for B–P GCLs was attributed to the effect of polymer elution. • Hydraulic conductivity tests were conducted up to 4 years to test long-term hydraulic conductivity of B–P GCLs. • The ratios of K L /K 6766 for B–P GCLs to synthetic CCP leachate were higher than that of Na–B GCLs (e.g., 3.5 to 14.7 vs. 1.7). • Polymer elution from B–P GCLs affects the long-term hydraulic conductivity of B–P GCLs. • The polymer elution should be measured and considered as an additional termination criterion in ASTM D6766. [ABSTRACT FROM AUTHOR]

Metal–ligand coordinated cross-linked polymer composites, have been recognized as promising candidates to address the shortcomings of conventional cross-linked composites. In this report, we present how the carboxylic functional group of carboxylated nitrile rubber (XNBR) is exploited to coordinate with ferric ions (Fe3+), resulting in a cross-linked rubber composite via a simple but efficient approach. FeCl3 content could be reached as high as 30 mmol, for a practically usable composite, by judiciously employing a tertiary aliphatic amine viz. triethylamine, TEA that is otherwise not possible. The development of metal–ligand assisted cross-links in the XNBR matrix is established by rheological and swelling studies. The cross-linking mechanism and ferric-carboxylate interaction are investigated by Fourier transform infrared spectroscopy (FT-IR). Strong and favorable ferric-carboxylate interaction leads to adequate improvement of mechanical and viscoelastic properties of the composite. [ABSTRACT FROM AUTHOR]

Thermosetting polymers crosslinked through covalent bonds are widely used in various fields due to their excellent mechanical properties and chemical stability. However, the non-recyclable nature of their fossil-based constituents hinders their post-service recycling and reshaping. This not only results in resource waste but also leads to environmental pollution, contradicting the principles of green and sustainable development. Dynamic covalent crosslinks are incorporated to turn conventional thermoset into covalent adaptable networks (CANs), enabling them to be processible and recyclable via bond exchange under specific stimuli. Normal covalent adaptable networks are highly flammable, which limits their applications and poses safety hazards. This review aims to provide insights to address this challenge. The state of the art of the molecular design of flame retarded CANs is summarized and classified through types of dynamic covalent bonds including classical ester exchange, imine exchange, disulfide exchange, Diels Alder reaction and transformation based on recently developed diselenide bonds, borate esters bonds, phenol carbamate bonds. Mechanical strength, dynamic behavior and flame retardancy of each type of CANs are described and compared quantitatively. Furthermore, the future prospects and challenges for development and application of these novel high-performance polymeric materials will be discussed. [ABSTRACT FROM AUTHOR]

The results of a study on the kinetics of the decrease in strength of polyamide fibers made from polyamide PA-6 (poly-ε-caprolactam) irradiated in air with X-rays in the range of absorbed dose rates of 0.16–10 Gy/s are presented. It has been shown that the strength of irradiated polyamide fibers decreases to a certain limiting value depending on the dose rate and can be described by the rate law of a reversible pseudo-first-order reaction. A structural–kinetic model of radiation-oxidative aging of fibers is considered, which takes into account the opposite influence of degradation and crosslinking of tie macromolecules on the strength of the oriented polymer (fiber) and the structural features of the oriented polymer. The model agrees well with experiment and makes it possible to describe the change in the strength of an oriented polymer (fibers) and a unidirectional composite based on them while the processes of radiation-oxidative degradation and chain crosslinking occur simultaneously. [ABSTRACT FROM AUTHOR]

Modification and improvement of aging resistance in nuclear power environment for the ethylene‐propylene‐diene (EPDM) rubber has been attracting the attention of scientists. In this article, graphite modified EPDM composites (ultrafine graphite [UG]/EPDM) were prepared, and effect of graphite with sizes of 13, 2.6, and 1.3 μm on the processability, vulcanization parameters, mechanical properties, stability of radiation aging of EPDM composites were investigated, respectively. The results showed that EPDM rubber was an irradiated crosslinked polymer. The Mooney viscosity and crosslinking density of EPDM gradually increased with increasing graphite content under the effect of physical and chemical cross‐linking of graphite. The lamellar structure of graphite particles in the rubber matrix is beneficial to improvement of the mechanical properties and aging resistance of the EPDM composites and play a reinforcing role, and the sp2 hybrid structure of graphite can trap and quench free radicals, delayed the irradiation aging of EPDM. UG/EPDM composites irradiation stability was improved with increasing graphite dispersion in EPDM matrix. Under the cumulative irradiation dose of 1000 kGy, the tensile strength of blank sample and UG‐2.6 μm−10 decreased by 51.1% and 17.7%, respectively, and the hardness increased by 8.7% and 4.9%, respectively. The energy storage modulus and the corresponding glass transition temperature (Tg) of UG/EPDM composites enhanced with graphite, while the thermal stability of the composites was improved. [ABSTRACT FROM AUTHOR]

This paper reports hybrid gels combining a low‐molecular‐weight gelator (LMWG) and a photoinitiated crosslinked polymer gel (PG). The presence of the PG enhanced the stiffness and strength of the gel. The gels were loaded with heparin, and in the hybrid gel, the interpenetrated LMWG and PG networks somewhat restricted its release. In terms of stem cell growth, the hybrid gel significantly improved the performance of the PG because of the presence of the LMWG, which is an excellent substrate for stem cells in its own right. Furthermore, the presence of heparin in the hybrid gels also enhanced stem cell proliferation over longer timescales. Finally, these gels were photopatterned within the well‐plates used for tissue culture, with patterning helping control stem cell proliferation. In summary, these hybrid gels combine the advantageous features of both LMWG and PG: rheological performance is endowed by the PG with stem cell compatibility provided by the LMWG. The hybrid gels also control the release of the bioactive agent heparin and have capacity to be shaped and patterned. Patterned gels such as these, capable of directing stem cell growth, have potential in regenerative medicine. [ABSTRACT FROM AUTHOR]

Melt blending is a reliable and well‐demonstrated strategy for improving the mechanical, thermal, rheological, and surface properties of biopolymers. Poly(hydroxy‐3‐butyrate‐co‐3‐hydroxyvalerate) (PHBV) and poly(butylene adipate‐co‐terephthalate) (PBAT) are the two popular choices for blending polymers due to their diverse properties and complementary soil biodegradable behaviour. Due to their immiscibility, however, blending with the help of processing additives is necessary to reap the most significant benefits from this process and to avoid immiscibility issues. This study utilized the additives (peroxides and epoxy‐based chain extender) to compatibilize the biodegradable polymers PHBV and PBAT in a 60:40 blending ratio. The tensile strength and Young's modulus of the PHBV/PBAT(60/40) blend were improved by 32% and 64%, respectively, after adding a combination of peroxide (0.02 phr) and chain extender (0.3 phr) due to the formation of a complex network structure with increased chain length. The positive effect of an additive addition was also reflected by a 30°C increment in heat deflection temperature of biodegradable blend due to its high modulus value as supported by mechanical properties. The combined action of a peroxide and chain extender demonstrated a significantly higher complex viscosity of the PHBV/PBAT(60/40) blend due to the formation of a crosslinked polymer network as analyzed by rheological analysis. Our research demonstrated the effect of additives and their combined impact on analytical properties of PHBV/PBAT(60/40) blend to guide future work in improving their candidature to serve as a drop‐in solution in replacing non‐biodegradable petro‐based plastic products. [ABSTRACT FROM AUTHOR]

Organic–inorganic hybrid coating has been applied on metallic corrosion protection effectively. Molybdenum disulfide (MoS2) nanosheets with graphene-like two-dimensional lamellar structure were an anticorrosion inorganic additive, rendering the organic coating better corrosion resistant. However, the aggregation and poor solubility are still current issues that should be addressed. Functionalization MoS2 nanosheets with surface modified by polydopamine (PDA) and silane coupling agent (KH560) were prepared in polyurethane (PU) composite coatings to obtain dense and intact multilayer network structure coatings for corrosion protection. KH560-PDA-MoS2/PU coating with crosslinked polymer network structure has a high impedance modulus, large contact angle, and strong hydrophobicity. The coating meets the national technical standards for salt spray testing and nitric acid (HNO3) titration testing, demonstrating excellent corrosion resistance. [ABSTRACT FROM AUTHOR]

We report the synthesis of a heterogenous silver catalyst stabilized by bidentate N-heterocyclic carbene ligands. The heterogeneous nature of the catalyst is inherently derived from the unprecedented internal structural features observed for the catalyst. X-ray studies show that the silver complex forms a two-dimensional cross-linked system, where one dimension of the network is formed by inorganic polymer strings and the second direction is formed by the interconnection of these inorganic strings with NHC bidentate ligands. This organized internal arrangement renders the complex insoluble in many common organic solvents and enables its utilization as a reusable heterogeneous catalyst in multicomponent A3 coupling reactions. Notably, propargylic amines were obtained with yields of up to 97%, and the catalyst demonstrated reusability for six cycles. These results can facilitate the further development of heterogeneous NHC catalysts. [ABSTRACT FROM AUTHOR]

A series of poly(ethylene glycol)‐block‐poly(propylene glycol) (PEG/PPG)‐ and 5,6‐di(9H‐carbazol‐9‐yl)isoindoline‐1,3‐dione (2CZPImide)‐based crosslinked rubbery polymer membranes, denoted as PEG/PPG‐2CZPImide (x:y), are prepared from the norbornene‐functionalized PEG/PPG oligomer (NB‐PEG/PPG‐NB) and 2‐(bicyclo[2.2.1]hept‐5‐en‐2‐ylmethyl)‐5,6‐di(9H‐carbazol‐9‐yl)isoindoline‐1,3‐dione (2CZPImide‐NB) via ring‐opening metathesis polymerization (ROMP). The molar ratio (x:y) of the NB‐PEG/PPG‐NB (x) to 2CZPImide‐NB (y) monomers is varied from 10:1 to 6:1. X‐ray diffraction (XRD), scanning electron microscopy‐energy dispersive X‐ray spectroscopy (SEM‐EDS), and pure gas permeability studies reveal that the comonomer 2CZPImide‐NB successfully increases the d‐spacing among the crystalline PEG/PPG segments, hence enhancing the diffusivity of gases through the membranes. The synthesized membranes exhibit good CO2 separation performance, with CO2 permeabilities ranging from 311.1 to 418.1 Barrer and CO2/N2 and CO2/CH4 selectivities of 39.4–52.0 and 13.4–16.0, respectively, approaching the 2008 Robeson upper bound. Moreover, PEG/PPG‐2CZPImide (6:1), displaying optimal CO2 permeability and CO2/N2 and CO2/CH4 selectivities, shows long‐term stability against physical aging and plasticization resistance up to 20 days and 10 atm, respectively. [ABSTRACT FROM AUTHOR]

AbstractInverse vulcanization utilizes alkenyl monomers and elemental sulfur, an excessive by-product of oil and gas refineries, to synthesize dynamically crosslinked sulfur-rich polymers, therefore providing a new way to construct sustainable and versatile materials. The inverse vulcanization of the biological extracts and natural polymers gives rise to a variety of bio-based polysulfides aligning with the concept of green chemistry. In this paper, the development of synthesis strategies, corresponding mechanisms, scope of renewable cross-linking agents, and the properties as well as the potential applications of polysulfides are reviewed. In particular, the progress in the preparation of various polysulfides from fossil resources to bio-based counterparts is deliberated with multiple modification methods elucidated. The bio-derived polysulfides are proved to be outstanding materials and prominent alternatives for traditional petroleum-based products especially for the use as effective ion absorbents, Li-S battery cathode materials, adhesives and controlled release fertilizers, etc. Finally, a few prospects and challenges about the future of these intriguing sulfur-based polymers are raised and discussed. [ABSTRACT FROM AUTHOR]

A universal approach for enhancing water affinity in polymer photocatalysts by covalently attaching hydrophilic photocrosslinkers to polymer chains is presented. A series of bisdiazirine photocrosslinkers, each comprising bisdiazirine photophores linked by various aliphatic (CL‐R) or ethylene glycol‐based bridge chains (CL‐TEG), is designed to prevent crosslinked polymer photocatalysts from degradation through a safe and efficient photocrosslinking reaction at a wavelength of 365 nm. When employing the hydrophilic CL‐TEG as a photocrosslinker with polymer photocatalysts (F8BT), the hydrogen evolution reaction (HER) rate is considerably enhanced by 2.5‐fold compared to that obtained using non‐crosslinked F8BT photocatalysts, whereas CL‐R‐based photocatalysts yield HER rates comparable to those of non‐crosslinked counterparts. Photophysical analyses including time‐resolved photoluminescence and transient absorption measurements reveal that adding CL‐TEG accelerates exciton separation, forming long‐lived charge carriers. Additionally, the in‐depth study using molecular dynamics simulations elucidates the dual role of CL‐TEG: it enhances water penetration into the polymer matrix and stabilizes charge carriers after exciton generation against undesirable recombination. Therefore, the strategy highlights endowing a high‐permittivity environment within polymer photocatalyst in a controlled manner is crucial for enhancing photocatalytic redox reactivity. Furthermore, this study shows that this hydrophilic crosslinker approach has a broad applicability in general polymer semiconductors and their nanoparticulate photocatalysts. [ABSTRACT FROM AUTHOR]

Hydrogels are formed of crosslinked polymer chains arranged in three-dimensional (3D) networks. These chains have good water-containing capacity and are soft and malleable. Hydrogels have good biocompatibility due to their significant water content, flexible structure, and numerous holes. These characteristics make them analogous to biological tissues. Despite the publication of 8700 literature related to hydrogel biomedical applications in the past 52 years (1973 ~ 2024), studies on the use of hydrogels in biomedicine are few. To gain a comprehensive understanding of their current development status, research trends, and prospects in the biomedical application field, it is imperative to conduct a thorough retrospective analysis. In this study, we employ bibliometric analysis and CiteSpace software to quantitatively and visually analyze articles published in this field. Firstly, we provide a quantitative analysis of authorship and institutional publications over the past 52 years to elucidate the fundamental development status regarding hydrogel biomedical applications. Secondly, we did visual studies on terms that are high-frequency, explosive, keyword clustering, and so on, to understand the directionality and evolution of the main research hotspots during each period. Notably, our findings emphasize that fabricating hydrogels into wound healing-promoting dressings emerges as a prominent hotspot within the application field. We anticipate that this paper will inspire researchers with novel ideas for advancing hydrogel applications in biomedicine. [ABSTRACT FROM AUTHOR]

Reported herein is a continuous one‐step melt extrusion approach for high‐density polyethylene (HDPE) vitrimers. A grafting agent and a coagent were used to produce high‐performing vitrimers. Maleic anhydride (MA) served as a reactive agent to facilitate crosslinking, while dimethyl maleate (DM) acted as a grafting enhancer by reducing the surface energy of HDPE grafted with MA. For comparison, MA alone was also tested as a grafting agent. The vitrimers obtained displayed superior mechanical properties compared with HDPE. The storage modulus, as well as crystallinity, were determined for the HDPE vitrimers. These vitrimers are reprocessable, thus supporting recycling efforts despite their crosslinked nature, owing to very fast relaxation due to low activation energy for the transesterification reaction. Consequently, these vitrimers are not only recyclable but also exhibit enhanced thermal and mechanical properties compared with conventional HDPE. [ABSTRACT FROM AUTHOR]

Epoxy thermosets are indispensable in various industrial applications due to their exceptional material properties. However, their limited recyclability poses a significant challenge for sustainability. To address this issue, integrating recyclable imine moieties into epoxy systems has emerged as a promising strategy. Despite recent advancements, challenges persist concerning the hydrolytic stability of imine‐based epoxy thermosets and the formation of irregular oligomeric structures upon depolymerization. In this study, these shortcomings are solved by designing a liquid imine monomer with secondary amine functionalities, which is subsequently reacted with commercially available epoxy monomers to produce high‐performance epoxy thermosets. Remarkably, the developed imine‐based epoxy system shows no sign of hydrolysis even under high‐temperature aqueous conditions, underscoring its potential for various industrial applications. Only the treatment with aqueous HCl results in the selective formation of exclusively well‐defined molecules, in high isolated yields after depolymerization. Crosslinking these building blocks once again yields recycled polymers with properties identical to pristine material. Moreover, it is discovered that, despite the crosslinked nature of the epoxy thermoset, the complete dissolution of the intact polymer in dichloromethane allowed for simple solvent‐based recycling. Through design on the molecular level, the recycling of imine‐based epoxy polymers is achieved via chemical and solvent‐based techniques. [ABSTRACT FROM AUTHOR]

Stimuli‐responsive surfaces have garnered intensive research attention in addressing the challenges of severe information leakage problems, but they exhibit limitations in terms of intricate preparation and compatibility. Herein, the study reports a time‐dependent wrinkled surface controlled by photo‐induced stress relaxation of azobenzene‐ containing crosslinked polymer network comprised of furan‐containing polymer (PEA‐Fu) and maleimide‐substituted azobenzene (AZO‐2MI) as skin layer. Two kinds of wrinkled surfaces induced by two crosslinked networks (thermal‐ and UV‐induced) can be prepared by Diels‐Alder reaction and UV‐induced radical coupling reaction, exhibiting distinct amplitude decrease rate resulted from different stress relaxation rate induced by photo‐isomerization of azobenzene. By UV preprogramming with photomasks, various time‐dependent wrinkle patterns are obtained and can be identified at specific times under 450 nm irradiation. The time window for information read out can be preset through different UV preprogramming time and boundary conditions to achieve multi‐level information encryption. Furthermore, the written information can be camouflaged as another “false” information by regional‐selective irradiation under 450 nm irradiation, which offers a new method for information protection. Based on distinctive time‐dependent characteristics and excellent stability, this responsive wrinkled surface offers bright prospects in multi‐level information encryption. [ABSTRACT FROM AUTHOR]

Controlled release of low molecular weight hydrophilic drugs, administered locally, allows maintenance of high concentrations at the target site, reduces systemic side effects, and improves patient compliance. Injectable hydrogels are commonly used as a vehicle. However, slow release of low molecular weight hydrophilic drugs is very difficult to achieve, mainly due to a rapid diffusion of the drug out of the drug delivery system. Here we present an injectable and self-healing hydrogel based entirely on the self-assembly of liposomes. Gelation of liposomes, without damaging their structural integrity, was induced by modifying the cholesterol content and surface charge. The small hydrophilic molecule, sodium fluorescein, was loaded either within the extra-liposomal space or encapsulated into the aqueous cores of the liposomes. This encapsulation strategy enabled the achievement of controlled and adjustable release profiles, dependent on the mechanical strength of the gel. The hydrogel had a high mechanical strength, minimal swelling, and slow degradation. The liposome-based hydrogel had prolonged mechanical stability in vivo with benign tissue reaction. This work presents a new class of injectable hydrogel that holds promise as a versatile drug delivery system. The porous nature of hydrogels poses a challenge for delivering small hydrophilic drug, often resulting in initial burst release and shorten duration of release. This issue is particularly pronounced with physically crosslinked hydrogels, since their matrix can swell and dissipate rapidly, but even in cases where the polymers in the hydrogel are covalently cross-linked, small molecules can be rapidly released through its porous mesh. Here we present an injectable self-healing hydrogel based entirely on the self-assembly of liposomes. Small hydrophilic molecules were entrapped inside the extra-liposomal space or loaded into the aqueous cores of the liposomes, allowing controlled and tunable release profiles. [Display omitted] [ABSTRACT FROM AUTHOR]

Highlights The over‐loading of heat‐resistant fillers in silicone rubber creates a contradiction between heat resistance and mechanical properties, thus greatly limiting the durability of silicone rubber products in cutting‐edge applications and complex scenarios. To address this issue, silicone rubber was filled with octavinyl polyhedral oligomeric silsesquioxane (POSS) and carbon nanotubes (CNT) and crosslinked with 2,5‐dimethyl‐2,5‐di(tert‐butylperoxy)hexane (DBPMH) in an attempt to obtain composites with excellent mechanical properties and great thermal stability. Optical microscopy and X‐ray diffraction analyses revealed the size of POSS crystals decreased and the characteristic peaks disappeared after the peroxide crosslinked the polymer at elevated temperature. Specifically, silicone rubber composite filled with 0.1 phr POSS and 1.0 phr CNT exhibited a tensile strength of 10.2 MPa and elongation at a break of 450%. Further, the strength and elongation could be kept after thermo‐oxidative aging at 250°C for 32 h. Thermogravimetric analysis results demonstrate that the addition of POSS and CNT into silicone rubber exhibits a synergistic effect, markedly improving the thermal stability of the material. This method provides a valuable reference for manufacturing silicone rubber products that possess both excellent mechanical properties and high thermal stability under extreme working conditions. A novel silicone rubber composite with excellent mechanical properties and thermal stability was prepared. A small amount of octavinyl polyhedral oligomeric silsesquioxane (POSS) and carbon nanotubes exhibited a synergistic effect to improve thermal stability. The dependence of the morphological evolution of POSS crystals in SR on the 2,5‐dimethyl‐2,5‐di(tert‐butylperoxy)hexane and temperature was studied. [ABSTRACT FROM AUTHOR]

Poly(1,2,3‐triazolium) (PTAM) is a dynamic reversible crosslinking polymer based on 1,2,3‐triazolium. Structural rearrangement of PTAM can occur through dynamic exchange reactions of 1,2,3‐triazolium. But there are not any applications derived from the dynamic reversible crosslinking properties of 1,2,3‐triazolium. In the paper, to expand the function and application of PTAM, a reprocessable PTAM resin has been prepared and the reprocess ability is studied in detail. PTAM can achieve complete stress relaxation within 2 min at 160°C through the exchange reaction of dynamically reversible crosslinked 1,2,3‐triazolium. Under the condition of 160°C and 10 MPa pressure, PTAM can achieve mechanical properties recovery after 2 h of reprocessing. The recovery rate of tensile strength can reach 94.2%. After four consecutive cycles reprocessing, the recovery rate of tensile strength is maintained at about 90%. And the thermal stability of PTAM is unchanged. PTAM has a possible application in the recycling of thermoset‐based plastics and composites. The result provides a reference for the functional application and development of dynamic reversible crosslinking polymers. [ABSTRACT FROM AUTHOR]

Dihydrophenazine (DHP)-based cathode electrode materials have been considered as distinctive candidates for next-generation green batteries. However, limited efficient and cost-effective synthetic approaches are available so far. Herein, two ester-linked DHP-polymers (PPDC and PPTC) are effectively achieved through typical esterification reactions from industrial waste product phenazine. As cathode materials for lithium ion batteries, PPDC and PPTC exhibit superior performance with high specific capacities up to 180 and 120 mA h g−1, respectively, at a current density of 0.2 A g−1, long-term cycling stability (capacity remains of 109 and 78 mA h g−1, respectively, after 1000 cycles at a current density of 1.0 A g−1), and high rate capability (141 and 64 mA h g−1, respectively, at 2 A g−1). [ABSTRACT FROM AUTHOR]

The structure of the sidechain crosslinked Tyr‐Leu‐Trp peptide produced by the biarylitide crosslinking cytochrome P450Blt from Micromonospora sp. MW‐13 has been reanalysed by a series of NMR, computational and isotope labelling experiments and shown to contain a C−N rather than a C−O bond. Additional in vivo experiments using such a modified peptide show there is a general tolerance of biarylitide crosslinking P450 enzymes for histidine to tryptophan mutations within their minimal peptide substrate sequences despite the lack of such residues noted in natural biarylitide gene clusters. This work further highlights the impressive ability of P450s from biarylitide biosynthesis pathways to act as biocatalysts for the formation of a range of sidechain crosslinked tripeptides. [ABSTRACT FROM AUTHOR]

The structure of the sidechain crosslinked Tyr‐Leu‐Trp peptide produced by the biarylitide crosslinking cytochrome P450Blt from Micromonospora sp. MW‐13 has been reanalysed by a series of NMR, computational and isotope labelling experiments and shown to contain a C−N rather than a C−O bond. Additional in vivo experiments using such a modified peptide show there is a general tolerance of biarylitide crosslinking P450 enzymes for histidine to tryptophan mutations within their minimal peptide substrate sequences despite the lack of such residues noted in natural biarylitide gene clusters. This work further highlights the impressive ability of P450s from biarylitide biosynthesis pathways to act as biocatalysts for the formation of a range of sidechain crosslinked tripeptides. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The effect of spatial inhomogeneity on the dimensions of network polymers is investigated by using model networks containing highly crosslinked domains. It is found that the dimensions of network architecture consisting of densely crosslinked domains connected by long chains are larger than those of loosely crosslinked domains connected by short chains, given the cycle rank is the same. The cases with the domains connected by the domains are also investigated. In all cases, the dimensions are larger than the corresponding randomly crosslinked homogeneous networks. This is because the loosely crosslinked regions dominate the dimensions of network polymers. The master curve relationship found for the statistical networks is applicable also for the present types of spatial inhomogeneous network polymers when the cycle rank is increased to make the network well‐developed in a homologous series of networks. [ABSTRACT FROM AUTHOR]

Crosslinked polymer films, formed via sol–gel and UV photocrosslinking, serve as gel polymer electrolytes (GPEs) in lithium‐ion batteries. Combining polyurethane acrylate (PUA), polyurethane methacrylate (PUMA), pentaerythritol tetrakis (3‐mercaptopropionate) (PETMP), and 3‐mercaptopropyl trimetoxysilane (MPTMS) yields flexible membranes, enhancing stability and liquid electrolyte compatibility. The resulting GPE displays higher ionic conductivity (1.46 × 10−3 S cm−1) than Celgrad2500, with PUA‐PUMA's hydrophilicity and PETMP's SH groups preventing leakage. GPPF1, the developed GPE, offers improved ionic conductivity, a stable electrochemical window up to 3.8 V, and heightened safety for versatile energy storage systems. [ABSTRACT FROM AUTHOR]

[Display omitted] • One-step synthesis of hydroxyl-functionalized ionic hyper-cross-linked polymers. • IHCPs exhibited an outstanding CO 2 uptake of 157.5 mg·g−1 at 273 K and 1 bar. • The CO 2 adsorption was significantly influenced by the structure of the cross-linking agents. • IHCPs served as both efficient and easily recoverable catalysts for CO 2 conversion. • Enhanced the catalytic reactivity originated from a hydrogen bond synergistic catalytic effect. Ionic liquid-based functional materials have attracted significant attention for their distinctive structure in the field of CO 2 capture and conversion. In this work, a series of hydroxyl-functionalized ionic hyper-cross-linked polymers are prepared through a one-step Friedel-Crafts reaction involving hypoxanthine (HX) and benzimidazole (BI) as the monomers, along with various halohydrocarbon crosslinking agents. These polymers demonstrate a high specific surface area (558–1480 m2·g−1), well-developed microporous structure, and unique ion sites, enabling them to exhibit remarkable and reversible CO 2 adsorption properties. Particularly noteworthy is their CO 2 adsorption capacity, which surpasses that of similar ionic polymers documented in the literature, reaching 157.5 mg·g−1 at 273 K and 1 bar. Additionally, these polymers function as recyclable catalysts in the cycloaddition reaction of CO 2 and epoxides, enabling the conversion of CO 2 into cyclic carbonates with yields of up to 99 % even without a co-catalyst. Mechanism investigation reveals that the introduction of hydroxyl groups in the polymer is the key to improving catalytic activity through a synergistic catalytic effect. This research provides a novel concept for designing ionic functional materials with capabilities in both CO 2 adsorption and catalytic activity. [ABSTRACT FROM AUTHOR]

Owing to the highly targeted affinity of cytosine moieties toward the surface of cancer cells, cytosine-functionalized supramolecular nanogels undergo substantially enhanced specific uptake by cancer cells, which increases the cytotoxicity of the encapsulated anticancer drugs, thereby allowing safer, more effective induction of apoptosis in cancer cells. [Display omitted] • Supramolecular polymers containing cytosine groups (PECH-PEG-Cy) were developed. • PECH-PEG-Cy forms self-assembled nanogels with unique physical properties in water. • The nanogels with cytosine moieties exhibit high specificity for cancer cells. • Drug-loaded PECH-PEG-Cy selectively induces programmed cell death in cancer cells. • This new system has high potential for development of targeted cancer treatment. We demonstrate that cytosine moieties within physically cross-linked supramolecular polymers not only manipulate drug delivery and release, but also confer specific targeting of cancer cells to effectively enhance the safety and efficacy of chemotherapy—and thus hold significant potential as a new perspective for development of drug delivery systems. Herein, we successfully developed physically cross-linked supramolecular polymers (PECH-PEG-Cy) comprised of hydrogen-bonding cytosine pendant groups, hydrophilic poly(ethylene glycol) side chains, and a hydrophobic poly(epichlorohydrin) main chain. The polymers spontaneously self-assemble into a reversibly hydrogen-bonded network structure induced by cytosine and directly form spherical nanogels in aqueous solution. Nanogels with a high hydrogen-bond network density (i.e., a higher content of cytosine moieties) exhibit outstanding long-term structural stability in cell culture substrates containing serum, whereas nanogels with a relatively low hydrogen-bond network density cannot preserve their structural integrity. The nanogels also exhibit numerous unique physicochemical characteristics in aqueous solution, such as a desirable spherical size, high biocompatibility with normal and cancer cells, excellent drug encapsulation capacity, and controlled pH-responsive drug release properties. More importantly, in vitro experiments conclusively indicate the drug-loaded PECH-PEG-Cy nanogels can selectively induce cancer cell-specific apoptosis and cell death via cytosine receptor-mediated endocytosis, without significantly harming normal cells. In contrast, control drug-loaded PECH-PEG nanogels, which lack cytosine moieties in their structure, can only induce cell death in cancer cells through non-specific pathways, which significantly inhibits the induction of apoptosis. This work clearly demonstrates that the cytosine moieties in PECH-PEG-Cy nanogels confer selective affinity for the surface of cancer cells, which enhances their targeted cellular uptake, cytotoxicity, and subsequent induction of programmed cell death in cancer cells. [ABSTRACT FROM AUTHOR]

Patterning polymeric materials with controllable microstructures can meet diversified requirements and realize promising applications. Exploring micro‐/nano‐pattern methodology offers possibilities for future techniques, however, the self‐organized growth of polymeric materials has some limitations and the development of direct and noncontact patterning processes is still challenging. In this work, the study presents a facile strategy for endowing polymers with spatially regulated microstructures by direct photo‐printing, which incorporates both advantages of typical top‐down and bottom‐up approaches. By employing the photodimerization of anthracene‐containing semi‐crystallized polymers, the gradient crosslinking results in a mismatch of thermal expansion coefficients between the crosslinked surface and the uncrosslinked bottom layer. After heating treatment, constrained by the crosslinked surface, the uncrosslinked bottom polymer of the molten state in the exposed region tends to flow and migrate toward the unexposed region, similar to a volcanic eruption, which accurately determines the height and morphology of pattern. Besides, the well‐defined patterns can controllably grow upon thermal treatment due to phase transformation and migration. The versatility of the proposed strategy not only provides a brand‐new reliable platform to pattern functional materials with photo‐regulated and reversible microstructures, but also promotes the development of smart materials that can find applications in information safety, reversible microfluidics, and electronic devices. [ABSTRACT FROM AUTHOR]

Two novel chiral nematic cellulose nanocrystal (CNC) composite films composed of CNCs, gluconic acid (GA), polyvinyl pyrrolidone or polyacrylamide (CNC-GA-PVP and CNC-GA-PAM) were fabricated mainly by evaporation-induced self-assembly process. The visible iridescent color and chiral nematic structure of the obtained CNC-based films could be readily regulated by altering the content of GA in a wide color range. Both CNC composite films possessed good tensile strength. Worthy to be mentioned, the CNC-GA-PAM films exhibited rather high flexibility (elongation reached 222.53%) and could be curled into any shape, indicating the effective contribution of the polymer cross-linked networks from the non-ionic PAM. The reversible humidity responses were also observed for both CNC films with good sensitivity, probably due to the high hygroscopicity of GA. In addition, the CNC-GA-PAM films revealed exceptional water resistance without losing the regular chiral structure and structural color of CNCs. The influences of the content of tougheners and adding way of the polymers on the properties of CNC films were further investigated. This work presents a novel strategy for construction of multifunctional CNC-based nanomaterials for various applications. [ABSTRACT FROM AUTHOR]

Petroleum hydrocarbons (PHCs) are produced from industrial discharges, storage leakages, accidental spills, and operational failures. The hazardous nature of PHCs causes serious health risks and threatens the entire aquatic habitat. In this research work, the investigation of the removal of total petroleum hydrocarbons (TPHs) from the contaminated water is carried out utilizing a novel hypercross-linked resin, MAICY, which is generated by condensation of commercially available precursors. The chemical structures of MAICY have been examined extensively by FESEM, FT-IR, solid (CP-MAS) 13C-NMR, and TGA. A comprehensive analysis for adsorption parameters of TPHs has been performed, and different models such as Langmuir and Freundlich isotherms have been employed where the Freundlich isotherm was found to be the best fit for removal of THPs (R2= 0.9991). The results revealed that the performance of MAICY for the adsorption of TPHs from contaminated water gives a maximum adsorption capacity (qe) of 146 mg.g−1. The results of various parameters hinted that the contact time (0.25–4 h), the dosage of adsorbent (0.17 g/L), pH (7), and concentration of TPHs (26.5 mg/L) have controlled the overall adsorptive performance. Moreover, the kinetic data of qe(expt.) and qe(calc.) for adsorption of TPHs disclosed the regression values (R2) for pseudo-first order (R2= 0.9921) and pseudo-second order (R2= 0.9891). Additionally, based on CHI factor (X2) error estimations, the data was shown to be more consistent with pseudo-first-order kinetics. Moreover, MAICY demonstrated excellent reusability and recycling properties for up to four consecutive adsorption–desorption cycles. [ABSTRACT FROM AUTHOR]

Hydrogels endure various dynamic stresses, demanding robust mechanical properties. Despite significant advancements, matching hydrogels' strength to biological tissues and plastics is often challenging without applying potentially harmful crosslinkers. Using hydrogen bonds as sacrificial bonds offers a promising strategy to produce tough, versatile hydrogels for biomedical and industrial applications. Poly(methacrylic acid) (PMA)/gelatin hydrogels were synthesized by thermally induced free-radical polymerization and crosslinked only by physical bonds, without adding any chemical crosslinker. The addition of gelatin increased the formation of hydrophobic domains in the structure of the hydrogels, which acted as permanent crosslinking points. The increase in PMA and gelatin contents generally led to a lower equilibrium water content (WC), higher thermal stability and better mechanical properties. The values of tensile strength and toughness reached up to 1.44 ± 0.17 MPa and 4.91 ± 0.51 MJ m−3, respectively, while the compressive modulus and strength reached up to 0.75 ± 0.06 MPa and 24.81 ± 5.85 MPa, respectively, with the WC being higher than 50 wt.%. The obtained values for compressive mechanical properties are comparable with super-strong hydrogels reported in the literature. In addition, hydrogels exhibited excellent fatigue resistance and biocompatibility, as well as great shape memory properties, which make them prominent candidates for a wide range of biomedical applications. [ABSTRACT FROM AUTHOR]

Insulating ceramics are widely used in power systems, but their high polarity makes them prone to wet and pollution flashover. In this paper, an Ar/polydimethylsiloxane dielectric barrier discharge excited by a parametric nanosecond-pulse power source is utilized for plasma polymerization to enhance ceramic surface insulating performance. Diagnosis of the discharge characteristics and surface physiochemical properties is conducted at different repetition frequencies to investigate the mechanism associated with the relationship between repetition frequency and the plasma polymerization process. The results indicate that a superhydrophobic surface can be achieved at repetition frequencies above 2 kHz. This transformation brings about multiple effects, including a decrease in surface polarity, an increase in charge dissipation, and an improvement in surface dry and wet flashover voltages. It is discovered that the discharge mode shifts from homogeneous to filamentary due to the memory effect of high repetition frequencies. Additionally, several filaments are generated simultaneously during a single pulse, facilitating the polymerization reactions. For high repetition frequencies, a low-polarity silicon-containing film with micro-nanometer structures is deposited on the ceramic surface, while scattered polymer fragments are generated on the surface without a cross-linked film for repetition frequencies below 2 kHz, despite longer treatment durations. [ABSTRACT FROM AUTHOR]