Interpenetrated Network Research Articles

Ultrafast Luminescence Detection with Selective Adsorption of Carbon Disulfide in a Gold(I) Metal−Organic Framework

Although a widely used and important industrial chemical, carbon disulfide (CS2) also poses a number of hazards due to its volatility and toxicity. As such, the development of multifunctional materials for the selective capture and easy recognition of CS2 is one of the crucial issues. Herein, we demonstrate completely selective CS2 adsorption among trials involving H2O, alcohols, volatile organic compounds (including thiol derivatives), N2, H2, O2, CH4, CO, NO, and CO2. We also showcase its fine detection using remarkable luminescent response in an Au(I)‐based metal−organic framework (MOF) of {ZnII(pz)[AuI(CN)2]2} (pz = pyrazine; 1) with a two‐fold interpenetration network. Ex situ single crystal X‐ray diffraction for 1 and CS2 accommodated 1 suggested that the Au···Au atoms are not only luminescent centers but also act as interaction sites for CS2 modulating the Au···Au contacts. These experiments revealed the specificity of CS2 and how changes in the CS2‐induced structure. Based on the obtained structural formation, 1 exhibited a sensitive detecting ability for CS2 with an ultrafast response time of less than 10 s. Ex situ time‐resolved photoluminescence analyses developed in this work implied that CS2 varied the energetic relaxation at the excited states related to the luminescent efficiency of the resultant MOF system.

Single-Crystalline 3D Covalent Organic Frameworks with Exceptionally High Specific Surface Areas and Gas Storage Capacities.

Single-crystalline covalent organic frameworks (COFs) are highly desirable toward understanding their pore chemistry and functions. Herein, two 50-100 μm single-crystalline three-dimensional (3D) COFs, TAM-TFPB-COF and TAPB-TFS-COF, were prepared from the condensation of 4,4',4″,4‴-methanetetrayltetraaniline (TAM) with 3,3',5,5'-tetrakis(4-formylphenyl)bimesityl (TFPB) and 3,3',5,5'-tetrakis(4-aminophenyl)bimesityl (TAPB) with 4,4',4″,4‴-silanetetrayltetrabenzaldehyde (TFS), respectively, in 1,4-dioxane under the catalysis of acetic acid. Single-crystal 3D electron diffraction reveals the triply interpenetrated dia-b networks of TAM-TFPB-COF with atom resolution, while the isostructure of TAPB-TFS-COF was disclosed by synchrotron single-crystal X-ray diffraction and synchrotron powder X-ray diffraction with Le Bail refinements. The nitrogen sorption measurements at 77 K disclose the microporosity nature of both activated COFs with their exceptionally high Brunauer-Emmett-Teller surface areas of 3533 and 4107 m2 g-1, representing the thus far record high specific surface area among imine-bonded COFs. This enables the activated COFs to exhibit also the record high methane uptake capacities up to 28.9 wt % (570 cm3 g-1) at 25 °C and 200 bar among all COFs reported thus far. This work not only presents the structures of two single-crystalline COFs with exceptional microporosity but also provides an example of atom engineering to adjust permanent microporous structures for methane storage.

Design of interpenetration network in light-based 3D printing for robust and sustainable dielectric insulators

The sustainability and additive manufacturing of dielectric insulators are the development direction of the power system. Introducing dynamic covalent bonds in light-based 3D printing have attracted considerable attention as the reversible crosslinks allow for the reprocessing of printed objects. However, there generally exists a trade-off between mechanical strength, glass transition temperature (Tg), and reconfigurability for dynamic covalent networks. The reconfiguring process of the dynamic covalent network often requires high mobility of molecular chains and large free volumes, which in turn decreases the mechanical strength, Tg, and electrical insulating performance. Herein, we demonstrate a novel strategy for developing a kind of mechanically robust and sustainable vitrimer by building a rigid-flexible coupling inter-penetration network (IPN). Specifically, a two-stage curing approach was used to prepare high-performance 3D-printing vitrimers by using the plant oil-epoxy hybrid resin, which brings a lot of ester bonds and β-hydroxyl ester for the crosslinking network. Computational techniques with molecular dynamics calculation are used for the design and optimization of the crosslinking network, and then the optimized IPN is prepared by digital light processing 3D printing and subsequent heat curing. In the IPN, the epoxy backbone is rigid to enhance the Tg and tensile strength, while the plant-based methacrylate is flexible to guarantee topological rearrangement at elevated temperatures. Compared to reported epoxy vitrimers, the resultant IPN exhibits simultaneous high Tg (111 °C), outstanding tensile strength and toughness (tensile strength of 70 MPa, elongation at break of 17.58 %), good topological rearrangement, and excellent dielectric properties (permittivity less than 4, breakdown strength of 49.3 kV/mm). This work provides a new strategy for balancing the strength, toughness, electrical insulating and sustainability of 3D-printed thermosets.

Central Metal-Triggered Structural Transformation of a 2D Layered MOF: Mechanistic Studies and Applications.

The structural transformation of metal-organic frameworks (MOFs) has attracted increasing interests, which has not only produced various new structures but also served as a fantastic platform for MOF-based kinetic analysis. Multiple reaction conditions have been documented to cause structural transformation; nevertheless, central metal-induced topological alteration of MOFs is rare. Herein, we reported a structural transformation of a 2D layered Cd-MOF driven by Cd(II) ions. After being submerged in the aqueous solution of cadmium nitrate, the twofold interpenetrated 2D network of [Cd(hsb-2)(bdc)·5H2O]n [HSB-W10; bdc: 1,4-benzenedicarboxylate; hsb-2:1,2-bis(4'-pyridylmethylamino)-ethane] was converted into a novel noninterpenetrated 2D network [Cd1.5(hsb-2)(bdc)1.5(H2O)2·H2O]n (HSB-W16). This partial dissolution-recrystallization process was investigated by integrating controlled experiments, 1H NMR spectra, and photographic tracking analysis. Furthermore, a novel strategy combining in situ multicomponent dye encapsulation and central metal-triggered structural transformation was developed for the fabrication of MOF materials with white-light emission. By adopting this strategy, different dye guest molecules were concurrently introduced into the HSB-W16 host matrix, leading to a range of white-light-emitting MOF composites. This work will enable detailed studies of solid-state transformations and demonstrate a promising application prospect for structural transformation.

Accelerated full-thickness skin wound tissue regeneration by self-crosslinked chitosan hydrogel films reinforced by oxidized CNC-AgNPs stabilized Pickering emulsion for quercetin delivery

BackgroundThe non-toxic self-crosslinked hydrogel films designed from biocompatible materials allow for controlled drug release and have gathered remarkable attention from healthcare professionals as wound dressing materials. Thus, in the current study the chitosan (CS) film is infused with oil-in-water Pickering emulsion (PE) loaded with bioactive compound quercetin (Qu) and stabilized by dialdehyde cellulose nanocrystal-silver nanoparticles (DCNC-AgNPs). The DCNC-AgNPs play a dual role in stabilizing PE and are involved in the self-crosslinking with CS films. Also, this film could combine the advantage of the controlled release and synergistic wound-healing effect of Qu and AgNPs.ResultsThe DCNC-AgNPs were synthesized using sodium periodate oxidation of CNC. The DCNC-AgNPs were used to stabilize oil-in-water PE loaded with Qu in its oil phase by high speed homogenization. Stable PEs were prepared by 20% v/v oil: water ratio with maximum encapsulation of Qu in the oil phase. The Qu-loaded PE was then added to CS solution (50% v/v) to prepare self-crosslinked films (CS-PE-Qu). After grafting CS films with PE, the surface and cross-sectional SEM images show an inter-penetrated network within the matrix between DCNC and CS due to the formation of a Schiff base bond between the reactive aldehyde groups of DCNC-AgNPs and amino groups of CS. Further, the addition of glycerol influenced the extensibility, swelling ratio, and drug release of the films. The fabricated CS-PE-Qu films were analyzed for their wound healing and tissue regeneration potential using cell scratch assay and full-thickness excisional skin wound model in mice. The as-fabricated CS-PE-Qu films showed great biocompatibility, increased HaCat cell migration, and promoted collagen synthesis in HDFa cells. In addition, the CS-PE-Qu films exhibited non-hemolysis and improved wound closure rate in mice compared to CS, CS-Qu, and CS-blank PE. The H&E staining of the wounded skin tissue indicated the wounded tissue regeneration in CS-PE-Qu films treated mice.ConclusionResults obtained here confirm the wound healing benefits of CS-PE-Qu films and project them as promising biocompatible material and well suited for full-thickness wound healing in clinical applications.Graphical

Carbodiimide‐Driven Toughening of Interpenetrated Polymer Networks

AbstractRecent work has demonstrated that temporary crosslinks in polymer networks generated by chemical “fuels” afford materials with large, transient changes in their mechanical properties. This can be accomplished in carboxylic‐acid‐functionalized polymer hydrogels using carbodiimides, which generate anhydride crosslinks with lifetimes on the order of minutes to hours. Here, the impact of the polymer network architecture on the mechanical properties of transiently crosslinked materials was explored. Single networks (SNs) were compared to interpenetrated networks (IPNs). Notably, semi‐IPN precursors that give IPNs on treatment with carbodiimide give much higher fracture energies (i.e., resistance to fracture) and superior resistance to compressive strain compared to other network architectures. A precursor semi‐IPN material featuring acrylic acid in only the free polymer chains yields, on treatment with carbodiimide, an IPN with a fracture energy of 2400 J/m2, a fourfold increase compared to an analogous semi‐IPN precursor that yields a SN. This resistance to fracture enables the formation of macroscopic complex cut patterns, even at high strain, underscoring the pivotal role of polymer architecture in mechanical performance.

Carbodiimide-Driven Toughening of Interpenetrated Polymer Networks.

Recent work has demonstrated that temporary crosslinks in polymer networks generated by chemical "fuels" afford materials with large, transient changes in their mechanical properties. This can be accomplished in carboxylic-acid-functionalized polymer hydrogels using carbodiimides, which generate anhydride crosslinks with lifetimes on the order of minutes to hours. Here, the impact of the polymer network architecture on the mechanical properties of transiently crosslinked materials was explored. Single networks (SNs) were compared to interpenetrated networks (IPNs). Notably, semi-IPN precursors that give IPNs on treatment with carbodiimide give much higher fracture energies (i.e., resistance to fracture) and superior resistance to compressive strain compared to other network architectures. A precursor semi-IPN material featuring acrylic acid in only the free polymer chains yields, on treatment with carbodiimide, an IPN with a fracture energy of 2400 J/m2, a fourfold increase compared to an analogous semi-IPN precursor that yields a SN. This resistance to fracture enables the formation of macroscopic complex cut patterns, even at high strain, underscoring the pivotal role of polymer architecture in mechanical performance.

Structure-Property Relationships of Granular Hybrid Hydrogels Formed through Polyelectrolyte Complexation.

Hybrid hydrogels are hydrogels that exhibit heterogeneity in the network architecture by means of chemical composition and/or microstructure. The different types of interactions, together with structural heterogeneity, which can be created on different length scales, determine the mechanical properties of the final material to a large extent. In this work, the microstructure-mechanical property relationships for a hybrid hydrogel that contains both electrostatic and covalent interactions are investigated. The hybrid hydrogel is composed of a microphase-separated polyelectrolyte complex network (PEC) made of poly(4-styrenesulfonate) and poly(diallyldimethylammonium chloride) within a soft and elastic polyacrylamide hydrogel network. The system exhibits a granular structure, which is attributed to the liquid-liquid phase separation into complex coacervate droplets induced by the polymerization and the subsequent crowding effect of the polyacrylamide chains. The coacervate droplets are further hardened into PEC granules upon desalting the hydrogel. The structure formation is confirmed by a combination of electron microscopic imaging and molecular dynamics simulations. The interpenetration of both networks is shown to enhance the toughness of the resulting hydrogels due to the dissipative behavior of the PEC through the rupture of electrostatic interactions. Upon cyclic loading-unloading, the hydrogels show recovery of up to 80% of their original dissipative behavior in less than 300 s of rest with limited plasticity. The granular architecture and the tough and self-recoverable properties of the designed hybrid networks make them good candidates for applications, such as shape-memory materials, actuators, biological tissue mimics, and elastic substrates for soft sensors.

Fast growth of single-crystal covalent organic frameworks for laboratory x-ray diffraction.

The imine-exchange strategy makes single-crystal growth of covalent organic frameworks (COFs) with large size (>15 microns) possible but is a time-consuming process (15 to 80 days) that has had limited success (six examples) and restricts structural characterization to synchrotron-radiation sources for x-ray diffraction studies. We developed a CF3COOH/CF3CH2NH2 protocol to harvest single-crystal COFs within 1 to 2 days with crystal sizes of up to 150 microns. The generality was exemplified by the feasible growth of 16 high-quality single-crystal COFs that were structurally determined by laboratory single-crystal x-ray diffraction with resolutions of up to 0.79 angstroms. The structures obtained included uncommon interpenetration of networks, and the details of the structural evolution of conformational isomers and host-guest interaction could be determined at the atomic level.

Charge-Assisted Ionic Hydrogen-Bonded Organic Frameworks: Designable and Stabilized Multifunctional Materials.

Hydrogen-bonded organic frameworks (HOFs) are a class of crystalline framework materials assembled by hydrogen bonds. HOFs have the advantages of high crystallinity, mild reaction conditions, good solution processability, and reproducibility. Coupled with the reversibility and flexibility of hydrogen bonds, HOFs can be assembled into a wide diversity of crystalline structures. Since the bonding energy of hydrogen bonds is lower than that of ligand and covalent bonds, the framework of HOFs is prone to collapse after desolventisation and the stability is not high, which limits the development and application of HOFs. In recent years, numerous stable and functional HOFs have been developed by π-π stacking, highly interpenetrated networks, charge-assisted, ligand-bond-assisted, molecular weaving, and covalent cross-linking. Charge-assisted ionic HOFs introduce electrostatic attraction into HOFs to improve stability while enriching structural diversity and functionality. In this paper, we review the development, the principles of rational design and assembly of charge-assisted ionic HOFs, and introduces the different building block construction modes of charge-assisted ionic HOFs. Highlight the applications of charge-assisted ionic HOFs in gas adsorption and separation, proton conduction, biological applications, etc., and prospects for the diverse design of charge-assisted ionic HOFs structures and multifunctional applications.

ENHANCING CARTILAGE TISSUE FORMATION IN GELMA/ALGINATE-TYRAMINE INTERPENETRATED NETWORKS (IPNS) WITH LOW INTENSITY PULSE ULTRASOUND STIMULATION (LIPUS)

In the native articular cartilage microenvironment, chondrocytes are constantly subjected to dynamic physical stimuli that maintains tissue homeostasis. They produce extra cellular matrix (ECM) components such as collagens (type II mainly, 50-75%), proteoglycans (10-30%) and other type of proteins1 . While collagen offers a large resistance in tension, proteoglycans are the responsible of the viscoelastic response under compression due to the negative charge they confer to the ECM allowing it to entrap a large amount of interstitial fluid. In pathologic states (e.g. osteoarthritis), this ECM is degenerated and the negative charge becomes unbalanced, losing the chondroprotective properties and resulting on an overloaded chondrocytes that further degenerate the matrix.Low-Intensity Pulsed Ultrasound Stimulation (LIPUS) has been used to generate acoustic (pressure) waves that create bubbles that collapse with cells, inducing a stimulus that can modulate cell response2. This mechanical stimulation promotes the expression of type II collagen, type X collagen, aggrecan and TGF-β, appearing as a great strategy to regenerate cartilage. However, current strategies make use of extrinsic forces to stimulate cartilage formation overlooking the physico-chemical properties of the degenerated cartilage, resulting in an excessive load-transfer to chondrocytes and the consequent hypertrophy and degeneration.Here, interpenetrated networks (IPNs) with different compositions were created using methacrylated gelatin (GelMA), to mimic the collagen, and alginate functionalized with tyramine (Alg-tyr) to mimic glycosaminoglycans and to introduce a negative charge in the model. Within the matrix chondrocytes where encapsulated and stimulated under different conditions to identify the ultrasound parameters that enhance tissue formation. Samples with and without stimulation were compared analysing the expression and deposition of collagen II, aggrecan, collagen X and TGF-β. The results suggested that the chondrogenic marker expression of the samples stimulated for 10 minutes per day for 28 days, was two times higher overall in all of the cases, which was correlated to the tissue formation detected.Acknowledgments: The authors would like to thank the Basque Government for the “Predoctoral Training Program for Non-Doctoral Research Staff 2021-2022” (Grant ref.: PRE_2021_1_0403). This work was supported by the RETOS grant PID2020-114901RA-I00 of the Ministry of Science and Innovation (MICINN).

Long-Term Follow-Up of the Behavior of Facial Volumizing Cross-Linked Hyaluronic Acid Gels

Introduction: We present the long-term follow-up photographic and MRI data on 4 patients 42-44 months after cross-linked Hyaluronic Acid (HA) gel injection into the temple region. All injected HA gels were produced using the registered and patented “Inter Penetration Network Like®” (IPN-Like® cross-linking technology) (LABORATOIRES VIVACY, France). The initial results following injection and up to 24 months were previously reported [1,2]. Material and methods: Our study population comprised 4 Caucasian patients who were enrolled into our two previous studies that compared Stylage XL versus Stylage XL-Lido (incorporating lidocaine added at manufacturing) [1] and Stylage XL versus Stylage XXL [2]. Patients, radiologists and the independent evaluators were blinded to the type of product used. The 4 patients were each injected in both temporal fossae using the 2 different HA gels being compared (one on either side). All patients had their follow-up at month 42 after injection (M42) with the exception of one patent who her MRI and photographs taken at the same setting on month 44 (M44). Photographic assessments were undertaken by the injector and 2 independent experts using Merz-Analogic Scale® (MAS®) and the Global Aesthetic Improvement Scale (GAIS). Results: Except for participant 2 (Stylage® XL vs. Stylage® XL-Lido) on the Stylage® XL-Lido side, all the other participants were considered to have a degree of persisting improvement compared to baseline, according to experts scoring of photographs on MAS and GAIS, However, there was a gradual deterioration in the level of improvement compared to the other assessment time-points. MRI: Although the bolus of injected gel was spherical at D0, we observed a change in the shape of the implant over time on MRI, where it changed from a round to a “teardrop” shape. Slow resorption occurred from 18 months onwards. At M42-44, the gel appearance on MRI remained similar to that previously reported at M18. The MRI residual volume calculation showed persistent increased volume compared to the volume initially injected. The product location appeared stable. There were no radiological or clinical signs of inflammatory reaction in tissues adjacent to the gel. Conclusion: At long-term follow-up 42-44 months after initial injection there was still an improvement in the aesthetic appearance of the temporal fossa and the MRI images show the continued presence of the gel. We also noticed that Stylage®XL (without lidocaine) seemed to absorb more water than its counterpart with lidocaine. Likewise, Stylage® XL seemed to absorb more water than Stylage® XXL.

‘Green’ fabrication of PVC ultrafiltration membranes with high-flux and improved hydrophilicity by in-situ interpenetration of hydrophilic crosslinking networks

High-flux polyvinyl chloride (PVC) membranes with hydrophilic interpenetrating networks were fabricated by a ‘green’ (without toxic initiator) in-situ method in this study. The interpenetration between the polyvinyl chloride (PVC) molecules and the hydrophilic network was formed during the phase separation process, where the cross-linking was initialized by water in a solidification bath between siloxanes in aminopropyltrimethoxysilane-b-poly (ethylene glycol) diglycidyl ether synthesized in the PVC dissolution process. From the reconstruction of the PVC membrane, high hydrophilicity and porosity, and narrow pore size distribution have been achieved. As results, compared to the pristine membrane. the pure water flux was increased 17 times to 1177.4 L m−2 h−1, the flux recovery rate was increased by 15.9 %, and the strength was also increased slightly.

A novel Zn(II) coordination polymer with mixed N- and O-donor linker: Room temperature synthesis, comprehensive characterization and Hirshfeld surface analysis

The present study describes the room temperature synthesis of a new two-dimensional (2D) coordination polymer (CP) having the formula [Zn(H-PCA)2]n (CP1), where H-PCA stands for 4-pyrazolecarboxylate. The mixture of Zn(OAc)2·2H2O and multitopic mixed N- and O-donor 4-pyrazolecarboxylic acid (H2-PCA) were self-assembled in a one-pot in methanol. The synthesis produced good yield and purity, and this method makes it simple to obtain multigram quantities of CP1 within a short period. Notably, this synthetic method selectively deprotonates the carboxylic acid group while maintaining pyrazole moiety in its protonated form. CP1 has been characterized by single-crystal X-ray diffraction, FTIR spectroscopy, elemental analysis, scanning electron microscopy, thermogravimetric analysis and powder X-ray diffraction. CP1 exhibits a 4-connected, 2-fold interpenetrated 2D network with the point symbol {44.62} – sql net topology. Due to the presence of the protonated pyrazole, these 2D layers further extended into a three-dimensional (3D) non-porous supramolecular network through strong 'intermolecular' NH···O hydrogen bonds between adjacent layers. Additionally, a 3D Hirshfeld Surface analysis accompanied by quantitative 2D-fingerprint plots was also investigated to explore the 'intermolecular' interactions.

Synthesis of novel interpenetrated network for ocular co-administration of timolol maleate and dorzolamide hydrochloride drugs

In the present work, novel interpenetrated networks (IPNs) of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide) (SBMA) and poly(vinyl alcohol) (PVA) were prepared for the ocular co-administration of timolol maleate (TIM) and dorzolamide hydrochloride (DORZ), two drugs widely used for the treatment of glaucoma. The successful polymerization of SBMA, in the presence of PVA, led to the formation of semi-interpenetrated pSBMA-PVA networks (IPNs), in the form of sponges, exhibiting intrinsic antimicrobial properties attributed to SBMA. Fourier-transform infrared spectroscopy (FTIR) was utilized to confirm the successful synthesis of the IPNs. Further assessments, including contact angle and water sorption measurements, highlighted their significant hydrophilicity, a feature that makes them suitable for ocular applications. Differential scanning calorimetry (DSC) measurements indicated that PVA serves as a plasticizer, while an assessment of the water sorption capacity of these materials suggested that although the incorporation of PVA results in slightly less hydrophilic materials, the prepared sponges still remain sufficiently hydrophilic for ocular use. Following their characterization, the optimal pSBMA-PVA IPN was used to encapsulate TIM and DORZ. Irritation tests, performed using the HET-CAM method, confirmed that the drug-loaded sponges were safe and potentially well-tolerated for ophthalmic use. Finally, the co-release study for the two drugs revealed a sustained release pattern in both cases, while drug release from the sponges was primarily controlled by diffusion.

Poly[di-aqua-[μ-1,4-bis-(pyridin-4-ylmeth-yl)pip-era-zine][μ-4-(carboxyl-atoeth-yl)benzoato]nickel(II)

The title compound, [Ni(C10H8O4)(C16H20N4)(H2O)2]n, contains NiII cations octa-hedrally surrounded within an [O4N2] coordination set. The cations are linked by 4-(carb-oxy-eth-yl)benzoate (ceb) and 1,4-bis-(pyridin-4-ylmeth-yl)piperazine (bpmp) ligands into tri-periodic diamondoid (dia) networks. The fivefold inter-penetrated dia networks are held into the crystal structure by means of O-H⋯O hydrogen bonding between bound water mol-ecules and unligated carboxyl-ate O atoms of the ceb ligands.

A light-responsive wound dressing hydrogel: Gelatin based self-healing interpenetrated network with metal-ligand interaction by ferric citrate.

Interpenetrated network (IPN) hydrogels with desired mechanical properties were prepared based on gelatin. A copolymer of dimethyl aminoethyl methacrylate (DMAEMA) with 2-Acrylamido-2-methylpropane sulfonic acid (AMPS) in gelatin was chemically cross-linked with methylene bis acrylamide (MBA) to form a semi-IPN hydrogel. Also, IPN hydrogel is fabricated from the AMPS-co-DMAEMA and gelatin in the presence of ferric ions with both chemical and physical cross-linkers. According to the compression test, the metal-ligand interaction has a remarkable impact on the mechanical strength of hydrogel. Ferric ions caused a decrease in the pores size confirmed by the SEM images of hydrogels, resulting in preserving its mechanical stability during the swelling test due to a more robust structure of hydrogel. Ferric to ferrous ions reduction is observed under visible light irradiation, which results in a light-sensitive hydrogel with a higher rate of biodegradation compared to semi-IPN hydrogels. MTT assay results implied that the synthesized hydrogels are non-toxic for the L-929 cell line. Also, for more detailed investigations, histological studies are conducted as in vivo tests. With regards to the improvements of mechanical properties harnessed in IPN hydrogels by ferric ions along with the extraordinary self-healing capability, IPNs would be considered an appropriate option for tissue engineering.

Regulation of the Interface Compatibility of the 3D-Printing Interpenetration Networks Toward Reduced Structure Anisotropy and Enhanced Performances.

Digital light processing three-dimensional (DLP 3D) printing, as a promising manufacturing technology with the capability of fabricating 3D objects with complex shapes, typically develops inconsistent material properties due to the stair-stepping effect caused by weak layer-interface compatibility. Here, we report the regulation of the interface compatibility of the 3D-printing resin with versatile photocuring characteristics and the subsequent mechanical, thermal, and dielectric performances by introducing the interpenetration network (IPN). The preparation procedures, interface structure, flexural and tensile strength, modulus, and dielectric performances of the IPN are presented. The greater penetration depth in 3D printing and the subsequently thermocured epoxy network passing through the printing interface synergistically enhance the interface compatibility of 3D-printing samples, with an unobvious printing texture on the surface of the 3D-printing objects. The mechanical performances of the IPN demonstrate little anisotropy, with a bending strength twice as much as the photosensitive resin. Dynamic mechanical analysis of the IPN indicates that the storage modulus increases by 70% at room temperature and the glass transition temperature (Tg) increases by 57%. The dielectric performance of the IPN demonstrates a 36% decrease in dielectric constant and a 28.4% increase in breakdown strength. Molecular dynamics studies have shown that the IPN takes on higher nonbonded energies and hydrogen bonds than the photosensitive resin, indicating a stronger bonding force between molecular chains, thus leading to better physical properties. These results illustrate the effectiveness of the IPN toward enhanced 3D-printing interlayer compatibility for excellent mechanical, thermal, and electrical performances.

Engineering 3D Interpenetrated ZIF-8 Network in Poly(ethylene oxide) Composite Electrolyte for Fast Lithium-Ion Conduction and Effective Lithium-Dendrite Inhibition

A novel 3D ZIF-8 network-reinforced polyethylene oxide (PEO) composite polymer electrolyte (Z-C-PAN-PEO) is successfully built, in which the network with an interpenetrated structure is tactfully developed by in situ assembling ZIF-8 nanoparticles on electrospinning carboxylated polyacrylonitrile (C-PAN) nanofiber surfaces. ZIF-8 with high porosity and unsaturated open metal sites will act as the bridge between C-PAN nanofibers and the PEO matrix. It is proven that the selected ZIF-8 can play a significant role in facilitating Li+ conduction and transference by effectively interacting with the oxygen atoms of C–O–C to promote the segmental movement of PEO and immobilizing TFSI– anions to release more free Li+. The 3D interpenetrating structure of Z-C-PAN further enables the conduction channels more consecutive and long-ranged, endowing the Z-C-PAN-PEO electrolyte with an optimum ionic conductivity of 4.39 × 10–4 S cm–1 and a boosted Li+ transference number of 0.42 at 60 °C. Other improvements occurring in the reinforced electrolytes are the broaden electrochemical stability window of ∼4.9 V and sufficient mechanical strength. Consequently, the stable Li-plating/stripping for 1000 cycles at 0.1 mA cm–1 witnesses the splendid compatibility against Li dendrite. The cycling performance of LiFePO4/Z-C-PAN-PEO/Li cells with a reversible capacity of 116.2 mAh g–1 after 600 cycles at 0.2 C guarantees the long-term running potential in lithium metal batteries. This study puts forward new insights in designing and exploiting the active role of MOFs for high-performance solid polymer electrolytes.

Evaluation of a biobased polycarbonate interpenetrated network in a dental resin composite

Silanization of filler particles in a dental resin composite is achieved by the formation of Si-O-Si bonds, however, these bonds are especially vulnerable to hydrolysis because this covalent bond has a significant ionic character due to the electronegativity differences between the atoms. The objective of this study was to evaluate the use of an interpenetrated network (IPN) as alternative of silanization reaction and to assess its effect in selected properties of experimental photopolymerizable resin composites. The interpenetrate network was obtained during the photopolymerization reaction of organic matrix (BisGMA/TEGDMA) with a biobased polycarbonate. Its characterization was performed via FTIR, flexural strength, flexural modulus, depth of cure, sorption water and solubility. A resin composite formulated with non-silanized filler particles was used as control. The IPN with a biobased polycarbonate was successfully synthesized. The results showed that the IPN based resin composite had higher values of flexural strength, flexural modulus, and degree of double bond conversion than the control (p < 0.05). Polymerization shrinkage, water sorption and solubility were statistically significantly lower than the control resin (p < 0.05). Finally, this study shows there were no statistically significant differences for the biocompatibility outcomes (p > 0.05). The biobased IPN replaces the silanization reaction in resin composites, improving physical and chemical properties. Therefore, IPN with a biobased polycarbonate could be potentially useful in the formulation of dental resin composites.