Poly(ethylene Glycol) Diacrylate Research Articles

Dual-Catalysts-Embedded spontaneously propelling asymmetric micromotors using triple emulsion microfluidic synthesis for highly efficient nano/microplastic removal

Plastics, which are pivotal in modern technological progress and have a broad range of applications, now pose a significant environmental and health risk globally. Despite their detrimental environmental effects, there is a lack in research on effective plastic removal and treatment strategies. Addressing this urgent issue necessitates the development of innovative and efficient materials and methods for removing plastics from contaminated environments. In this study, we utilized a microfluidic technique to create novel and eco-friendly asymmetrically structured micromotors made of glucose oxidase (GOx)/catalase (Cat) embedded in polyethylene glycol diacrylate (PEGDA). These micromotors are specifically engineered to efficiently remove substantial amounts of plastics from ecosystems. The microfluidic process enabled the production of micromotors with uniform yet asymmetric shapes through aqueous two-phase separation and UV polymerization. By incorporating functional nanomaterials, these micromotors can be customized for specific wastewater treatment needs. Our design utilizes GOx and Cat to consume glucose as fuel, generating oxygen microbubbles. These bubbles not only propel the micromotors but also capture suspended plastic nano/micro-particles, effectively removing them from aquatic environments. The high surface tension of the bubbles allows for the entrapment of plastics at their interface, facilitating their removal from the water. In addition, non-toxic nature of these GOx/Cat PEGDA micromotors makes them especially suitable for environmental remediation and biological applications, addressing the urgent need for environmentally benign solutions to plastic pollution.

A Biomimetic Leaflet Scaffold for Aortic Valve Remodeling.

Heart valve disease poses a significant clinical challenge, especially in pediatric populations, due to the inability of existing valve replacements to grow or respond biologically to their microenvironment. Tissue-engineered heart valves (TEHVs) provide a solution by facilitating patient-specific models for self-repair and remodeling. In this study, a 3D bioprinted TEHV is designed to emulate the tri-layer leaflet structure of an aortic valve. A cell-laden hydrogel scaffold made from gelatin-methacrylate and polyethylene glycol diacrylate (GelMA/PEGDA) incorporates valvular interstitial-like (VIC-like) cells, being reinforced with a layer of polycaprolactone (PCL). The composition of the hydrogel scaffold remains stable over 7 days, having increased mechanical strength compared to pure GelMA. The scaffold maintains VIC-like cell function and promotes extracellular matrix (ECM) protein expression up to 14 days under two dynamic culture conditions: shear stress and stretching; replicating heart valve behavior within a more physiological-like setting and suggesting remodeling potential via ECM synthesis. This TEHV offers a promising avenue for valve replacements, closely replicating the structural and functional attributes of a native aortic valve, leading to mechanical and biological integration through biomaterial-cellular interactions. This article is protected by copyright. All rights reserved.

Injectable, stable, and biodegradable hydrogel with platelet-rich plasma induced by l-serine and sodium alginate for effective treatment of intrauterine adhesions

The combination of pharmacological and physical barrier therapy is a highly promising strategy for treating intrauterine adhesions (IUAs), but there lacks a suitable scaffold that integrates good injectability, proper mechanical stability and degradability, excellent biocompatibility, and non-toxic, non-rejection therapeutic agents. To address this, a novel injectable, degradable hydrogel composed of poly(ethylene glycol) diacrylate (PEGDA), sodium alginate (SA), and l-serine, and loaded with platelet-rich plasma (PRP) (referred to as PSL-PRP) is developed for treating IUAs. l-Serine induces rapid gelation within 1 min and enhances the mechanical properties of the hydrogel, while degradable SA provides the hydrogel with strength, toughness, and appropriate degradation capabilities. As a result, the hydrogel exhibits an excellent scaffold for sustained release of growth factors in PRP and serves as an effective physical barrier. In vivo testing using a rat model of IUAs demonstrates that in situ injection of the PSL-PRP hydrogel significantly reduces fibrosis and promotes endometrial regeneration, ultimately leading to fertility restoration. The combined advantages make the PSL-PRP hydrogel very promising in IUAs therapy and in preventing adhesions in other internal tissue wounds.

Digital light processing printing of porous ceramics using interparticle photo-cross-linkable Pickering emulsions

Digital light processing (DLP) printing using photo-curable Pickering emulsion is a promising route to fabricate porous ceramics having on-demand structures. However, the long duration for debinding/sintering due to the large organic contents remained in the photo-cured bodies and the insufficient long-term stability of the emulsions needs to be solved toward efficient manufacturing. Herein, a new interparticle photo-cross-linkable Pickering emulsion having improved stability, which can be photo-cured using reduced amounts of monomers, were designed for the rapid production of porous ceramics using DLP printing. The Pickering emulsion was obtained by mixing isopropyl myristate into a dimethyl sulfoxide (DMSO) aqueous suspension of SiO2 particles with pre-dissolved polyethylene glycol diacrylate (PEGDA) and a photo-radical initiator. Further, functionalized polyethyleneimine (PEI) was designed to ensure the dispersion of SiO2 particles and formation of a Pickering emulsion. The photo-irradiation of the designed Pickering emulsion resulted in the successful photo-curing by the radical polymerization of PEGDA, followed by a Michael addition reaction between the reactive amine of PEI and acryloyl groups of PEGDA. The improved stability of the emulsion over time and reduced amounts of monomer facilitated the application of the designed emulsion to DLP printing, followed by a rapid firing process without any structural collapse.

Structure-properties relationships of defined CNF single-networks crosslinked by telechelic PEGs

The high structural anisotropy and colloidal stability of cellulose nanofibrils' enable the creation of self-standing fibrillar hydrogel networks at very low solid contents. Adding methacrylate moieties on the surface of TEMPO oxidized CNFs allows the formation of more robust covalently crosslinked networks by free radical polymerization of acrylic monomers, exploiting the mechanical properties of these networks more efficiently. This technique yields strong and elastic networks but with an undefined network structure. In this work, we use acrylate-capped telechelic polymers derived from the step-growth polymerization of PEG diacrylate and dithiothreitol to crosslink methacrylated TEMPO-oxidized cellulose nanofibrils (MATO CNF). This combination resulted in flexible and strong hydrogels, as observed through rheological studies, compression and tensile loading. The structure and mechanical properties of these hydrogel networks were found to depend on the dimensions of the CNFs and polymer crosslinkers. The structure of the networks and the role of individual components were evaluated with SAXS (Small-Angle X-ray Scattering) and photo-rheology. A thorough understanding of hybrid CNF/polymer networks and how to best exploit the capacity of these networks enable further advancement of cellulose-based materials for applications in packaging, soft robotics, and biomedical engineering.

Molecularly Imprinted Macroporous Hydrogel Promotes Bone Regeneration via Osteogenic Induction and Osteoclastic Inhibition.

Macroporous hydrogels offer physical supportive spaces and bio-instructive environment for the seeded cells, where cell-scaffold interactions directly influence cell fates and subsequently affect tissue regeneration post-implantation. Effectively modifying bioactive motifs at the inner pore surface provides appropriate niches for cell-scaffold interactions. A molecular imprinting method and sacrificial templates are introduced to prepare inner pore surface modification in the macroporous hydrogels. In detail, acrylated bisphosphonates (Ac-BPs) chelating to templates (CaCO3 particles) are anchored on the inner pore surface of the methacrylated gelatin (GelMA)-methacrylated hyaluronic acid (HAMA)-poly (ethylene glycol) diacrylate (PEGDA) macroporous hydrogel (GHP) to form a functional hydrogel scaffold (GHP-int-BP). GHP-int-BP, but not GHP, effectively crafts artificial cell niches to substantially alter cell fates, including osteogenic induction and osteoclastic inhibition, and promote in situ bone regeneration. These findings highlight that molecular imprinting on the inner pore surface in the hydrogel efficiently creates orthogonally additive bio-instructive scaffolds for bone regeneration.

Fabrication of Perfluoropolyether Microfluidic Devices Using Laser Engraving for Uniform Droplet Production

A perfluoropolyether (PFPE)-based microfluidic device with cross-junction microchannels was fabricated with the purpose of producing uniform droplets. The microchannels were developed using CO2 laser engraving. PFPE was chosen as the main material because of its excellent solvent resistance. Polyethylene glycol diacrylate (PEGDA) was mixed with PFPE to improve the hydrophilic properties of the inner surface of the microchannels. The microchannels of the polydimethylsiloxane microfluidic device had a blackened and rough surface after laser engraving. By contrast, the inner surface of the microchannels of the PFPE-PEGDA microfluidic device exhibited a smooth surface. The lower power and faster speed of the laser engraving resulted in the development of microchannels with smaller dimensions, less than 30 μm in depth. The PFPE and PFPE-PEGDA microfluidic devices were used to produce uniform water and oil droplets, respectively. We believe that such a PFPE-based microfluidic device with CO2-laser-engraved microchannels can be used as a microfluidic platform for applications in various fields, such as biological and chemical analysis, extraction, and synthesis.

Bioinspired Flexible Hydrogelation with Programmable Properties for Tactile Sensing.

Tactile sensing requires integrated detection platforms with distributed and highly-sensitive haptic sensing capabilities along with biocompatibility, aiming to replicate the physiological functions of the human skin and empower industrial robotic and prosthetic wearers to detect tactile information. In this regard, short peptide-based self-assembled hydrogels show promising potential to act as bioinspired supramolecular substrates for developing tactile sensors showing biocompatibility and biodegradability. However, the intrinsic difficulty to modulate the mechanical properties severely restricts their extensive employment. Herein, by controlling the self-assembly of 9-fluorenylmethoxycarbonyl-modifid diphenylalanine (Fmoc-FF) through introduction of polyethylene glycol diacrylate (PEGDA), wider nanoribbons are achieved by untwisting from well-established thinner nanofibers, and the mechanical properties of the supramolecular hydrogels can be enhanced 10-fold, supplying bioinspired supramolecular encapsulating substrate for tactile sensing. Furthermore, by doping with PEDOT:PSS and 9-fluorenylmethoxycarbonyl-modifid 3,4-dihydroxy-L-phenylalanine (Fmoc-DOPA), the Fmoc-FF self-assembled hydrogels can be engineered to be conductive and adhesive, providing bioinspired sensing units and adhesive layer for tactile sensing applications. Therefore, the integration of these modules results in peptide hydrogelation-based tactile sensors, showing high sensitivity and sustainable responses with intrinsic biocompatibility and biodegradability. Our findings establish the feasibility of developing programmable peptide self-assembly with adjustable features for tactile sensing applications. This article is protected by copyright. All rights reserved.

Single-Cell Screening through Cell Encapsulation in Photopolymerized Gelatin Methacryloyl

This study evaluated the potential of gelatin methacryloyl (GelMA) for single-cell screening compared to polyethylene glycol diacrylate (PEGDA). GelMA photopolymerized at 1000–2000 mJ/cm2 produced consistent patterns and supported HeLa cell viability. GelMA (5%w/v) facilitated better cell collection within 2 days due to its shape retention. GelMA demonstrated biocompatibility with HeLa cells exhibiting exponential proliferation and biodegradation over 5 days. The average cell displacement over 2 days was 16 µm. Two targeted cell recovery strategies using trypsin were developed: one for adherent cells encapsulated at 800 mJ/cm2, and another for floating cells encapsulated at 800 mJ/cm2, enabling the selective removal of unwanted cells. These findings suggest GelMA as a promising biomaterial for single-cell screening applications, offering advantages over PEGDA in cell encapsulation and targeted recovery.

Conversion of Biopolymer to UV‐Cross‐Linkable Conductive Ink with High Conductivity, Biocompatibility, and Biodegradability

AbstractBiocompatible, sustainable, and conductive inks are of special interest and are highly valued in the printable bioelectronics. However, the conventional inks, which increase electrical conductivity by mixing metal particles or graphene, can cause long‐term damage when applied to the body and environment. Herein, a method for creating a stable matrix based on a UV‐cross‐linkable polymer to which a conductive polymer can be grafted is investigated to solve the above problems by recycling biomass. Through this, it is possible to achieve high conductivity using only biocompatible and sustainable polymers. Here, conductive inks for printable bioelectronics are developed by grafting polypyrrole on methacrylate‐modified sericin and poly(ethylene glycol) diacrylate (PEGDA). The highest electrical conductivity is achieved by adjusting the ratio of the pyrrole monomers polymerized on each polymer until the conductivity is optimized. Owing to the photoreactive nature of PEGDA, the prepared conductive inks are cross‐linked by UV light, thus giving them easy‐printing properties. The biodegradability, biocompatibility, and electrical properties of the printed patterns are systematically analyzed. This study has significant implications in the field of sustainable and printable bioelectronics as it has developed of a conductive ink with the biocompatibility, biodegradability, and high conductivity that is safer and simpler than conventional methods.

Unveiling the effect law of carbon dots with polyfunctional groups on interface structure and ion migration in polymer electrolytes for solid lithium battery

Solid polymer electrolyte (SPE) has been considered as promising candidate electrolyte for solid-state lithium metal battery. However, the low ion conductivity and poor interface stability seriously hinder the development of SPE. Introducing the functional filler is a commonly used and effective approach to solving these issues. The poor compatibility and ambiguous mechanism of action are currently the main challenges. In this study, we design and synthesize carbon dots (NSFCDs) with quaternary functional groups, which are introduced into the SPE in the polymerization process of hybrid polymer electrolyte (HPE). The detailed effect law of polyfunctional groups on the polymer chain structure, interface structure of electrolyte/electrode and ion migration is systematically revealed. The dense polymer network endows HPE with enhanced mechanical properties. Through the regulation of polymer segments, the coordination environment of lithium ions is altered, promoting ion transport. The solid electrolyte interface (SEI) induced by NSFCDs and lithium salt anions effectively improves the morphology of lithium ion deposition and alleviates volume strain. As a result, the HPE based on polyethylene oxide (PEO) constructed by free radical polymerization of NSFCDs and polyethylene glycol diacrylate (PEGDA) exhibits excellent comprehensive performance, the assembled Li symmetric battery can cycle stably for 4000 h.

In vitro evaluation of bone cell response to novel 3D-printable nanocomposite biomaterials for bone reconstruction.

Critically-sized segmental bone defects represent significant challenges requiring grafts for reconstruction. 3D-printed synthetic bone grafts are viable alternatives to structural allografts if engineered to provide appropriate mechanical performance and osteoblast/osteoclast cell responses. Novel 3D-printable nanocomposites containing acrylated epoxidized soybean oil (AESO) or methacrylated AESO (mAESO), polyethylene glycol diacrylate, and nanohydroxyapatite (nHA) were produced using masked stereolithography. The effects of volume fraction of nHA and methacrylation of AESO on interactions of differentiated MC3T3-E1 osteoblast (dMC3T3-OB) and differentiated RAW264.7 osteoclast cells with 3D-printed nanocomposites were evaluated in vitro and compared with a control biomaterial, hydroxyapatite (HA). Higher nHA content and methacrylation significantly improved the mechanical properties. All nanocomposites supported dMC3T3-OB cells' adhesion and proliferation. Higher amounts of nHA enhanced cell adhesion and proliferation. mAESO in the nanocomposites resulted in greater adhesion, proliferation, and activity at day 7 compared with AESO nanocomposites. Excellent osteoclast-like cells survival, defined actin rings, and large multinucleated cells were only observed on the high nHA fraction (30%) mAESO nanocomposite and the HA control. Thus, mAESO-based nanocomposites containing higher amounts of nHA have better interactions with osteoblast-like and osteoclast-like cells, comparable with HA controls, making them a potential future alternative graft material for bone defect repair.

Low-Concentration Gelatin Methacryloyl Hydrogel with Tunable 3D Extrusion Printability and Cytocompatibility: Exploring Quantitative Process Science and Biophysical Properties.

Three-dimensional (3D) bioprinting of hydrogels with a wide spectrum of compositions has been widely investigated. Despite such efforts, a comprehensive understanding of the correlation among the process science, buildability, and biophysical properties of the hydrogels for a targeted clinical application has not been developed in the scientific community. In particular, the quantitative analysis across the entire developmental path for 3D extrusion bioprinting of such scaffolds is not widely reported. In the present work, we addressed this gap by using widely investigated biomaterials, such as gelatin methacryloyl (GelMA), as a model system. Using extensive experiments and quantitative analysis, we analyzed how the individual components of methacrylated carboxymethyl cellulose (mCMC), needle-shaped nanohydroxyapatite (nHAp), and poly(ethylene glycol)diacrylate (PEGDA) with GelMA as baseline matrix of the multifunctional bioink can influence the biophysical properties, printability, and cellular functionality. The complex interplay among the biomaterial ink formulations, viscoelastic properties, and printability toward the large structure buildability (structurally stable cube scaffolds with 15 mm edge) has been explored. Intriguingly, the incorporation of PEGDA into the GelMA/mCMC matrix offered improved compressive modulus (∼40-fold), reduced swelling ratio (∼2-fold), and degradation rates (∼30-fold) compared to pristine GelMA. The correlation among microstructural pore architecture, biophysical properties, and cytocompatibility is also established for the biomaterial inks. These photopolymerizable bio(material)inks served as the platform for the growth and development of bone and cartilage matrix when human mesenchymal stem cells (hMSCs) are either seeded on two-dimensional (2D) substrates or encapsulated on 3D scaffolds. Taken together, this present study unequivocally establishes a significant step forward in the development of a broad spectrum of shape-fidelity compliant bioink for the 3D bioprinting of multifunctional scaffolds and emphasizes the need for invoking more quantitative analysis in establishing process-microstructure-property correlation.

Three-Dimensional Printed Filters Based on Poly(ethylene glycol) Diacrylate Hydrogels Doped with Silver Nanoparticles for Removing Hg(II) Ions from Water.

Nowadays, due to water pollution, more and more living beings are exposed to dangerous compounds, which can lead to them contracting diseases. The removal of contaminants (including heavy metals) from water is, therefore, a necessary aspect to guarantee the well-being of living beings. Among the most used techniques, the employment of adsorbent materials is certainly advantageous, as they are easy to synthesize and are cheap. In this work, poly(ethylene glycol) diacrylate (PEGDA) hydrogels doped with silver nanoparticles (AgNPs) for removing Hg(II) ions from water are presented. AgNPs were embedded in PEGDA-based matrices by using a photo-polymerizable solution. By exploiting a custom-made 3D printer, the filters were synthesized. The kinetics of interaction was studied, revealing that the adsorption equilibrium is achieved in 8 h. Subsequently, the adsorption isotherms of PEGDA doped with AgNPs towards Hg(II) ions were studied at different temperatures (4 °C, 25 °C, and 50 °C). In all cases, the best isotherm model was the Langmuir one (revealing that the chemisorption is the driving process and the most favorable one), with maximum adsorption capacities equal to 0.55, 0.57, and 0.61 mg/g, respectively. Finally, the removal efficiency was evaluated for the three temperatures, obtaining for 4 °C, 25 °C, and 50 °C the values 94%, 94%, and 86%, respectively.

In Situ Polymerized Quasi-Solid Electrolytes Compounded with Ionic Liquid Empowering Long-Life Cycling of 4.45 V Lithium-Metal Battery.

High-voltage resistant quasi-solid-state polymer electrolytes (QSPEs) are promising for enhancing the energy density of lithium-metal batteries in practice. However, side reactions occurring at the interfaces between the anodes or cathodes and QSPEs considerably reduce the lifespan of high-voltage LMBs. In this study, a copolymer of vinyl ethylene carbonate (VEC) and poly(ethylene glycol) diacrylate (PEGDA) was used as the framework, with a cellulose membrane (CE) as the supporting layer. Based on density functional theory calculations, 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI), an ionic liquid, was screened because of its lowest unoccupied molecular orbital energy level as a modifying agent for the in situ P(VECx-EGy)/Pyrz/LiTFSI@CE QSPEs synthesis. Pyr14+, with a lithiophobic alkyl chain, forms a dense positive ion shielding layer on the protruding tips of deposited lithium, facilitating uniform and smooth lithium deposition. Pyr14TFSI assists in constructing a stable solid electrolyte interphase (SEI) layer on the Li surface enriched with LiF, Li3N, and RCOOLi. The modulation of lithium deposition behavior on the anode by Pyr14TFSI ensures stable Li plating/stripping for >1500 h. A Li-Cu cell exhibits stable cycling for >200 cycles at a current density of 0.05 mA cm-2, with an average Coulombic efficiency of 92.7%. In situ polymerization ensures that P(VECx-EGy)/Pyrz/LiTFSI@CE QSPEs exhibit excellent interface compatibility with the anode and the cathode. The CR2032 button cell Li|P(VEC1-EG0.06)/Pyr0.4/LiTFSI@CE|LiCoO2 demonstrates stable cycling with a negligible capacity decay of 0.083% per cycle for >390 cycles at 25 °C and 0.2 C when using a high-voltage LiCoO2 (4.45 V) cathode. Furthermore, a 7.1 mAh pouch cell achieves stable charge-discharge cycles, confirming the pronounced stability of the as-fabricated QSPE at the interfaces of the high-voltage LiCoO2 cathode and Li anode.

Evaluation of Various Types of Alginate Inks for Light-Mediated Extrusion 3D Printing.

Naturally derived biopolymers modifying or combining with other components are excellent candidates to promote the full potential of additive manufacturing in biomedicine, cosmetics, and the food industry. This work aims to develop new photo-cross-linkable alginate-based inks for extrusion 3D printing. Specifically, this work is focused on the effect of the addition of cross-linkers with different chemical structures (polyethylene glycol diacrylate (PEGDA), N,N'-methylenebisacrylamide (NMBA), and acrylic acid (AA)) in the potential printability and physical properties of methacrylated alginate (AlgMe) hydrogels. Although all inks showed maximum photo-curing conversions and gelation times less than 2 min, only those structures printed with the inks incorporating cross-linking agents with flexible and long chain structure (PEGDA and AA) displayed acceptable size accuracy (~0.4-0.5) and printing index (Pr ~1.00). The addition of these cross-linking agents leads to higher Young's moduli (from 1.6 to 2.0-2.6 KPa) in the hydrogels, and their different chemical structures results in variations in their mechanical and rheological properties. However, similar swelling ability (~15 swelling factor), degradability (~45 days 100% weight loss), and cytocompatibility (~100%) were assessed in all the systems, which is of great importance for the final applicability of these hydrogels.

Improving the 3D Printability and Mechanical Performance of Biorenewable Soybean Oil-Based Photocurable Resins.

The general requirement of replacing petroleum-derived plastics with renewable resources is particularly challenging for new technologies such as the additive manufacturing of photocurable resins. In this work, the influence of mono- and bifunctional reactive diluents on the printability and performance of resins based on acrylated epoxidized soybean oil (AESO) was explored. Polyethylene glycol di(meth)acrylates of different molecular weights were selected as diluents based on the viscosity and mechanical properties of their binary mixtures with AESO. Ternary mixtures containing 60% AESO, polyethylene glycol diacrylate (PEGDA) and polyethyleneglycol dimethacrylate (PEG200DMA) further improved the mechanical properties, water resistance and printability of the resin. Specifically, the terpolymer AESO/PEG575/PEG200DMA 60/20/20 (wt.%) improved the modulus (16% increase), tensile strength (63% increase) and %deformation at the break (21% increase), with respect to pure AESO. The enhancement of the printability provided by the reactive diluents was proven by Jacobs working curves and the improved accuracy of printed patterns. The proposed formulation, with a biorenewable carbon content of 67%, can be used as the matrix of innovative resins with unrestricted applicability in the electronics and biomedical fields. However, much effort must be done to increase the array of bio-based raw materials.

Vat photopolymerization of dual-scale porosity alumina honeycombs using phase-separable camphene porogen dissolved in binary photopolymer blends

Dual-scale porosity ceramics comprised of macro-scale pore networks surrounded by porous frameworks manufactured by additive manufacturing (AM) can offer significantly enhanced functions compared to conventional porous ceramics. However, exploring new ways of more tightly controlling micro-scale porous structures for AM still remains challenging. Here, we propose a novel type of vat photopolymerization using camphene as a phase-separable porogen dissolved in binary photopolymer blends for manufacturing dual-scale porosity alumina honeycombs. More specifically, solid camphene with various contents (40 vol%, 50 vol%, and 60 vol%) could be completely dissolved in blends of triethylene glycol dimethacrylate (TEGDMA) and polyethylene glycol diacrylate (PEGDA) used as solvent and anti-solvent, respectively, at room temperature and then crystallize dendritically at ∼ 5 °C via phase separation. After which, thin layers of phase-separated alumina suspensions could be selectively photopolymerized by a digital light processing (DLP) engine to construct 3-dimensionally interconnected macro-scale pore channels. In addition, micro-scale pores could be created in alumina frameworks by removing camphene-rich crystals by freeze-drying. This new approach enabled manufacturing of well-defined macro-scale honeycomb structures with tailored micro-scale porosities. As the camphene content increased from 40 vol% to 60 vol%, micro-scale porosity increased from 39.1 ± 0.5 vol% to 57.5 ± 0.6 vol%, and thus the overall porosity increased from 58.5 ± 0.1 vol% to 68.8 ± 0.3 vol%, while the compressive strength decreased from 355.6 ± 67.1 MPa to 97.6 ± 10.2 MPa.

Li6.28La3Zr2Al0.24O12-reinforced Single-ion Conducting Composite Polymer Electrolyte for Room-Temperature Li-Metal Batteries

Composite polymer electrolytes composed of inorganic fillers and organic polymers are promising electrolyte candidates for Li metal batteries, with benefits of improved safety and suppressed lithium dendrite growth. However, a severe concentration polarization effect often occurs when using conventional dual-ion electrolytes, and the increase in internal impedance during cycling results in decreased lifespan of the battery. To address this challenge, a plasticized single-ion conducting composite polymer electrolyte (SICE) was designed and fabricated by polymerizing the monomers of lithium (4-styrenesulfonyl) (trifluoromethanesulfonyl) imide (LiSTFSI) and poly(ethylene glycol) methyl ether acrylate (PEGMEA), crosslinker poly(ethylene glycol) diacrylate (PEGDA), silane-modified Li6.28La3Al0.24Zr2O12 nanofibers (s@LLAZO NFs), along with a PEG-based plasticizer tetraethylene glycol dimethyl ether (TEGDME), by heat-initiation. The anions were restrained and delocalized so that only Li cation migration occurred during the charging/discharging process, leading to a superior lithium-ion transference number. The s@LLAZO NFs enabled direct monomer grafting with the polymer matrix, resulting in controlled formation of an organic-inorganic network with increased filler content and improved filler distribution in the SICE system. The SICE membrane exhibited high ionic conductivity at room temperature, reduced activation energy and excellent oxidation stability. Most importantly, the all-solid-state Li-metal batteries assembled with the fabricated SICE demonstrated stable long-term cycling performance and remarkable rate capability at room temperature.

Photoredox dual catalysis using stimulus-responsive fluoresceins for colorimetric detection of Hg(II) ions

We demonstrate photoredox dual catalysis using fluorescein derivatives and apply it to polymerization-based signal amplification (PBA) under the irradiation of visible light. The mechanism of the photoredox dual catalysis is elucidated using electron paramagnetic resonance (EPR) and UV–Vis spectroscopies. We applied the photoredox dual catalysis to amplify and readout the signal of Hg(II) ions with the unaided eye through photoinitiated free-radical polymerization. Although PBA offers a reliable and rapid colorimetric method for analyte detection, its sensitivity remains a challenge compared with fluorescence detection. To address this issue, we designed a dual system involving activatable fluoresceins that selectively react to external stimuli, followed by their action as photoredox catalysts/initiators. As a proof-of-concept, we employed fluorescin and eosin hydrazide (EYHZ) as light- and Hg(II) ion-responsive probes, respectively. This dual system selectively initiated the polymerization of poly(ethylene glycol) diacrylate (PEGDA) in the presence of Hg(II) ions under visible light. Remarkably, this photoredox dual catalysis approach allowed the unaided eye to detect of Hg(II) ions as low as 90 nM in aqueous solution, demonstrating its potential for sensitive and versatile sensing applications.