Atom Transfer Radical Polymerization Research Articles

Fluorescence Sensing of Eclampsia Biomarkers via the Immunosorbent Atom Transfer Radical Polymerization Assay.

Accurate and quantitative detection of pre-eclampsia markers is crucial in reducing pregnancy mortality rates. This study introduces a novel approach utilizing a fluorescent biosensor by the immunosorbent atom transfer radical polymerization (immuno-ATRP) assay to detect the pre-eclampsia protein marker CD81. The critical step used in this sensor is the novel signal amplification strategy of fluorescein polymerization mediated by ferritin-enhanced controlled radical polymerization, which combines with a traditional enzyme-linked immunosorbent assay (ELISA) to further reduce the detection limit of the CD81 protein concentration. The fluorescence intensity was linear versus logarithmic CD81 protein concentration from 0.1 to 10,000 pg mL-1, and the detection limit was 0.067 pg mL-1. Surprisingly, in 30% normal human serum (NHS), the sensor can also detect target protein over 0.1-10,000 pg mL-1, with 0.083 pg mL-1 for the detection limit. Moreover, the proposed biosensor is designed to be cost-effective, making it accessible, particularly in resource-limited settings where expensive detection techniques may not be available. The affordability of this method enables widespread screening and monitoring of preeclampsia, ultimately benefiting many pregnant women by improving their healthcare outcomes. In short, developing of a low-cost and susceptible direct detection method for preeclampsia protein markers, such as CD81, through the use of the immuno-ATRP assay, has significant implications for reducing pregnancy mortality. This method holds promise for early detection, precise treatment, and improved management of preeclampsia, thereby contributing to better maternal and fetal health.

Photo-Deactivation Strategy for Switchable ATRP with the Assistance of Molecular Switches.

Light irradiation is an external stimulus, rapidly developed in switchable atom transfer radical polymerization (ATRP) via photo-activation methods in recent years. Herein, we introduce a photo-deactivation strategy to regulate ATRP with the assistance of photoswitchable hexaarylbiimidozole (HABI). Under visible light irradiation and in the presence of HABI, ATRP is greatly decelerated or quenched depending on the concentration of HABI. Interestingly, with visible light off, ATRP can proceed smoothly and follow a first-order kinetics. Moreover, photo-switchable ATRP alternatively with light off and on is demonstrated. Besides, the mechanism of photo-deactivation ATRP involving radical quenching is proposed in the presence of HABI. This article is protected by copyright. All rights reserved.

Removal of Cr(VI) from Wastewater Using Acrylonitrile Grafted Cellulose Extracted from Sugarcane Bagasse

A highly efficient low-cost adsorbent was prepared using raw and chemically modified cellulose isolated from sugarcane bagasse for decontamination of Cr(VI) from wastewater. First, cellulose pulp was isolated from sugarcane bagasse by subjecting it to acid hydrolysis, alkaline hydrolysis and bleaching with sodium chlorate (NaClO3). Then, the bleached cellulose pulp was chemically modified with acrylonitrile monomer in the presence Fenton’s reagent (Fe+2/H2O2) to carry out grafting of acrylonitrile onto cellulose by atom transfer radical polymerization. The developed adsorbent (acrylonitrile grafted cellulose) was analyzed by X-ray diffraction analysis (XRD), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR). Both raw cellulose and acrylonitrile grafted cellulose were used for chromium removal from wastewater. The effects of metal ion concentration, pH, adsorbent dose and time were studied, and their values were optimized. The optimum conditions for the adsorption of Cr(VI) onto raw and chemically modified cellulose were: metal ion concentration: 50 ppm, adsorbent dose: 1 g, pH: 6, and time: 60 min. The maximum efficiencies of 73% and 94% and adsorption capacities of 125.95 mg/g and 267.93 mg/g were achieved for raw and acrylonitrile grafted cellulose, respectively. High removal efficiency was achieved, owing to high surface area of 79.92 m2/g and functional active binding cites on grafted cellulose. Isotherm and kinetics studies show that the experimental data were fully fitted by the Freundlich isotherm model and pseudo first-order model. The adsorbent (acrylonitrile grafted cellulose) was regenerated using three different types of regenerating reagents and reused thirty times, and there was negligible decrease (19%) in removal efficiency after using it for 30 times. Hence, it is anticipated that acrylonitrile could be utilized as potential candidate material for commercial scale Cr(VI) removal from wastewater.

Unusual Stability of an end-on Superoxido Copper(II) Complex under Ambient Conditions.

Superoxido copper complexes play an important role as usually short-lived intermediates in biology and chemistry. The unusual stability of anend-onsuperoxido copper complex observed in an oxygen-enhanced atom transfer radical polymerization (ATRP) led to a detailed mechanistic investigation of the formation of [CuII(Me6tren)(O2•-)]+(Me6tren = tris(2-dimethyl-aminoethyl)amine) under ambient conditions. The persistence of the superoxido copper complex could be explained by a reaction cycle including the peroxido complex[(Me6tren)2CuII2(O2)]2+together with [CuI(Me6tren)(DMSO)]+and [CuII(Me6tren)(OH)]+in the overall reaction.

Covalently grafting polycation to bacterial cellulose for antibacterial and anti-cell adhesive wound dressings

Hydrogel-based wound dressings are becoming increasingly important for wound healing. Bacterial cellulose (BC) has been commonly used as wound dressings due to its good in vitro and in vivo biocompatibility. However, pure BC does not possess antibacterial properties. In this regard, polycation gel was grafted onto the BC using a surface-initiated activator regenerated by electron transfer atom transfer radical polymerization (SI-ARGET ATRP) with subsequent quaternization for antibacterial wound dressing. Dimethylethyl methacrylate (DMAEMA) was successfully polymerized on the BC surface which was confirmed by Fourier transform infrared spectroscopy and elemental analysis. The morphology structure, specific surface area, pore size, and mechanical properties were also characterized. The quaternized PDMAEMA grafted on the BC endowed it with excellent antibacterial activity against E. coli (Gram-negative) and S. aureus (Gram-positive) with a killing rate of 89.2 % and 93.4 %, respectively. The number of cells was significantly reduced on QPD/BC hydrogel, demonstrating its good anti-adhesion ability. In vitro cellular evaluation revealed that the antibacterial wound dressing exhibited good biocompatibility. Overall, this study provides a feasible method to develop antibacterial and anti-cell adhesive hydrogel, which has a promising potential for wound healing.

Janus Nanofibrous Patch with In Situ Grown Superlubricated Skin for Soft Tissue Repair with Inhibited Postoperative Adhesion.

The patch with a superlubricated surface shows great potential for the prevention of postoperative adhesion during soft tissue repair. However, the existing patches suffer from the destruction of topography during superlubrication coating and lack of pro-healing capability. Herein, we demonstrate a facile and versatile strategy to develop a Janus nanofibrous patch (J-NFP) with antiadhesion and reactive oxygen species (ROS) scavenging functions. Specifically, sequential electrospinning is performed with initiators and CeO2 nanoparticles (CeNPs) embedded on the different sides, followed by subsurface-initiated atom transfer radical polymerization for grafting zwitterionic polymer brushes, introducing superlubricated skin on the surface of single nanofibers. The poly(sulfobetaine methacrylate) brush-grafted patch retains fibrous topography and shows a coefficient of friction of around 0.12, which is reduced by 77% compared with the pristine fibrous patch. Additionally, a significant reduction in protein, platelet, bacteria, and cell adhesion is observed. More importantly, the CeNPs-embedded patch enables ROS scavenging as well as inhibits pro-inflammatory cytokine secretion and promotes anti-inflammatory cytokine levels. Furthermore, the J-NFP can inhibit tissue adhesion and promote repair of both rat skin wounds and intrauterine injuries. The present strategy for developing the Janus patch exhibits enormous prospects for facilitating soft tissue repair.

Precise synthesis of three-arm star polymethacrylates with high emission efficiency both in solution and in the solid state

Organic/polymeric fluorescent materials with bright emission both in solution and in the solid state have garnered growing interest in biological and optoelectronic fields. Herein, triphenylamine-derived boron ketoimine (TPA-BKI-3Br) was utilized as the initiator for atom transfer radical polymerization (ATRP) to prepare dual-state emission three-arm star polymethacrylates. Due to the intramolecular charge transfer (ICT) effect and highly distorted structure of the TPA-BKI unit, as well as the polymer arms constraining intramolecular motions, the resultant polymers displayed significant emission in solution. In the aggregated and solid states, the photophysical characteristics of the resultant polymethacrylates were notably impacted by the space charge transfer between the TPA-BKI unit and polymer chains. In addition, the TPA-BKI-based poly(2-(dimethylamino)ethyl methacrylate) (TPA-BKI-(PDMAEMA)3) exhibited fluorescence responses to temperature variations owing to the presence of dimethylamino group. This study presents an approach for the advancement of dual-state emission polymeric materials.

Nucleic Acid-Binding Dyes as Versatile Photocatalysts for Atom-Transfer Radical Polymerization.

Nucleic acid-binding dyes (NuABDs) are fluorogenic probes that light up after binding to nucleic acids. Taking advantage of their fluorogenicity, NuABDs have been widely utilized in the fields of nanotechnology and biotechnology for diagnostic and analytical applications. We demonstrate the potential of NuABDs together with an appropriate nucleic acid scaffold as an intriguing photocatalyst for precisely controlled atom-transfer radical polymerization (ATRP). Additionally, we systematically investigated the thermodynamic and electrochemical properties of the dyes, providing insights into the mechanism that drives the photopolymerization. The versatility of the NuABD-based platform was also demonstrated through successful polymerizations using several NuABDs in conjunction with diverse nucleic acid scaffolds, such as G-quadruplex DNA or DNA nanoflowers. This study not only extends the horizons of controlled photopolymerization but also broadens opportunities for nucleic acid-based materials and technologies, including nucleic acid-polymer biohybrids and stimuli-responsive ATRP platforms.

Surface-grafted macromolecular nanowires with pedant fluorescein chromophores by dense non-aggregated nanoarchitectonics as versatile photoactive platforms

In this paper, we present a facile method of synthesis and modification of poly(glycidyl methacrylate) brushes with 6-aminofluorescein (6AF) molecules. Polymer brushes were obtained using surface-grafted atom transfer radical polymerization (SI-ATRP) and functionalized in the presence of triethylamine (TEA) acting both as a reaction catalyst and an agent preventing aggregation of chromophores. Atomic force microscopy (AFM), FTIR, X-ray photoelectron spectroscopy (XPS) were used to study the structure and formation of obtained photoactive platforms. UV/Vis absorption and emission spectroscopy and confocal microscopy were conducted to investigate photoactivity of chromophores within the macromolecular matrix. Owing to the simplicity of fabrication and good ordering of the chromophore in a thin nanometric layer, the proposed method may open new opportunities for obtaining light sensors, photovoltaic devices, or other light-harvesting systems.

BaTiO3 catalyzed ultrasonic driven piezoelectric induced miniemulsion atom transfer radical polymerization (Piezo-miniATRP)

Compared with other stimulus such as light and heat, ultrasonic possesses much deeper penetration into tissues and organs and has lower scattering in heterogeneous systems as a noninvasive stimulus, and has already been used as the external stimulus to initiate reversible-deactivation radical polymerization (RDRP). However, the development of efficient ultrasonic drive RDRP in aqueous dispersed media remains a challenge. Here in this work, ultrasonic driven piezoelectric induced miniemulsion atom transfer radical polymerization (Piezo-miniATRP) was performed, with tetragonal BaTiO3 (BTO) nanoparticles as the piezoelectric catalyst. The Piezo-miniATRP exhibited features of controllable and livingness, such as linear increase of molar mass and narrow molar mass distributions (Mw/Mn < 1.30). The effect of different polymerization parameters on the polymerization reaction was investigated, including the amounts of surfactant, CuBr2 and BTO dosages. Excellent temporal control of the polymerization and the chain fidelity of polymers were illustrated by “ON and OFF” experiment and chain extension, separately. This novel BTO catalyzed Piezo-miniATRP process could also be extended to other aqueous dispersion RDRP systems.

An Innovative Approach for Tailoring Molecularly Imprinted Polymers for Biosensors—Application to Cancer Antigen 15-3

This work presents a novel approach for tailoring molecularly imprinted polymers (MIPs) with a preliminary stage of atom transfer radical polymerization (ATRP), for a more precise definition of the imprinted cavity. A well-defined copolymer of acrylamide and N,N′-methylenebisacrylamide (PAAm-co-PMBAm) was synthesized by ATRP and applied to gold electrodes with the template, followed by a crosslinking reaction. The template was removed from the polymer matrix by enzymatic/chemical action. The surface modifications were monitored via electrochemical impedance spectroscopy (EIS), having the MIP polymer as a non-conducting film designed with affinity sites for CA15-3. The resulting biosensor exhibited a linear response to CA15-3 log concentrations from 0.001 to 100 U/mL in PBS or in diluted fetal bovine serum (1000×) in PBS. Compared to the polyacrylamide (PAAm) MIP from conventional free-radical polymerization, the ATRP-based MIP extended the biosensor’s dynamic linear range 10-fold, improving low concentration detection, and enhanced the signal reproducibility across units. The biosensor demonstrated good sensitivity and selectivity. Overall, the work described confirmed that the process of radical polymerization to build an MIP material influences the detection capacity for the target substance and the reproducibility among different biosensor units. Extending this approach to other cancer biomarkers, the methodology presented could open doors to a new generation of MIP-based biosensors for point-of-care disease diagnosis.

Synergistic Drug-Loaded Shear-Thinning Star Polymer Hydrogel Facilitates Gastrointestinal Lesion Resection and Promotes Wound Healing.

Easy injection, long-lasting barrier, and drug loading are the critical properties of submucosal injection materials for endoscopic surgery. However, conventional injectable polymers face challenges in simultaneously attaining these properties due to the inherent conflict between injectability and in situ stability. Here, a multi-arm star polymer hydrogel (denoted as βCP hydrogel) with long-lasting submucosal barrier (exceeding 120 min), rapid hemostasis, and sustained antibacterial properties is successfully developed by grafting poly(oligo(ethylene glycol) methyl ether methacrylate)(PEGMA) side-chains from β-CD via atom transfer radical polymerization (ATRP). During the onset of shearing, βCP hydrogel experiences the unwinding of polymer side-chains between neighboring star polymers, which facilitates the process of endoscopic injectability. After submucosal injection, βCP hydrogel undergoes the winding of polymer side-chains, thereby establishing a long-lasting barrier cushion. Meanwhile, owing to its distinctive structures with a hydrophobic inner cavity and an outer layer of hydrophilic polymer side-chains, βCP hydrogel enables simultaneous loading and on-demand release of diverse categories ofdrugs. This unique performance can adapt to the diverse demands during different stages of wound healing in a porcine endoscopic surgery model. These results indicate an appealing prospect for new application of star polymers as a good submucosal injection material in endoscopic treatments.

Hairy quaternary ammonium-functionalized metal organic framework integrated in polyacrylonitrile nanofiber membrane for efficient removal of arsenate

In this work, the metal–organic framework (MOF) particles (i.e., UiO-66-NH2) was covalently modified with poly(4-vinylpyridine) (P4VP) through surface-initiated atom transfer radical polymerization (SI-ATRP) method. The hair MOF product, referred to as UiO-66-g-P4VP, was then subjected to quaternization with 1-bromoethane, resulting in UiO-66-g-qP4VP (quaternized P4VP is denoted as qP4VP). Finally, these UiO-66-g-qP4VP particles were incorporated into a polymer matrix made of polyacrylonitrile (PAN) to develop a nanofibrous composite membrane using the electrospinning technique. After modification of quaternized P4VP, the surface of the MOFs carry strong positive charges. Therefore, the electrospun UiO-66-g-qP4VP/PAN nanofiber membrane can serve as an adsorbent in efficient removal of negatively charged arsenate through strong electrostatic interactions. The adsorptive efficacy of the nanofiber membrane exhibited considerable stability within the pH spectrum extending from 4 to 10, indicating that the membrane could potentially maintain its functionality across a broad range of pH conditions. Our developed approach opens up an avenue for manufacturing of polyelectrolyte-functionalized MOF nanofiber membranes, which hold great promise for application in water remediation.

Selective and Controlled Grafting from PVDF-Based Materials by Oxygen-Tolerant Green-Light-Mediated ATRP.

Poly(vinylidene fluoride) (PVDF) shows excellent chemical and thermal resistance and displays high dielectric strength and unique piezoelectricity, which are enabling for applications in membranes, electric insulators, sensors, or power generators. However, its low polarity and lack of functional groups limit wider applications. While inert, PVDF has been modified by grafting polymer chains by atom transfer radical polymerization (ATRP), albeit via an unclear mechanism, given the strong C-F bonds. Herein, we applied eosin Y and green-light-mediated ATRP to modify PVDF-based materials. The method gave nearly quantitative (meth)acrylate monomer conversions within 2 h without deoxygenation and without the formation of unattached homopolymers, as confirmed by control experiments and DOSY NMR measurements. The gamma distribution model that accounts for broadly dispersed polymers in DOSY experiments was essential and serves as a powerful tool for the analysis of PVDF. The NMR analysis of poly(methyl acrylate) graft chain-ends on PVDF-CTFE (statistical copolymer with chlorotrifluoroethylene) was carried out successfully for the first time and showed up to 23 grafts per PVDF-CTFE chain. The grafting density was tunable depending on the solvent composition and light intensity during the grafting. The initiation proceeded either from the C-Cl sites of PVDF-CTFE or via unsaturations in the PVDF backbones. The dehydrofluorinated PVDF was 20 times more active than saturated PVDF during the grafting. The method was successfully applied to modify PVDF, PVDF-HFP, and Viton A401C. The obtained PVDF-CTFE-g-PnBMA materials were investigated in more detail. They featured slightly lower crystallinity than PVDF-CTFE (12-18 vs 24.3%) and had greatly improved mechanical performance: Young's moduli of up to 488 MPa, ductility of 316%, and toughness of 46 × 106 J/m3.

Electrochemically Mediated Atom Transfer Radical Polymerization Driven by Alternating Current.

Alternating current (AC) and pulsed electrolysis are gaining traction in electro(organic) synthesis due to their advantageous characteristics. We employed AC electrolysis in electrochemically mediated Atom Transfer Radical Polymerization (eATRP) to facilitate the regeneration of the activator CuI complex on Cu0 electrodes. Additionally, Cu0 served as a slow supplemental activator and reducing agent (SARA ATRP), enabling the activation of alkyl halides and the regeneration of the CuI activator through a comproportionation reaction. We harnessed the distinct properties of Cu0 dual regeneration, both chemical and electrochemical, by employing sinusoidal, triangular, and square-wave AC electrolysis alongside some of the most active ATRP catalysts available. Compared to linear waveform (DC electrolysis) or SARA ATRP (without electrolysis), pulsed and AC electrolysis facilitated slightly faster and more controlled polymerizations of acrylates. The same AC electrolysis conditions could successfully polymerize eleven different monomers across different mediums, from water to bulk. Moreover, it proved effective across a spectrum of catalyst activity, from low-activity Cu/2,2-bipyridine to highly active Cu complexes with substituted tripodal amine ligands. Chain extension experiments confirmed the high chain-end fidelity of the produced polymers, yielding functional and high molecular-weight block copolymers. SEM analysis indicated the robustness of the Cu0 electrodes, sustaining at least 15 consecutive polymerizations.

A ratiometric electrochemical biosensor based on ARGET ATRP for detection of HER2 gene

Human epidermal growth factor receptor 2 (HER2), a common proto-oncogene, is overexpressed in a subset of breast cancer patients. It is essential to track HER2 expression for early breast cancer diagnosis. Herein, a ratiometric electrochemical biosensor for detection of HER2 based on activators generated by electron transfer for atom transfer radical polymerisation (AGET ATRP) and hairpin DNA was developed. Specifically, hairpin DNA was first self-assembled on the gold electrode by Au–S bond. Upon capturing HER2, the stem-loop structure of hairpin DNA was unfolded, the signal value of methylene blue (MB) decreased as it moved away from the electrode surface. cDNA was linked with HER2 by complementary base pairing to introduce amino group. Then, the initiator 2-bromo-2-methylpropionic acid (BMP) were connected to the amino group on the cDNA to activate ARGET ATRP. The detection performance of biosensors for HER2 was explored by the ratio signal between two signal molecules. Under optimal conditions, this ratiometric electrochemical biosensor shows good selectivity and stability with a wide detection range of 1–1 × 106 pM and a detection limit of 78.47 fM. Furthermore, the biosensor exhibits satisfactory anti-interference ability due to the hairpin DNA and dual signal system, and has promising application prospects in the detection of other DNA disease markers.

Electrochemically Mediated Atom Transfer Radical Polymerization Driven by Alternating Current

Alternating current (AC) and pulsed electrolysis are gaining traction in electro(organic) synthesis due to their advantageous characteristics. We employed AC electrolysis in electrochemically mediated Atom Transfer Radical Polymerization (eATRP) to facilitate the regeneration of the activator CuI complex on Cu0 electrodes. Additionally, Cu0 served as a slow supplemental activator and reducing agent (SARA ATRP), enabling the activation of alkyl halides and the regeneration of the CuI activator through a comproportionation reaction. We harnessed the distinct properties of Cu0 dual regeneration, both chemical and electrochemical, by employing sinusoidal, triangular, and square‐wave AC electrolysis alongside some of the most active ATRP catalysts available. Compared to linear waveform (DC electrolysis) or SARA ATRP (without electrolysis), pulsed and AC electrolysis facilitated slightly faster and more controlled polymerizations of acrylates. The same AC electrolysis conditions could successfully polymerize eleven different monomers across different mediums, from water to bulk. Moreover, it proved effective across a spectrum of catalyst activity, from low‐activity Cu/2,2‐bipyridine to highly active Cu complexes with substituted tripodal amine ligands. Chain extension experiments confirmed the high chain‐end fidelity of the produced polymers, yielding functional and high molecular‐weight block copolymers. SEM analysis indicated the robustness of the Cu0 electrodes, sustaining at least 15 consecutive polymerizations.

Chitosan oligosaccharide-functionalized nano-prodrug for cascade chemotherapy through oxidative stress amplification

Redox nanoparticles have been extensively developed for chemotherapy. However, the intracellular oxidative stress induced by constant aberrant glutathione (GSH), reactive oxygen species (ROS) and gamma-glutamyl transpeptidase (GGT) homeostasis remains the primary cause of evading tumor apoptosis. Herein, an oxidative stress-amplification strategy was designed using a pH-GSH-H2O2-GGT sensitive nano-prodrug for precise synergistic chemotherapy. The disulfide bond- conjugated doxorubicin prodrug (DOX-ss) was constructed as a GSH-scavenger. Then, phenylboronic acid (PBA), DOX-ss and poly (γ-glutamic acid) (γ-PGA) were successively conjugated using chitosan oligosaccharide (COS) to obtain the nano-prodrug PBA-COS-ss-DOX/γ-PGA. The PBA-COS-ss-DOX/γ-PGA prodrug could tightly attach to the polymer chain segment by atom transfer radical polymerization. Simultaneously, the drug interacted relatively weakly with the polymer by encapsulating ionic crosslinkers in DOX@PBA-COS/γ-PGA. The disulfide bond of the DOX-ss prodrug as a GSH-scavenger could be activated using overexpressed GSH to release DOX. Particularly, PBA-COS-ss-DOX/γ-PGA could prevent premature drug leakage and facilitate DOX delivery by GGT-targeting and intracellular H2O2-cleavable linker in human hepatocellular carcinoma (HepG2) cells. Concurrently, the nano-prodrug induced strong oxidative stress and tumor cell apoptosis. Collectively, the pH-GSH-H2O2-GGT responsive nano-prodrug shows potential for synergistic tumor therapy.

Synthesis of grafted bromoisobutyryl esterified starch using electron transfer atom transfer radical polymerization method with high-performance adhesion and film properties

Nowadays, few investigations on the process parameters of grafted starch synthesized using electron transfer atom transfer radical polymerization (ARGET ATRP) and its applications in warp sizing and paper-making are presented. Therefore, this study aimed to survey the appropriate process parameters of bromoisobutyryl esterified starch-g-poly(acrylic acid) (BBES-g-PAA) synthesized by the ARGET ATRP, and also aimed to provide a new biobased BBES-g-PAA adhesive. The appropriate synthesis process parameters were 1.2, 0.32, and 0.6 in the molar ratios of vitamin C, CuBr2, and pentamethyldivinyltriamine to BBES, respectively, at 40 °C for 5 h. The BBES-g-PAA samples with a grafting ratio range of 4.63–14.14 % exhibited bonding forces of 57.8–64.6 N to wool fibers [55.5 N (BBES) and 53.8 N (ATS)], and their films showed breaking elongations of 3.29–3.80 % [2.74 % (BBES) and 2.49 % (ATS)] and tensile strengths of 29.1–25.4 MPa [30.4 MPa (BBES) and 34.7 MPa (ATS)]. Compared with BBES, significantly increased bonding forces and film elongations, and decreased film strengths for the BBES-g-PAA samples with grafting ratios ≥10.54 % were displayed (p < 0.05). The time (100–42 s) taken for the BBES-g-PAA films was significantly shorter than that of ATS (246 s) and BBES (196 s) films (p < 0.05), corresponding to better desizability.

ARGET-ATRP-Mediated Grafting of Bifunctional Polymers onto Silica Nanoparticles Fillers for Boosting the Performance of High-Capacity All-Solid-State Lithium-Sulfur Batteries with Polymer Solid Electrolytes.

The shuttle effect in lithium-sulfur batteries, which leads to rapid capacity decay, can be effectively suppressed by solid polymer electrolytes. However, the lithium-ion conductivity of polyethylene oxide-based solid electrolytes is relatively low, resulting in low reversible capacity and poor cycling stability of the batteries. In this study, we employed the activator generated through electron transfer atom transfer radical polymerization to graft modify the surface of silica nanoparticles with a bifunctional monomer, 2-acrylamide-2-methylpropanesulfonate, which possesses sulfonic acid groups with low dissociation energy for facilitating Li+ migration and transfer, as well as amide groups capable of forming hydrogen bonds with polyethylene oxide chains. Subsequently, the modified nanoparticles were blended with polyethylene oxide to prepare a solid polymer electrolyte with low crystallinity and high ion conductivity. The resulting electrolyte demonstrated excellent and stable electrochemical performance, with a discharge-specific capacity maintained at 875.2 mAh g-1 after 200 cycles.