Ethylene Oxide Research Articles

Attapulgite Enhanced Polyethylene Oxide-Polyvinylidene Difluoride-Based Composite Solid-State Electrolyte for All Solid State Li-Ion Batteries

We report an attapulgite-modified poly(ethylene oxide) (PEO) based solid-state composite electrolyte film by solution casting method. The influence of attapulgite and polyvinylidene difluoride (PVDF) on the electrical properties of PEO-based solid-state electrolytes was investigated and it is found that an optimal 3% attapulgite and 10% PVDF in the electrolyte film (0.9PEO-0.1PVDF-LiClO4-3% attapulgite) exhibited a high ionic conductivity of 2.55×10−4 S cm−1 at room temperature and electronic conductivity of 2.25×10−11 S cm−1. Furthermore, The LiFePO4/0.85PEO-0.15PVDF-LiClO4-3% attapulgite/Li all-solid battery exhibited a promising initial discharge capacity of 120 mAh g−1, and even after 10 cycles at 0.1 C, the specific capacity values of the all-solid battery remained above 60 mAh g−1.

Rapid-Response Water-Shrink Films with High Output Work Density Based on Polyethylene Oxide and α-Cyclodextrin for Autonomous Wound Closure.

Conventional wound closure methods, including sutures and tissue adhesives, present significant challenges for self-care treatment, particularly in the context of bleeding wounds. Existing stimuli-responsive contractile materials designed for autonomous wound closure frequently lack sufficient output work density to generate the force needed to bring the wound edges into proximity or necessitate stimuli that are not compatible with the human body. Here, semi-transparent, flexible, and water-responsive shrinkable films, composed of poly(ethylene oxide) and α-cyclodextrin, are reported. These films exhibit remarkable stability under ambient conditions and demonstrate significant contraction (≈50%) within 6 s upon exposure to water, generating substantial contractile stress (up to 6MPa) and output work density (≈1028kJ m-3), which is 100 times larger than that of conventional hydrogel and 25 times larger than that of skeletal muscles. Remarkably, upon hydration, these films are capable of lifting objects 10000 times their own weight. Leveraging this technology, water-shrink tapes, which, upon contact with water, effectively constrict human skin and autonomously close bleeding wounds in animal models within 10 seconds, are developed further. This work offers a novel approach to skin wound management, showing significant potential for emergency and self-care scenarios.

Catalytic Hydroxyethylation of Phenols with Renewable Ethylene Glycol Diester as an Alternative to Ethylene Oxide

AbstractPolyol esters are abundant bio‐based resources. Integration of polyol esters into the production chain of fine chemicals would reduce carbon emissions and improve the sustainability of the chemical industry. An efficient synthetic route to phenoxyethanols was developed through catalytic hydroxyethylation of phenols with ethylene glycol diacetate as the reagent. This method showed the potential of ethylene glycol diester as a safe and sustainable substitute for ethylene oxide, a useful but toxic reagent. A variety of phenoxyethanol esters were produced in high yield under simple catalytic conditions. Mechanistic studies revealed that the reaction underwent a neighboring group participation process.

Coal-Based Branched Vicinal Diol Ethoxylates Versus Guerbet Alcohol Ethoxylates: Role of Tertiary Hydroxyl Groups.

Branched surfactants exhibit a lower surface tension, excellent low defoaming performance, and better wetting ability compared with linear surfactants, making them promising for applications in industrial cleaning. In this study, 2-hexyl-1-decene (C8 olefin dimer), obtained from the dimerization of 1-octene, was used as the hydrophobe to synthesize branched nonionic surfactants via hydroxylation and ethoxylation. The hydroxylation of the C8 olefin dimer to synthesize 2-hexyldecane-1,2-diol (C8 BD) using H2O2 and HCOOH was investigated systematically. Under the optimal reaction conditions (H2O2/C8 olefin dimer molar ratio: 1.5, HCOOH/C8 olefin dimer molar ratio: 4.0, reaction time: 10 h, reaction temperature: 50 °C), the conversion of the C8 olefin dimer and selectivity toward C8 BD were found to reach 99.96 and 79.89%, respectively. Further, branched nonionic surfactants (C8 BDEn) were synthesized via ethoxylation of C8 BD with ethylene oxide and characterized using FTIR, LCMS, 1H NMR, and 13C NMR techniques. The presence of a tertiary hydroxyl group in C8 BD increases the reactivity of the primary hydroxyl group, leading to a narrower range of products and lower residual substrate content. The physicochemical properties and surface properties of C8 BDEn with different degrees of ethoxylation at various concentrations were investigated and compared with those of commercially available Guerbet alcohol polyoxyethylene ethers (C8 GAEO9 and C6 GAEO9). The results show that, compared with C8 GAEO9 and C6 GAEO9, C8 BDE6 displayed a higher surface activity with a lower equilibrium surface tension (27.14 mN·m-1), superior wettability with a smaller contact angle (39.2°), better emulsification performance with a longer emulsification time of 548 s, and excellent foaming properties (initial foam volume of 11.6 mL). This strategy of utilizing coal-based α-olefins for the synthesis of branched nonionic surfactants presents a route to prepare value-added fine chemicals from coal-based resources.

Contact Angle Modulation: In Situ Polymer Deposition during Sessile Drop Evaporation.

The drying kinetics of a sessile drop on a solid surface are a widely studied phenomenon because of their relevance to various fields such as coating, printing, medical diagnostics, sensing, and microfluidic technology. Typically, the drop undergoes drying either at a constant contact radius (R) with a decrease in the three-phase contact angle or at a constant contact angle (θ) with a reduction in the radius with time. These two drying modes are referred to as CCR and CCA, respectively. It is not uncommon where both R and θ may decrease during drying, especially in the penultimate stage of drying. In this work, we report a scenario wherein the θ increases while R decreases during the drying process of an aqueous polymer solution on a high surface energy substrate. This behavior is observed across different polymer systems (such as poly(ethylene oxide) and polyvinyl pyrrolidine), varying molecular weights, and polymer concentrations. As the drop dries, the polymer gets deposited at the three-phase contact line, thus reducing the surface energy of the substrate and leading to an increase in the contact angle. The drop responds by attempting to reach a new equilibrium contact angle through slipping. The temporal increase in contact angle follows a power law scaling behavior. This study demonstrates an in situ modulation of contact angle facilitated by evaporation and polymer deposition, showcasing unconventional drying dynamics.

High-Strength, Thin, and Lightweight Solid Polymer Electrolyte for Superior All-Solid-State Sodium Metal Batteries.

The utilization of solid polymer electrolytes (SPEs) in all-solid-state sodium metal batteries has been extensively explored due to their excellent flexibility, processability adaptability to match roll-to-roll manufacturing processes, and good interfacial contact with a high-capacity Na anode; however, SPEs are still impeded by their inadequate mechanical strength, excessive thickness, and poor stability with Na anodes. Herein, a robust, thin, and cost-effective polyethylene (PE) film is employed as a skeleton for infiltrating poly(ethylene oxide)-sodium bis(trifluoromethanesulfonyl)imide (PEO/NaTFSI) to fabricate PE-PEO/NaTFSI SPE. The resulting SPE features a remarkable thickness of 25 μm, lightweight property (2.1 mg cm-2), superior mechanical strength (tensile strength = 100.3 MPa), and good flexibility. The SPE also shows an ionic conductivity of 9.4 × 10-5 S cm-1 at 60 °C and enhanced interfacial stability with a sodium metal anode. Benefiting from these advantages, the assembled Na-Na symmetric cells with PE-PEO/NaTFSI show a high critical current density (1 mA cm-2) and excellent long-term cycling stability (3000 h at 0.3 mA cm-2). The all-solid-state Na||PE-PEO/NaTFSI||Na3V2(PO4)3 coin cells exhibit a superior cycling performance, retaining 93% of the initial capacity for 190 cycles when matched with a 6 mg cm-2 cathode loading. Meanwhile, the pouch cell can work stably after abuse testing, proving its flexibility and safety. This work offers a promising strategy to simultaneously achieve thin, high-strength, and safe solid-state electrolytes for all-solid-state sodium metal batteries.

Hybrid Single Crystals of Poly(ε‐caprolactone) Homopolymers and Poly(ε‐caprolactone)‐b‐Poly(ethylene oxide) Block Copolymers

AbstractHybrid single crystals (HSCs) of different poly(ε‐caprolactone) (PCL) homopolymers with a poly(ε‐caprolactone)‐b‐poly(ethylene oxide) (PCL‐b‐PEO) block copolymer (BCP) are prepared. The effects of PCL length, PCL/PCL‐b‐PEO molar ratio, crystallization temperature (Tc), and solvent on crystal morphology are investigated. The optimal Tc for the formation of more perfect HSCs is between those for homocrystals of individual PCL and PCL‐b‐PEO and roughly increases with the length of PCL and PCL/PCL‐b‐PEO molar ratio. The chain folding in the HSCs is studied by comparing the experimentally measured heights obtained by atomic force microscopy (AFM) and theoretically calculated ones based on a sandwich structure model. Under most situations, the PCL homopolymers adopt a larger chain folding number in the HSCs than that in their homocrystals, while the chain folding of BCP remains unaltered. However, when both PCL homopolymer and PCL‐b‐PEO BCP crystallize slowly and the overcrowding of the PEO is effectively alleviated, thicker HSCs can be formed, in which the PCL homopolymer preserves the chain folding in its homocrystals but the BCP adopts a reduced chain folding number as compared with that in its homocrystals. The relative crystallization rate of PCL homopolymer versus BCP also affects the real composition and overall height of the HSCs.

Molecular dynamics study of free volume coalescence around nonyl ethoxylate in polyethylene with vinyl acetate‐modified branches

AbstractPolyethylene (PE) is susceptible to environmental stress cracking (ESC). In the presence of an amphiphilic compound and subjected to stress, ESC starts with cavitation followed by slow crack growth and ends with brittle fracture. In this study, we used molecular dynamics simulation to study how branch ends which were chemically modified with vinyl acetate groups affect free volume coalescence around an amphiphilic compound, nonyl ethoxylate (NE), dispersed in branched PE models. Branch ends modified with vinyl acetate significantly impact the free volume coalescence dynamics around NE. Compared with methyl branch ends, vinyl acetate branch ends show a much higher affinity, as quantified by the corresponding radial distribution functions, for the hydrophilic ethylene oxide‐segment of NE. However, this is not the case for the hydrophobic ethylene‐segment. Interestingly, vinyl acetate branch ends tend to reduce the power (amplitude) of the free volume size fluctuations around both the ethylene oxide‐ and ethylene‐segments. Indeed, the powers of the fluctuations with different PE branching characteristics decrease with increasing vinyl acetate concentration. We believe that free volume coalescence leads to cavitation and that vinyl acetate branches could inhibit cavitation, thereby crack propagation in PE. The power results seem to be consistent with the experimental observation that the addition of copolymer ethylene vinyl acetate to low‐density polyethylene improves the ESC resistance of the blend.Highlights Vinyl acetate branches reduce free volume coalescence activities. Vinyl acetate branches are attracted to the hydrophilic segment of NE. Cavitation likely starts from the free volume coalescence around NE.

A highly flexible and adhesive polymer electrolyte with fast ion conduction prepared via UV-induced in-situ polymerization for lithium metal batteries

Cathode–electrolyte integration via in-situ polymerization is an effective strategy to reduce interfacial resistance in solid-state/quasi-solid-state lithium batteries; however, ion conduction in the fraction of polymer electrolyte is still to be enhanced. Herein, we demonstrate a separator-free cathode–electrolyte integrated structure employing a novel poly(di(ethylene glycol) ethyl ether acrylate)-based quasi-solid polymer electrolyte (LiTFSI-poly(DEGA)-FEC QSPE, denoted as PDEGA-QSPE), prepared via UV-assisted in-situ polymerization. Poly(DEGA) as a linear polymer contains abundant ethylene oxide (EO) segments in its branched chain, exhibiting excellent flexibility and high adhesion. Benefited from the flexible molecular structure, PDEGA-QSPE exhibits a glass transition temperature (Tg) as low as around −68 °C and a good room-temperature ionic conductivity of 2.3 × 10−4 S cm−1, and it also shows an oxidative potential up to 4.7 V. The LiFePO4|PDEGA-QSPE|Li battery possesses an initial capacity of 149.2 mAh g−1 and a capacity retention of 92.5 % after 300 cycles at 0.2C under room temperature, and poly(DEGA)-based QSPE also has the potential to be applied to the high-voltage NCM811||Li battery. Compared with widely-employed monomers for in-situ polymerization such as poly(ethylene glycol) diacrylate (PEGDA), poly(DEGA) possesses remarkably improved flexibility and ion conduction capability, exhibiting broad research and application prospects.

The role of chlorine promoters in mediating particle size effects in silver-catalyzed ethylene epoxidation

Measured chlorine coverages over Ag/α-Al2O3 catalysts with varying Ag weight loadings (1.3–35 wt%) and different Ag particle size distributions when parsed in terms of Cl coverages over particles of varying size constituted in the distribution reveal that Ag particles of size below ∼30 nm are covered in more than 1 monolayer (ML) of chlorine in presence of 3.5 ppm C2H5Cl. These assessments of Cl coverages were made possible by correlating the cumulative Cl coverage to the lognormal surface area distribution of 22 Ag/α-Al2O3 samples using a single exponential decay function. Fully chlorided small Ag particles exhibit low rates of epoxidation and only large Ag particles which exhibit sub-monolayer Cl coverages catalyze ethylene epoxidation with high ethylene oxide (EO) rates and selectivity. The Ag particle size dependence of Cl coverages plausibly explains why ≥ 100 nm Ag particles are typical in promoted Ag/α-Al2O3 ethylene epoxidation catalysts.

Regulating Zn2+Migration-Diffusion Behavior by Spontaneous Cascade Optimization Strategy for Long-Life and Low N/P Ratio Zinc Ion Batteries.

Parasitic side reactions and dendrite growth on zinc anodes are formidable issues causing limited lifetime of aqueous zinc ion batteries (ZIBs). Herein, a spontaneous cascade optimization strategy is first proposed to regulate Zn2+ migration-diffusion behavior. Specifically, PAPE@Zn layer with separation-reconstruction properties is constructed in-situ on Zn anode. In this layer, well-soluble poly(ethylene oxide) (PEO) can spontaneously separation to bulk electrolyte and weaken the preferential coordination between H2O and Zn2+ to achieve primary optimization. Meanwhile, poor-soluble polymerized-4-acryloylmorpholine (PACMO) is reconstructed on Zn anode as hydrophobic flower-like arrays with abundant zincophilic sites, further guiding the de-solvation and homogeneous diffusion of Zn2+ to achieve the secondary optimization. Cascade optimization effectively regulates Zn2+ migration-diffusion behavior, dendrite growth and side reactions of Zn anode are negligible, and the stability is significantly improved. Consequently, symmetrical cells exhibit stability over 4000 h (1 mA cm-2). PAPE@Zn//NH4+-V2O5 full cells with a high current density of 15 A g-1 maintains 72.2% capacity retention for 12000 cycles. Even better, the full cell demonstrates excellent performance of cumulative capacity of 2.33 Ah cm-2 at ultra-low negative/positive (N/P) ratio of 0.6 and a high mass-loading (~17 mg cm-2). The spontaneous cascade optimization strategy provides novel path to achieve high-performance and practical ZIBs.

Lithium Borate Polycarbonates for High-Capacity Solid-State Composite Cathodes.

Improving composite cathode function is key to the success of the solid-state battery. Maximizing attainable cathode capacity and retention requires integrating suitable polymeric binders that retain a sufficiently high ionic conductivity and long-term chemo-mechanical stability of the cathode active material-solid-electrolyte-carbon mixture. Herein, we report block copolymer networks composed of lithium borate polycarbonates and poly(ethylene oxide) that improved the capacity (200 mA h g-1 at 1.75 mA cm-2) and capacity retention (94% over 300 cycles) of all-solid-state composite cathodes with nickel-rich LiNi0.8Co0.1Mn0.1O2 cathode active material, Li6PS5Cl solid electrolyte, and carbon. Tetrahedral B(OR)2(OH)2- anions immobilized on the polycarbonate segments provide hydrogen-bonding chain crosslinking and selective Li-counterion conductivity, parameterized by Li-ion transference numbers close to unity (tLi+ ~ 0.94). With 90 wt% polycarbonate content and a flexible low glass transition temperature backbone, the single-ion conductors achieved high Li-ion conductivities of 0.2 mS cm-1 at 30°C. The work should inform future binder design for improving the processability of cathode composites towards commercialising solid-state batteries, and allow use in other cell configurations, such as lithium-sulphur cathode designs.

Effects of Polymers on Cocrystal Growth in a Drug-Drug Coamorphous System: Relations between Glass-to-Crystal Growth and Surface-Enhanced Crystal Growth.

Coamorphous and cocrystal drug delivery systems provide attractive crystal engineering strategies for improving the solubilities, dissolution rates, and oral bioavailabilities of poorly water-soluble drugs. Polymeric additives have often been used to inhibit the unwanted crystallization of amorphous drugs. However, the transformation of a coamorphous phase to a cocrystal phase in the presence of polymers has not been fully elucidated. Herein, we investigated the effects of low concentrations of the polymeric excipients poly(ethylene oxide) (PEO) and poly(vinylpyrrolidone) (PVP) on the growth of carbamazepine-celecoxib (CBZ-CEL) cocrystals from the corresponding coamorphous phase. PEO accelerated the growth rate of the cocrystals by increasing the molecular mobility of the coamorphous system, while PVP had the opposite effect. The coamorphous CBZ-CEL system exhibited two anomalously fast crystal growth modes: glass-to-crystal (GC) growth in the bulk and accelerated crystal growth at the free surface. These two fast growth modes both disappeared after doping with PEO (1-3% w/w) but were retained in the presence of PVP, indicating a potential correlation between the two fast crystal growth modes. We propose that the different effects of PEO and PVP on the crystal growth modes arose from weaker effects of the polymers on cocrystallization at the surface than in the bulk. This work provides a deep understanding of the mechanisms by which polymers influence the cocrystallization kinetics of a multicomponent amorphous phase and highlights the importance of polymer selection in stabilizing coamorphous systems or preparing cocrystals via solid-based methods.

Multiaxial filament winding of biopolymer microfibers with a collagen resin binder for orthobiologic medical device biomanufacturing.

Multiaxial filament winding is an additive manufacturing technique used extensively in large industrial and military manufacturing yet unexplored for biomedical uses. This study adapts filament winding to biomanufacture scalable, strong, three-dimensional microfiber (3DMF) medical device implants for potential orthopedic applications. 
 Methods: Polylactide, polydioxanone, or nanocellulose microfiber filaments were wound through a collagen "resin" bath to create organized, stable orthobiologic implants, which are sized for common ligament (e.g., anterior cruciate ligament) and tendon (e.g., rotator cuff) injuries and can be manufactured at industrial scale using a small footprint, economical, high-output benchtop system. Ethylene oxide or electron beam sterilized 3DMF samples were analyzed by scanning electron microscopy (SEM), underwent ASTM1635-based degradation testing, tensile testing, ISO 10993-based cytocompatibility, and biocompatibility testing, quantified for human platelet-rich plasma (PRP) absorption kinetics, and examined for adhesion of bioceramics and lyophilized collagen after coating. 
 Results: 3DMF implants had consistent fiber size and high alignment by SEM. Negligible mass and strength loss were noted over 4 months in culture. 3DMF implants initially exceeded 1,000 N hydrated tensile strength and retained over 70% strength through 4 months in culture, significantly stronger than conventionally produced implants made by fused fiber deposition 3D printing. 3DMF implants absorbed over 3x their weight in PRP within 5 minutes, were cytocompatible and biocompatible, and could readily bind tricalcium phosphate and calcium carbonate coatings discretely on implant ends for further orthobiologic material functionalization. The additive manufacturing process further enabled engineering implants with suture-shuttling passages for facile arthroscopic surgical delivery. 
 Conclusion and Clinical Significance: This accessible, facile, economical, and rapid microfiber manufacturing platform presents a new method to engineer high-strength, flexible, low-cost, bio-based implants for orthopedic and extended medical device applications.&#xD.

Chiral Luminophore Guided Self-Assembly of Achiral Block Copolymers for the Amplification of Circularly Polarized Luminescence.

This work aims to examine the effect of self-assembly on the chiroptic responses of the achiral block copolymer (BCP) polystyrene-b-poly(ethylene oxide) (PS-b-PEO) associated with chiral luminophores, (R)- or (S)-1,1'-bi-2-naphthol ((R)- or (S)-BINOL), through hydrogen bonding. With the formation of a well-ordered helical phase (H*), significantly induced circular dichroism (ICD) signals for the PEO block in the mixture can be found. Most interestingly, a remarkable amplification with an extremely large dissymmetry factor of luminescence (glum) from 10-3 to 0.3 (i.e., induced circular polarized luminescence (iCPL) behavior) for the chiral BINOLs in the mixture can be achieved by the formation of the helical phase (H*) via mesochiral self-assembly. As a result, by taking advantage of BCP for mesochiral self-assembly, it is feasible to create a nanostructured monolith with substantial optical activities, offering promising applications in the design of chiroptic devices.

Influence of Screw Design and Process Parameters on the Product Quality of PEO:LiTFSI Solid Electrolytes Using Solvent-Free Melt Extrusion

All-solid-state battery (ASSB) technology is a new energy system that reduces the safety concerns and improves the battery performance of conventional lithium-ion batteries (LIB). The increasing demand for such new energy systems makes the transition from laboratory scale production of ASSB components to larger scale essential. Therefore, this study investigates the dry extrusion of poly(ethylene oxide):lithium bis (trifluoromethylsulfonyl)imide (PEO:LiTFSI) all-solid-state electrolytes at a ratio of 20:1 (EO:Li). We investigated the influence of different extruder setups on the product quality. For this purpose, different screw designs consisting of conveying, kneading and mixing elements are evaluated. To do so, a completely dry and solvent-free production of PEO:LiTFSI electrolytes using a co-rotating, intermeshing, twin-screw extruder under an inert condition was successfully carried out. The experiments showed that the screw design consisting of kneading elements gives the best results in terms of process stability and homogeneous mixing of the electrolyte components. Electrochemical impedance spectroscopy was used to determine the lithium-ion conductivity. All electrolytes produced had an ionic conductivity (σionic) of (1.1–1.8) × 10−4 S cm−1 at 80 °C.

Optimized Approach for Measuring Ethylene Oxide in Mobile Source Exhaust

Optimized Approach for Measuring Ethylene Oxide in Mobile Source Exhaust

Neuron‐Like Silicone Nanofilaments@Montmorillonite Nanofillers of PEO‐Based Solid‐State Electrolytes for Lithium Metal Batteries with Wide Operation Temperature

AbstractPoly(ethylene oxide) (PEO)‐based composite solid electrolytes (CSEs) are promising to accelerate commercialization of solid‐state lithium metal batteries (SSLMBs). Nonetheless, this is hindered by the CSEs’ limited ion conductivity at room temperature. Here, we propose design, synthesis, and application of the bioinspired neuron‐like nanofillers for PEO‐based CSEs. The neuron‐like superhydrophobic nanofillers are synthesized by controllably grafting silicone nanofilaments onto montmorillonite nanosheets. Compared to various reported fillers, the nanofillers can greatly improve ionic conductivity (4.9×10−4 S cm−1, 30 °C), Li+ transference number (0.63), oxidation stability (5.3 V) and mechanical properties of the PEO‐based CSEs because of the following facts. The distinctive neuron‐like structure and the resulting synaptic‐like connections establish numerous long‐distance continuous channels over various directions in the PEO‐based CSEs for fast and uniform Li+ transport. Consequently, the assembled SSLMBs with the CSEs and LiFePO4 or NCM811 cathodes display superior cycling stability over a wide temperature range of 50 °C to 0 °C. Surprisingly, the pouch batteries with the large‐scale prepared CSEs kept working after being repeatedly bent, folded, cut or even punched in air. We believe that design of neuron‐like nanofillers is a viable approach to produce CSEs with high room temperature ionic conductivity for SSLMBs.

Neuron-Like Silicone Nanofilaments@Montmorillonite Nanofillers of PEO-Based Solid-State Electrolytes for Lithium Metal Batteries with Wide Operation Temperature.

Poly(ethylene oxide) (PEO)-based composite solid electrolytes (CSEs) are promising to accelerate commercialization of solid-state lithium metal batteries (SSLMBs). Nonetheless, this is hindered by the CSEs' limited ion conductivity at room temperature. Here, we propose design, synthesis, and application of the bioinspired neuron-like nanofillers for PEO-based CSEs. The neuron-like superhydrophobic nanofillers are synthesized by controllably grafting silicone nanofilaments onto montmorillonite nanosheets. Compared to various reported fillers, the nanofillers can greatly improve ionic conductivity (4.9×10-4 S cm-1, 30 °C), Li+ transference number (0.63), oxidation stability (5.3 V) and mechanical properties of the PEO-based CSEs because of the following facts. The distinctive neuron-like structure and the resulting synaptic-like connections establish numerous long-distance continuous channels over various directions in the PEO-based CSEs for fast and uniform Li+ transport. Consequently, the assembled SSLMBs with the CSEs and LiFePO4 or NCM811 cathodes display superior cycling stability over a wide temperature range of 50 °C to 0 °C. Surprisingly, the pouch batteries with the large-scale prepared CSEs kept working after being repeatedly bent, folded, cut or even punched in air. We believe that design of neuron-like nanofillers is a viable approach to produce CSEs with high room temperature ionic conductivity for SSLMBs.

Synergistic Nanomedicine Delivering Topoisomerase I Toxin (SN-38) and Inhibitors of Polynucleotide Kinase 3'-Phosphatase (PNKP) for Enhanced Treatment of Colorectal Cancer.

Inhibitors of a DNA repair enzyme known as polynucleotide kinase 3'-phosphatase (PNKP) are expected to show synergistic cytotoxicity in combination with topoisomerase I (TOP1) inhibitors in cancer. In this study, the synergistic cytotoxicity of a novel inhibitor of PNKP, i.e., A83B4C63, with a potent TOP1 inhibitor, i.e., SN-38, against colorectal cancer cells was investigated. Polymeric micelles (PMs) for preferred tumor delivery of A83B4C63, developed through physical encapsulation of this compound in methoxy poly(ethylene oxide)-poly(α-benzyl carboxylate-ε-caprolactone) (mPEO-b-PBCL) micelles, were combined with SN-38 in free or PM form. The PM form of SN-38 was prepared through chemical conjugation of SN-38 to the functional end group of mPEO-b-PBCL and further assembly of mPEO-b-PBCL-SN-38 in water. Moreover, mixed micelles composed of mPEO-b-PBCL and mPEO-b-PBCL-SN-38 were used to co-load A83B4C63 and SN-38 in the same nanoformulation. The loading content (% w/w) of the SN-38 and A83B4C63 to mPEO-b-PBCL in the co-loaded formulation was 7.91 ± 0.66 and 16.13 ± 0.11% (w/w), respectively, compared to 15.67 ± 0.34 (% w/w) and 23.06 ± 0.63 (% w/w) for mPEO-b-PBCL micelles loading individual drugs. Notably, the average diameter of PMs co-encapsulating both SN-38 and A83B4C63 was larger than that of PMs encapsulating either of these compounds alone but still lower than 60 nm. The release of A83B4C63 from PMs co-encapsulating both drugs was 76.36 ± 1.41% within 24 h, which was significantly higher than that of A83B4C63-encapsulated micelles (42.70 ± 0.72%). In contrast, the release of SN-38 from PMs co-encapsulating both drugs was 44.15 ± 2.61% at 24 h, which was significantly lower than that of SN-38-conjugated PMs (74.16 ± 3.65%). Cytotoxicity evaluations by the MTS assay as analyzed by the Combenefit software suggested a clear synergy between PM/A83B4C63 (at a concentration range of 10-40 μM) and free SN-38 (at a concentration range of 0.001-1 μM). The synergistic cytotoxic concentration range for SN-38 was narrowed down to 0.1-1 or 0.01-1 μM when combined with PM/A83B4C63 at 10 or 20-40 μM, respectively. In general, PMs co-encapsulating A83B4C63 and SN-38 at drug concentrations within the synergistic range (10 μM for A83B4C63 and 0.05-1 μM for SN-38) showed slightly less enhancement of SN-38 anticancer activity than a combination of individual micelles, i.e., A83B4C63 PMs + SN-38 PMs at the same molar concentrations. This was attributed to the slower release of SN-38 from the SN-38 and A83B4C63 co-encapsulated PMs compared to PMs only encapsulating SN-38. Cotreatment of cells with TOP1 inhibitors and A83B4C63 formulation enhanced the expression level of γ-HA2X, cleaved PARP, caspase-3, and caspase-7 in most cases. This trend was more consistent and notable for PMs co-encapsulating both A83B4C63 and SN-38. The overall result from the study shows a synergy between PMs of SN-38 and A83B4C63 as a mixture of two PMs for individual drugs or PMs co-encapsulating both drugs.