ACS Applied Polymer Materials最新文献

An organic conducting copolymer, poly(1,10-phenanthroline-5,6-dione-co-o-methoxyaniline) (PPD-co-OMA), is synthesized using an electrochemical polymerization methodon a carbon paper substrate and is utilized as the electrode materialfor energy storage in an aqueous electrolyte. PPD-co-OMA possesses a highly interconnected porous morphology and exhibitsa high specific capacity of 183.3 mAh g^–1 at a currentdensity of 1 A g^–1 in 1 M H₂SO₄. Compared to the homopolymers poly(1,10-phenanthroline-5,6-dione)(PPD) and poly(o-methoxyaniline) (POMA), lower chargetransfer resistance, abundant redox-active sites, and improved iondiffusion contribute to the enhanced charge storage performance ofPPD-co-OMA. The charge storage mechanism involvesthe reversible redox transitions of carbonyl/hydroxyl groups and amino/iminogroups, accompanied by reversible H⁺ intercalation/deintercalation.The symmetric solid-state supercapacitor constructed using two PPD-co-OMA electrodes demonstrates good durability, with a capacityretention of 87.2% after 2000 charge and discharge cycles at a currentdensity of 5 A g^–1. The device exhibits an energydensity of 65.8 Wh kg^–1 at a power density of 1280W kg^–1. These results demonstrate that the electrocopolymerizationstrategy provides a facile route for constructing conducting polymersas electrode materials with improved electrochemical energy storageperformance.

Poly(butylene succinate) (PBS), a representative bio-basedandbiodegradable polymer, exhibits great potential in food packagingand agricultural mulch films. However, its applications are limitedby high crystallinity, low toughness, low degradation rate, and pooroxygen barrier properties. To address these issues, PBS was modifiedby the introduction of both linear diols (C₂–C₁₂) and branched diols (1,2-dodecanediol) (1,2-do). First,the quaternary poly(butylene succinate-co-1,12-dodecanediolsuccinate-co-1,2-dodecanediol succinate) (PBDdS)copolyesters were synthesized by melt polycondensation. Although thebranched structure hinders crystallization, the mechanical propertiesof the copolyesters are significantly improved. The optimum elongationat break reaches 818.1%, which is five times that of PBS. Subsequently,the 1,12-dodecanediol (1,12-Do) segment was replaced by linear diolswith carbon chain lengths of 2, 6, 8, and 10. The influence of thecarbon length of the main chain and the content of the branched chainon the crystallization, mechanical properties, hydrophilicity, oxygenbarrier properties, and degradation properties was investigated. Accordingto the research, polymers containing shorter-chain units, such as1,2-ethylene glycol (1,2-EG), show higher tensile strength, superioroxygen barrier properties (2.3 times PBS), better hydrophobicity (97.00°),and a shorter degradation cycle. Conversely, polymers containing long-chainunits, such as 1,12-dodecanediol, exhibit superior toughness (5.0times PBS), better oxygen permeability, greater hydrophilicity (78.25°),and a longer degradation cycle. Furthermore, all copolymers exhibitgood thermal stability. These results demonstrate an effective strategyfor modulating the mechanical, barrier, surface, and degradation propertiesof PBS-based polyesters.

Hierarchicallystructured porous polymer films have attracted increasingattention for electrochemical sensing, biointerfaces, and advancedfunctional surfaces. Herein, we present a simple, machine-free, andscalable bottom-up strategy for fabricating dual-patterned polyaniline(PANI) porous films integrating ridge–valley morphologies throughvapor–liquid interfacial polymerization. The fabrication processemploys economical and readily accessible precursors, including benzoylperoxide (BPO) as the oxidant and poly[(Z)-1-(tert-butyl)cyclooct-4-en-1-ol] (P2) as a flexible polymercomponent that significantly enhances film flexibility relative topolystyrene (PS) substrates while maintaining structural integrity.Under ambient solution-processing conditions, spontaneous patternformation arises from the coupled effects of interfacial polymer growth,solvent evaporation, and stress relaxation, eliminating the need forlithographic patterning, templates, or external mechanical processing.Importantly, the dual-patterned porous architecture establishes aunique structure–function relationship for electroactive biomoleculeinteractions. The porous domains promote localized accumulation ofelectroactive biomolecules by serving as adsorption reservoirs, whereasthe interconnected conductive ridges facilitate efficient electron-transferpathways after desorption. Combined with the pH-responsive protonation/deprotonationbehavior of PANI, this hierarchical architecture enables reversiblecapture, electrochemical conversion, and detection of dopamine (DA),serotonin (5-HT), and ascorbic acid (AA). The behavior is attributedto reversible modulation of local electrostatic interactions and chargedistribution within the porous conductive network. As a result, theindividual pores within the porous film act as localized sites foranalyte accumulation, signal transduction, and molecular recognitionunder mild pH-switching conditions, demonstrating potential for responsivesensing applications as a smart film.

We report the formation of ordered mesoscale featureswhen a dilutepolymer solution (polystyrene, PS) is spin-coated over soft-lithographicallyfabricated, topographically patterned substrates, with square-box,hexagonal, and circular patterns. At lower concentrations, the dispensedsolution fails to form a continuous film over the topographicallypatterned substrates, resulting in isolated features arranged alongthe contours of the substrate patterns due to spin dewetting. We showthat the morphology of the spin-dewetted features is governed by theeffective initial film thickness (h_E), which increases with theconcentration of the dispensed polymer solution, and by the orientationof the topographically patterned regions with respect to the directionof the advancing meniscus during spin coating over square-box andhexagonally patterned substrates. With a progressive increase in h_E, the polymer progressively fills the recessed regions of the patternedsubstrate and eventually forms a continuous film over the topographicallypatterned substrates. We also show that subsequent thermal annealingof these depositions/films leads to multilength-scale ordered patternsalong the recessed and raised portions of the topographically patternedsurfaces. Our experiments reveal the critical role of the geometryof the substrate patterns, particularly how they intercept the advancingmeniscus during spin dewetting and the eventual ordering of the dewettedfeatures.

Unlike conventional solvent-borne systems, which raiseconcernsregarding volatile organic compound (VOC) emissions and toxicity,the waterborne polymer adhesives developed in this study incorporatemarine mussel-inspired catechol functionalities and zwitterionic/cationicmoieties into a terephthalate-based polyester backbone. The resultingpolymers, PSBD0–PSBD4, exhibit excellent hydrophilicity andrebondable adhesion. The optimal catechol-bearing formulation, PSBD2,shows a lap-shear strength of 2.09 ± 0.09 MPa, an 83% increaseover the catechol-free PSBD0. The polymers are further reinforcedby in situ generated Ti- or Si-based sol–gelinorganic nanoparticles. The corresponding PSBD composites achievedaverage lap-shear strengths of 2.47 ± 0.22 MPa (Ti-based) and2.72 ± 0.54 MPa (Si-based), corresponding to 18% and 30% increasesover neat PSBD2, and the highest single cycle lap-shear strengthsreached 3.27 ± 1.18 MPa (Ti-based) and 3.34 ± 0.78 MPa (Si-based)under the best conditions. Furthermore, the polymer can be hydrolyzedunder mild basic conditions. SEM and EDX analyses reveal that catecholincorporation enhances the morphological and sol–gel distributionhomogeneity of the materials, which likely accounts for the observedenhancement in macroscopic adhesion strength. TEM analysis revealscontinuous particle growth within the composites during the repeatedwetting/drying processes, and solid-state ²⁹Si NMR analysiswas used to characterize the corresponding chemical states. Finally,a scheme interpreting the reinforcement mechanism and the structure-performancerelationship is proposed. This study demonstrates a viable moleculardesign strategy for developing waterborne polymer adhesives.

Infectedwounds pose a significant challenge in clinical practice.Their persistent inflammatory response and bacterial colonizationnot only severely impede the healing process but may also lead tolife-threatening complications. It is essential to develop effectivestrategies for improving the healing of infected wounds. Therefore,a sprayable hydrogel was assembled from phenylboronic acid-functionalizedchitosan (CS-BA) and poly(vinyl alcohol) (PVA). The drug-loading micelleswere fabricated by self-assembly of amphiphilic ε-polylysine-octenylsuccinic anhydride (EPL-OSA), encapsulating immune-modulating curcumin(MC). The photothermal reagent, copper-doped polydopamine nanoparticles(PDA@Cu), was prepared by an in situ reduction method.The sprayable CS-BA/PVA hydrogel loaded MC and PDA@Cu rapidly formedwithin 30 s and exhibited synergistic antimicrobial activity fromEPL and an excellent photothermal antimicrobial effect from PDA@Cu.The curcumin released from the micelles suppressed pro-inflammatoryfactor expression, enhanced anti-inflammatory factor expression, andfacilitated M2 macrophage polarization. The synergistic antimicrobialand immunomodulatory effects accelerated the healing of infected wounds.Meanwhile, the hydrogel shows electrical conductivity and can be usedas a flexible sensor to achieve flexible sensing.

Polymers offer a promising alternative to establishedlipid nanoparticlesfor therapeutic RNA delivery. Here, we introduce alkyl-chain-quaternizedpoly(vinylpyrrolidone-co-4-vinylpyridine) copolymers(PVP-co-PVPy) for siRNA delivery, marking their firstreported use for this purpose to the best of our knowledge. Thesepolymers are easily synthesized via a two-step synthesis, startingwith a free-radical polymerization of two inexpensive monomers, followedby quaternization with an iodoalkane. Formulation involves simplebatch mixing in PBS, reproducibly yielding small spherical particles.The functional performance of the polymers as siRNA carriers, assessedby in vitro gene silencing of the enhanced greenfluorescent protein (eGFP) reporter gene, as well as their cytotoxicity,both depend on the ratio of the two monomers and the alkyl chain length.The best-performing polymers in this study both feature a decyl chainand monomer ratios of PVP/PVPy between 65/35 and 70/30, achievingeGFP knockdown of 70–80% while maintaining around 70–80%cell viability.

Flexible piezoresistive pressure sensors capable of resolvingweakdynamic mechanical signals are important for wearable health monitoring,human-machine interaction, and vibration-pattern recognition. However,integrating high sensitivity, a broad working range, cyclic repeatability,and machine-learning-based signal discrimination in a lightweightporous device remains challenging. Herein, an ultralight HVP/CNT spongepressure sensor (apparent density 0.08–0.15 g cm^–3, porosity 88–93%) was fabricated by incorporating hydroxylatedmultiwalled carbon nanotubes (MWCNT–OH) into a porous hydrolysis-stableHVP resin framework. The optimized HVP/CNT sensor showed a peak sensitivityof 9.17 kPa^–1 in the low-pressure region, distinguishablepiezoresistive responses over the tested pressure range, response/recoverytimes of 360/470 ms, and broadly maintained output during 2500 loading–unloadingcycles under the tested conditions. The sensor monitored representativehuman-motion signals and captured throat-vibration signals duringphonation. After the relative resistance-change signals were convertedinto image-like features and processed by an 11-layer convolutionalneural network (CNN), same-participant classification accuracies of97.625% for two language categories and 97.25% for eight spoken commandswere obtained under controlled acquisition conditions. These resultsdemonstrate a materials-device-algorithm route for wearable speech-relatedvibration classification; extension to industrial condition monitoringshould be supported by direct equipment-vibration tests, environmentalcross-sensitivity evaluation, and longer-term cyclic durability analysis.

Thehydrogel-based transpiration cooling holds promise for thermalmanagement of high-heat-flux electronics, yet its practical applicationis constrained by an inherent trade-off between high swelling capacityand environmental stability against dehydration and freezing. Here,this trade-off is decoupled by incorporating glycerol into a three-dimensionalsodium polyacrylate (PANa) network. Glycerol modulates the water statewithin the polymer network via hydrogen bonding with both polymerchains and water molecules, enabling reduced water loss while preservingwater for swelling and cooling. The resulting sodium polyacrylate/glycerol(PANa/Gly-3) hydrogel particles, prepared with a glycerol-to-watervolume ratio of 1:1, exhibit a weight retention of 93.5% ± 0.7%after 12 h at 25 °C and 70% RH, excellent freeze resistance byremaining unfrozen at −23 °C for 45 days, and a high swellingratio of 284 ± 3 g·g^–1. Under a simulatedhigh heat flux of 16 kW·m^–2, PANa/Gly-3 hydrogelparticles achieved cyclic transpiration cooling with a maximum temperaturereduction of 30–33 °C and improved temperature uniformityacross the heater surface compared with PANa particles. This studydemonstrates an effective strategy that improves the environmentalstability of PANa hydrogels while largely preserving their swellingcapacity and mitigating local drying during transpiration cooling,thereby offering a promising solution for efficient thermal managementof high-heat-flux electronics.

Marineorganisms such as diatoms and sponges fabricatehierarchicallyordered siliceous architectures with nanoscale precision under benignconditions. Inspired by these biological strategies, biomimetic approacheshave been developed to synthesize chiral silica-based materials undermild conditions. Here, we employed the molecular self-assembly ofa small molecule viz. l-NapF-EDA to templatethe formation of chiral, anisotropic silica nanotubular structures.The self-assembly of l-NapF-EDA spontaneously generates alocalized basic microenvironment near the nanofiber surface, directingsilica condensation and enabling the controlled formation of uniformsilica nanotubes without the need for an external base. The resultingnanotubes exhibit a well-defined hollow tubular morphology with anouter diameter of 61.26 ± 12.5 nm and an inner diameter of 39.6± 4.3 nm, yielding a high aspect ratio characteristic of one-dimensional(1D) nanostructures. Notably, the self-assembly templated mineralizationprocess affords a remarkably high product yield: 1.5 g of silica nanotubescan be produced from as little as 100 mg of gelator, underscoringthe efficient templating capability of the supramolecular scaffold.Postsynthetic amine functionalization imparts tunable surface chemistrywhile preserving the nanotubular morphology. Leveraging the elongatedarchitecture and interfacial functionality of these silica nanotubes,they were incorporated into sulfonated poly(vinyl alcohol) (SPVA)membranes, achieving 45% enhancement in proton conductivity at roomtemperature (61.1 ± 1.2 vs 42.1 ± 1.6 mS cm^–1) with an ultralow filler loading of 0.1 wt % relative to pristineSPVA. These results demonstrate how biomimetic mineralization andinterfacial engineering can be integrated to develop functional materialswith tailored properties.