ACS Applied Polymer Materials最新文献

Stretchablediodes are fundamental building blocks for rectificationand logic operations in soft integrated circuits; however, conventionaldiodes suffer from a persistent trade-off between rectification performanceand electromechanical durability. Although electronic diodes basedon rigid inorganic semiconductors deliver high rectification ratiosexceeding 10³, their intrinsic brittleness restricts theirapplication in deformable electronics. Conversely, conventional ionicdiodes utilizing compliant ionic conductors can accommodate largetensile strains (>50%), but they are typically limited to low-frequencyoperations (<1 Hz) with modest rectification ratios (<100).Herein, we demonstrate a highly robust stretchable organic electrochemicaldiode based on a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)(PEDOT:PSS) active layer. The rectifying behavior originates frombias-dependent hole injection and extraction at the junction betweenthe PEDOT:PSS active layer and an Ag flake composite anode, whichdynamically modulates the electrochemical doping state of the activelayer to induce a highly asymmetric interfacial impedance response.Remarkably, the organic electrochemical diode preserves a rectificationratio of 300 at 1 kHz even under 100% tensile strain, alongside exceptionalmechanical durability over 1,000 stretch–release cycles at20% strain. Using this robust high-frequency capability, integratedOR and AND logic gates are successfully demonstrated to process 1kHz alternating current (AC) signals. By simultaneously combiningsuperior electromechanical stability, a high rectification ratio,and practical kHz operation, this platform represents a significantleap forward in the realization of next-generation deformable electronicsystems.

The development of biocompatibleand biologically responsivescaffoldsremains a key challenge for bone tissue engineering. Here, we reportan enzyme-degradable, metal-free click-cross-linked organic–inorganicnanohybrid (Enz-Deg-Click-ON) scaffold with high biocompatibilityfor bone repair. The formulation was synthesized using a cyclooctyne-functionalizedpoly(propylene fumarate) polyphosphoester (PPF-poly(PE-BCN)) and azide-terminateddendritic polycaprolactone (PCL) with a polyhedral oligomeric silsesquioxanecore (POSS-PCL-N₃) via strain-promoted alkyne-azide cycloaddition(SPAAC) bioorthogonal click chemistry. The incorporation of phosphate-containinglinkages enabled alkaline phosphatase (ALP)-responsive degradation.The scaffold exhibited rapid catalyst-free crosslinking, tunable swelling,and suitable mechanical properties. In vitro studiesdemonstrated excellent cytocompatibility, robust stem cell proliferation,and enhanced osteogenic differentiation with an elevated level ofALP and Runx2 expression. Enzyme-triggered degradation was confirmedin the presence of ALP. In the in vivo rat calvarialdefect model, the scaffold significantly improved bone regeneration,as shown by an increased bone volume, mineral density, and defectcoverage. Histological and immunofluorescence analyses revealed enhancedcollagen deposition, angiogenesis, and osteogenesis. These resultsindicate that the Enz-Deg-Click-ON system provides a dynamic, bioresponsiveplatform for bone repair.

Cationicantimicrobial polymers exhibit potent antibacterial activitybut frequently suffer from nonspecific interactions, systemic toxicity,and unfavorable in vivo disposition. Glycosylationoffers a potential strategy to improve their biological compatibility;however, its effects on the in vivo pharmacokineticsand organ distribution of cationic antimicrobial polymers remain poorlyunderstood. Here, we report a glycosylated cationic block poly(β-peptide)synthesized via a ring-strain-driven, one-pot anionic ring-openingpolymerization (AROP) conducted at room temperature. The polymerizationwas rationally designed by exploiting the substantial difference inring strain between the sugar-derived β-lactam monomers andthe cationic β-lactam monomers. Compared with the non-glycosylatedhomopolymer, the glycosylated cationic block copolymer exhibited prolongedblood circulation, reduced systemic clearance, and increased systemicexposure. Glycosylation also altered organ distribution by reducingpredominant hepatic accumulation and promoting kidney-associated distributionand urinary elimination. These results establish ring-strain differentiationas a simple principle for room-temperature block copolymerizationand demonstrate that glycosylation can actively regulate the in vivo fate of cationic antimicrobial polymers.

Inthis work, we have reported a simple synthetic method for thebiofluorescence polyimine (PDMS-DM) film through a Schiff base reactionusing the scorpion-based fluorescent derivative dibenzaldehyde macrocyclicdiphthalate ester and aminopropyl-polydimethylsiloxane as precursors.Under the synergistic effect of dynamic imine bonds and flexible PDMS,the obtained PDMS-DM film shows strong interfacial adhesion and rapidself-healing behavior at room temperature. Meanwhile, inspired bythe structure of MDE extracted from the scorpion exoskeleton, thePDMS-DM films exhibit obvious fluorescence under UV illumination andefficient antibacterial properties against Gram-positive bacteria,Gram-negative bacteria, and fungi, demonstrating great potential foruse as antimicrobial packaging materials.

Thisstudy proposes a stepwise grafting strategy to simultaneouslyimpart flame retardancy and intelligent thermal-moisture managementto cotton fabrics, addressing both their inherent flammability andthe comfort degradation typically associated with conventional flame-retardanttreatments. First, ammonium vinylphosphonate (AVP) was covalentlyanchored onto cotton fabrics via P–O–C linkages througha Dicyandiamide-catalyzed pad-dry-cure finishing process, establishinga flame-retardant system. Subsequently, the introduced vinyl groupsserved as reactive sites for surface-initiated polymerization of atemperature-responsive poly(N-isopropylacrylamide)(PNIPAM) layer, forming a dynamic thermo-regulable architecture. Systematicevaluation reveals that the resulting fabric (Cotton/AVP-PNIPAM) exhibitssubstantially enhanced flame retardancy, with the limiting oxygenindex increasing from 18.1% to 34.0%, whereas the peak heat releaserate and total heat release decrease by 91.6% and 46.8%, respectively.Concurrently, the surface-grafted PNIPAM imparts temperature-dependentfunctionality, transitioning from a hydrophilic, expanded state below32 °C to a hydrophobic, contracted state above 32 °C, therebyenabling intelligent thermal-moisture regulation characterized bylow-temperature insulation and high-temperature cooling. By overcomingthe inherent trade-off between flame retardancy and wearing comfortthrough precise chemical functionalization, this work provides a designparadigm for next-generation high-performance textiles.

High-performance electrical insulating materials arecritical forensuring the safe and reliable operation of electrical equipment underhigh-voltage and high-integration conditions. In this study, aramidnanofiber (ANF)/hydroxyapatite (HAP) composite films were fabricatedvia a vacuum-assisted filtration process, combined with hot pressing.The results demonstrate that the incorporation of 10 wt % HAP enablesthe composite film to achieve a tensile strength of 155.8 MPa anda breakdown strength of 43.2 kV/mm, representing increases of 43.1%and 21.7%, respectively, compared to those of the pristine ANF film(108.9 MPa, 35.5 kV/mm). After hot pressing, the composite film with30 wt % HAP exhibits a breakdown strength of 203.5 kV/mm, which is80.4% higher than that of the hot-pressed pristine ANF film (112.8kV/mm) and markedly 498.5% higher than that of its nonhot-pressedcounterpart (34.0 kV/mm). Microstructural analysis reveals that hotpressing promotes the formation of a dense laminated structure withinthe film, which helps to suppress the propagation of the breakdownpaths. This strategy provides a facile and effective route for thepreparation of high-performance, insulating materials.

Thepervasive accumulation of microplastics (MPs) inaquatic environmentsposes a severe global threat, yet conventional membrane filtrationsuffers from rapid membrane fouling and low throughput. In this study,we report the fabrication of a silsesquioxane-cross-linked polyimide(PIOA) aerogel for highly efficient and robust MP remediation. Actingas critical 3D structural nodes, silsesquioxane (SQs) endow the aerogelwith a highly interconnected hierarchically porous network and anultralow, tunable apparent density. The optimized aerogel exhibitsan exceptional balance between a high permeate flux (112.6 L m^–2 h^–1) and a superior retention efficiency(95%) for polystyrene microplastics (PSMPs). Mechanistic investigationsreveal that the capture process is fundamentally driven by strongmultisite hydrogen bonding and localized electrostatic attractions,which act as robust active chemical anchors. Furthermore, the aerogeldemonstrates remarkable environmental resilience across diverse real-worldfreshwater matrices (86%–90% efficiency) and maintains outstandingcontinuous operational stability over 10 successive filtration cyclesunder high-loading conditions without requiring regeneration treatment.This work provides a highly scalable and structurally robust paradigmfor designing advanced polymer aerogel filters, opening avenues forsustainable wastewater purification and microplastic pollution mitigation.

Controllingpolymer-colloid morphology through a synthetic variablethat does not alter the principal monomer chemistry remains challenging.Here, monomer feed sequence was used to generate distinct feed-defined,ensemble-averaged organizations of pendant trithiocarbonate sitesalong methacrylate backbones and thereby regulate graft-growth-drivennanoassembly. One-pot reverse atom transfer radical polymerizationof poly(ethylene glycol) methyl ether methacrylate and a trithiocarbonate-bearingmethacrylate afforded simultaneous-feed, end-enriched, and center-enrichedmultifunctional macro-RAFT agents with the same target compositionand comparable apparent molar masses. The pendant trithiocarbonate-containingside groups were subsequently used to mediate grafting-from RAFT dispersionpolymerization of styrene. At [St]/[macro-RAFT] = 150, the three precursorsproduced compact particles, interconnected vesicle-like assemblies,and multicompartment-like nanoassemblies, respectively, under otherwiseidentical conditions. This pronounced morphology differentiation demonstratesthat the feed-programmed RAFT-site organization strongly influencesgraft-growth-driven colloidal assembly. Time-resolved ¹H NMR spectroscopy, transmission electron microscopy, dynamic lightscattering, and size-exclusion chromatography linked increasing styreneconversion and graft growth to aggregate growth, particle association,and the development of apparent internal domains. Repeated feed-conversioncycles extended the approach to nominal 7-, 5-, and 3-segment backbones,with feed-stage characterization supporting sequential monomer consumptionand population-level chain extension. These results establish feedhistory as a practical synthetic variable for controlling graft-copolymercolloidal morphology and internal organization, which may supportthe future development of polymer nanoassemblies for encapsulation,compartmentalized reaction media, and adaptive material platforms.

Developing membranes with high ion selectivity and long-termchemicalstability is essential for advancing vanadium redox flow battery (VRFB)technologies. In this work, uncross-linked and cross-linked anion-exchangemembranes (AEMs) based on PHFP grafted with 2-(dimethylamino)ethylmethacrylate were synthesized and quaternized using mono- and dibromohexane.Spectroscopic and microscopic analyses confirmed successful grafting,quaternization, and the formation of continuous hydrophilic ion-transportpathways. Cross-linking with DBH produced a highly compact and denselyinterconnected network that reduced water uptake and swelling whileimproving mechanical strength, oxidative stability, and Donnan exclusionagainst vanadium ions. The optimized PHFP-g-MA-DBHmembrane exhibited a VO²⁺ permeability of 7.35 × 10^–7 cm² min^–1, ionic selectivityof 0.912 × 10⁵ S min cm^–3, and ionicconductivity of 6.71 × 10^–2 S cm^–1. Single-cell VRFB performance of PHFP-g-MA-DBHmembrane showed a 2.03 times longer self discharge time and 1.34 timeshigher peak power density than Nafion-212. Moreover, PHFP-g-MA-DBH membrane exhibited 3.75 times higher capacity retentionover 300 charge–discharge cycles compared to the Nafion-212membrane. Long-term cycling at 100 mA cm^–2 demonstratedrobust durability, with a capacity decay rate of ∼0.13% percycle and retained efficiencies of CE = 97.88%, VE = 78.53%, and EE= 76.87% after 500 cycles. These results position PHFP-g-MA-DBH as a cost-effective and high-performance alternative to perfluorinatedmembranes for durable, high-efficiency VRFB systems.

Current strategies for preparing conductive hydrogels(CHs) ofteninevitably encompass the addition of small-molecule photoinitiators,toxic cross-linkers, or complex polymerization conditions, limitingtheir broader application in flexible wearable electronics. To addressthese issues, we developed a green in situ photoinitiation and organic–inorganichybrid cross-linking strategy based on vinyltrimethoxysilane-modifiedzinc oxide (VTMS-ZnO). By constructing a deep eutectic solvent (DES)system composed of betaine (BET), itaconic acid (IA), and glycerol(Gly), integrated through poly(ethylene glycol) diacrylate (PEGDA)covalent cross-linking, hydroxyethyl cellulose (HEC) chain entanglement,Zn²⁺ dynamic coordination, and DES-induced multiple hydrogen-bondinginteractions, we successfully fabricated HEC@P(2-hydroxyethyl methacrylate-co-sodium 4-styrenesulfonate) [P(HEMA-co-NaSS)]/VTMS-ZnO semi-IPN conductive eutectogels. In this system,VTMS-ZnO serves as the photoactive inorganic component to induce thein situ copolymerization of HEMA and NaSS under UV irradiation. Moreover,the surface vinyl groups of VTMS-ZnO participate in the network construction,allowing the ZnO nanoparticles to be embedded into the polymer networkas hybrid nodes. The optimized H_0.2 eutectogel demonstratedan elongation at break of approximately 1000%, a toughness of 96.96kJ m^–3, an ionic conductivity of 78.2 mS m^–1, a gauge factor of 0.270, and an adhesion strength of 6.11 kPa onpaper. It maintained stable sensing performance over 150 cycles at10% strain, remained flexible after storage at −53 °Cfor 12 h, and retained over 50% of its initial mass at 37 °Cand 35% relative humidity for 11 days. This comprehensive performanceenables the eutectogels to serve as versatile wearable sensors forthe real-time monitoring of human movements and weak physiologicalsignals (response time of 0.82 s). In addition, the eutectogel exhibitedinhibitory activity against Escherichia coli. Our work sheds light on a feasible and eco-friendly strategy forcustomizing multifunctional eutectogels, paving the way for innovativeflexible wearable devices.