ACS Applied Polymer Materials最新文献

Molecularlyimprinted polymers have evolved into versatile functionalplatforms that extend far beyond traditional separation science applications.This work reports the development of photoactive molecularly imprintednanoparticles (MINs) for the capture and photocatalytic degradationof the recalcitrant antibiotic pollutant oxolinic acid (OA) undervisible-light irradiation. Molecular dynamics simulations were usedto screen eight monomer formulations with varying ratios of (AA), N-isopropylacrylamide (NIPAm), N-tert-butylacrylamide(TBAm), N-(3-aminopropyl)methacrylamide hydrochloride(APMA), and the crosslinker N,N′-methylenebis(acrylamide)(BIS). The computational formulation with the highest affinity tothe template (40% AA, 8% NIPAm, 8% TBAm, 39% APMA, and 5% BIS) guidedthe synthesis of OA-imprinted MINs via high-dilution polymerizationin aqueous solution, followed by in situ conjugationwith the photosensitizer toluidine blue O (TBO) via EDC/NHS coupling.Dynamic light scattering, zeta potential, and TEM experiments confirmedthe nanoscale size and colloidal stability of the synthesized nanoparticles.Photoactive MINs achieved 20% OA binding capacity at 50 μmolL^–1 and sustained singlet oxygen generation underwhite LED light irradiation (150 mW cm^–2) for 1h. Immobilized MINs were tested as photocatalysts for OA degradationat 100 and 200 μmol L^–1, achieving 60–80%antibiotic removal after 6 h of irradiation. ¹H-NMR ofOA at an early degradation point suggests a possible fragmentationpathway involving dealkylation of the γ-pyridone-β-carboxylicring. OA degradation at concentrations exceeding the MINs bindingcapacity confirmed that the photocatalytic removal operates througha cavity-assisted mechanism comprising substrate capture, photochemicaldegradation, and product release. Despite the long irradiation timesrequired for OA degradation, our results show the potential of integratingmolecular imprinting and photosensitization to develop polymeric photocatalystsfor antibiotic remediation.

Achieving a balanced combinationof ultra-stretchability,electrostaticsafety, self-healing capability, and enhanced combustion performancein polymer-bonded explosives (PBXs) remains a critical challenge.Herein, we report a series of fluorine-rich ion-conductive elastomers(ICEs) derived from a polymerizable deep eutectic solvent (PDES) composedof 2,2,3,4,4,4-hexafluorobutyl acrylate (HFBA) and lithium bis(trifluoromethanesulfonyl)imide(LiTFSI). The formation mechanism of the PDES(HFBA₂-LiTFSI)system was elucidated via FT-IR spectroscopy, revealing that the carbonylgroups of HFBA participate in Li⁺ solvation, and a homogeneousPDES is formed at an HFBA:LiTFSI molar ratio of 2:1. Three elastomersystems, namely LiF₂C_No, LiF₂C_PEGDA and LiF₂C_VFSoil were systematicallyinvestigated. By introducing a fluorosiloxane crosslinker (VFSoil),the resulting LiF₂C_VFSoil exhibited the mostfavorable comprehensive performance with toughness of 23.23±0.05MJ·m^–3, ionic conductivity of 7.517×10^–5 S/m, thermally activated self-healing capability,and favorable hydrophobicity. When applied as a binder for cyclotetramethylenetetranitramine(HMX, octogen)-based composites, the H₅₀(LiF₂C_VFSoil)₅₀ formulation maintained excellentstretchability with an elongation at break of 578.12% and exhibitedthermally activated self-healing capability at 80 °C. Furthermore,the H₉₀(LiF₂C_VFSoil)₁₀ formulation improved both the mechanical and electrostatic safetyrelative to pristine HMX. Moreover, high-speed photography and infraredthermography revealed that the fluorine-rich binder LiF₂C_VFSoil effectively disrupted the alumina passivationshell, suppressed aluminum nanoparticles (nano-Al) agglomeration,and delivered superior combustion uniformity and sustained high flametemperatures in aluminized formulations. This work presents a promisingmolecular design platform for developing next-generation PBXs featuringultra-stretchability, thermally activated self-healing capability,and enhanced combustion performance.

Developing soft materials that integratehigh mechanicalperformance,self-healing, adhesion, and stimulus-responsive functions remainschallenging due to the trade-off between dynamic reversibility andmechanical resilience. Here, we report a P(AA-MA-OA-FHMA) hydrogelfabricated via one-pot free-radical copolymerization, in which hydrophobicassociation and multivalent hydrogen bonding are synergistically integratedas dual dynamic cross-linking mechanisms. The salicylaldehyde-derivedmonomer (FHMA) serves as a triple-functional building block, providinghydrophobic domains, hydrogen bonding sites, and metal-chelating coordinationsites. The hydrogel exhibits an ultrahigh fracture strain exceeding4000%, a tensile strength of 278 kPa, self-healing efficiency of ∼75%at room temperature, and an adhesion strength of 40 kPa on porcineskin. The FHMA moieties enable multicolor fluorescence (blue withZn²⁺, green with Al³⁺, and orange with hydrazinehydrate), while Al³⁺ coordination imparts selective antibacterialactivity against Escherichia coli withnearly 100% killing efficiency. The ionic conductivity further enablesstrain-responsive sensing for both joint movements and subtle physiologicalactivities. This work provides a simple platform for constructingmultifunctional hydrogels with potential applications in wearableelectronics, biointerfaces, and wound dressing.

Polyethylene (PE)and polypropylene (PP) blends are widelyencounteredin mixed plastic waste streams, yet their inherent immiscibility typicallyleads to poor mechanical performance without prior separation. Inthis work, immiscibility is instead exploited as a processing advantageto induce fibrillar reinforcement through two-dimensional multilayercoextrusion and thermal drawing. A 50/50 PE/PP blend and its correspondingunblended system were processed using a 6X3 multilayer architectureand subjected to controlled draw ratios to investigate structure–processing–propertyrelationships. Mechanical testing revealed substantial draw-directiondependent increases in modulus and tensile strength with draw ratioaccompanied by substantial reductions in strain at break and toughness,with blended systems outperforming unblended films at higher deformationlevels. Wide-angle X-ray scattering (WAXS) showed that drawing inducescooperative orientation in both PE and PP phases, accompanied by crystallographicredistribution and reflection-dependent crystalline reorganization.Unlike unblended materials, the blends exhibited non-monotonic orientationbehavior and dynamic intensity ratio evolution, indicating interphasecoupling during deformation. Thermal analysis confirmed moderate increasesin crystallinity; however, mechanical enhancement was disproportionatelylarge relative to crystallinity alone. Morphological analysis revealedsignificantly finer fibrillar structures in the blends, consistentwith enhanced microfibrillation driven by phase incompatibility. Theseresults demonstrate that multilayer coextrusion combined with mechanicaldeformation enables the transformation of immiscible polyolefin blendsinto hierarchically structured, higher draw-direction modulus, andtensile strength materials without compatibilization, providing apotentially scalable pathway for the upcycling of mixed plastic waste.

Durableand visually compatible protective coatings are crucialfor enhancing the durability of cultural heritage materials undercomplex environmental conditions. In this study, fluorinated waterbornepolyurethane (F-WPU) and fluorinated Paraloid B72 (F–B72) coatingswere prepared via fluorosilane modification and applied to bronzeas well as representative wooden substrates (pine wood and red sandalwood).On bronze surfaces, substrate-assisted interfacial regulation coupledwith fluorosilane-induced molecular organization promoted the formationof hierarchical particle-aggregate structures, which, combined withlow-surface-energy fluorinated groups, enhanced surface hydrophobicity.The water contact angle (WCA) of bronze increased from 27.4°to approximately 139°, while highly hydrophilic pine wood (6.5°)and red sandalwood (84.5°) were converted into stable hydrophobicsurfaces with WCAs around 139°. Both coatings demonstrated excellentdurability, maintaining WCAs above 120° after 2000 cm of mechanicalabrasion, above 115° after 21 days of temperature–humiditycycling, and above 130° after 21 days of UV irradiation. Thecoatings also exhibited stable electrochemical protection during a30-day immersion in 3.5 wt % NaCl solution, confirming their sustainedbarrier capability against corrosive media. Colorimetric analysisand gloss measurements confirmed visual compatibility, with ΔE*values consistently remaining below the conservation threshold of3 and only minor changes in surface gloss after coating application.Electrochemical tests in 3.5 wt % NaCl solution indicated that theF-WPU coating reduced the corrosion current density of bronze from1.4 × 10^–5 to 1.2 × 10^–7 A·cm^–2, achieving a corrosion inhibitionefficiency of 99.14%, and increased low-frequency impedance by nearlytwo orders of magnitude. These results demonstrate a substrate-adaptivecoating strategy that integrates hierarchical surface structuring,hydrophobicity, electrochemical protection, environmental durability,and visual compatibility. The developed coating system exhibits promisinglong-term protection potential for metallic and wooden cultural heritagematerials, although further validation under extended outdoor exposureconditions remains necessary.

Phase change materials (PCMs) haveexhibited favorable prospectsin thermal energy storage and thermal management systems. However,it is highly desirable to overcome the drawbacks of bulk PCMs, includinginherent leakage problem, low thermal conductivity, and single heat-storagefunctionality. Therefore, a reversible thermochromic composite PCMwith high energy storage capacity, good reliability, and anti-leakageperformance was developed by synergistic assembly through inter-molecularhydrogen bonds and interconnected cross-linking. The synergistic cross-linkednetwork enabled the shape and thermal stability of the composite PCMs,effectively preventing leakage problems. Simultaneously, the compositePCMs possessed a high heat storage capacity of 169.03 J/g, which exhibitedexcellent thermal reliability and cycling stability for experiencing200 thermal cycles at 80 °C, revealing effective temperatureregulation performance. Furthermore, the interconnected frameworkalso fulfilled the composite PCMs with an improved thermal conductivity,which was even 48.86% higher than that of pure PCMs. In addition,the TBC/CNC composite PCMs exhibited not only a rapid and reversiblethermochromic response but also good mechanical stability with a highcompressive modulus of 6.1597 MPa. This work provides a sustainablematerial design strategy for expanding the applications of PCMs.

All-polymer photodetectors, owing to their remarkableadvantagesof flexibility and mechanical durability, exhibit demonstrated potentialfor application in the field of wearable technology. Nevertheless,the frequently employed double-component active layer structure issusceptible to performance degradation during long-term use. Consequently,a copolymer PM6-co-TTY6 possessing both donor andacceptor properties was designed and synthesized. The single-componentactive layer devices based on PM6-co-TTY6 exhibitpronounced photomultiplication characteristics. The maximum externalquantum efficiency (EQE_max) of PM6-co-TTY6device with thin active layer reaches 365% or 336% under a bias voltageof +5 V or −5 V, respectively. Remarkably, the device showsbias-tunable spectral response with increasing active layer thickness:a narrowband response (800–900 nm) with a EQE_max of 25% and a narrow full width at half maximum (FWHM) of 30 nm undernegative bias, while a broadband response (300–900 nm) underpositive bias. At this stage, the device can be switched between broadbandand narrowband detection modes by reversing the polarity of the appliedbias.

β-Cyclodextrin (βCD)-based adsorbents haveemergedas promising materials for micropollutant removal owing to their host–guestrecognition capability toward diverse organic molecules. However,developing βCD-based monolithic adsorbents that simultaneouslyachieve high adsorption capacity and rapid mass transport remainschallenging. Here, we report a βCD-functionalized hierarchicallyporous polymer monolith fabricated by integrating digital light processing(DLP) 3D printing, polymerization-induced phase separation (PIPS),and supramolecular post-modification. By optimizing the porogenicsolvent composition of the printing inks, nanoporous polymer monolithswith interconnected submicron pores, a porosity of 23.49%, an averagepore diameter of 0.20 μm, a specific surface area of 28.33 m² g^–1, and adequate compressive strengthwere obtained. Subsequent βCD grafting introduced host–guestadsorption sites, enabling βCD-Nano-P to achieve an equilibriumBPA uptake of 77.52 mg g^–1 at 1 mM BPA, which was37.5% higher than that of the βCD-modified nonporous control.The βCD-Nano-P monolith also showed good reusability over fiveadsorption–desorption cycles and broad removal capability towarddifferent organic pollutants. Importantly, DLP printing enabled theconstruction of hierarchically porous monoliths with triply periodicminimal surface macropores, which accelerated adsorption kineticsby increasing the adsorption rate constant 12.4-fold compared withthe nanoporous monolith without macropores. This work demonstratesa multiscale design strategy that integrates βCD adsorptionsites, PIPS-generated nanopores, and DLP-designed macroporous flowpathways to simultaneously improve adsorption capacity and adsorptionkinetics in structured water-treatment adsorbents.

The valorization of whey, the main byproduct of cheesemanufacture,is hindered for small and medium-sized dairy enterprises (SMEs) bythe high cost of conventional separation technologies such as membranefiltration and chromatography. In this work, complex coacervationbetween whey proteins and carboxymethylcellulose (CMC) was scaledfrom 5 to 100 L to develop a simple, low-cost process for recoveringa protein- and lipid-enriched product. Five commercial CMCs with molecularweights ranging from 18 to 780 kDa were first evaluated at laboratoryscale. Intermediate-Mw CMC (400 kDa) provided the best balance betweenelectrostatic complexation and sedimentation, removing 99% of theinitial protein from the supernatant, as confirmed by residual proteinquantification and turbidity. Using the selected CMC, the processwas successfully scaled to 100 L in a conical-bottom tank with anoff-centered 45° four-blade turbine. Geometric similarity (H/Dt= 2.0–2.5, Da/Dt = 0.26–0.33) was applied, achievingfully turbulent flow at both scales (Re = 3.56 × 10⁴ and 1.41 × 10⁵). Protein recovery reached 76%, witha 3.4-fold concentration of proteins and nearly complete fat recoveryin the coacervate. The freeze-dried coacervate was readily redispersibleup to 20% (w/v). Its ζ-potential shifted from near-zero at pH3 to −40 mV above pH 6, reflecting the combined contributionof whey proteins and residual CMC. Thermal gelation of the coacervate(3.1% protein) was strongly pH-dependent: weak gels formed at acidicpH (G′ = 6–23 Pa), while strong, cohesivegels developed at alkaline pH (G′ = 325 Paat pH 9). The lactose-rich supernatant showed reduced COD and BODloads (12% and 28% reduction, respectively) and was successfully fermentedby kefir grains without nutrient supplementation. This scalable, food-gradecoacervation process offers an accessible alternative for dairy SMEsto transform whey from an environmental burden into a functional ingredient.

Long-term, high-fidelity electroencephalography acquisitionrequiresbioelectronic interfaces that simultaneously exhibit low skin–electrodeimpedance, stable electrical conductivity, mechanical compliance,and environmental stability. However, most conductive hydrogels sufferfrom progressive water loss, disruption of conductive pathways, andincreasing interfacial impedance during prolonged use, resulting insignal degradation and limiting their application in wearable brain–computerinterfaces. This paper reports a conductive hydrogel based on photocurablegelatin methacryloyl (GelMA), which integrates a covalently cross-linkedGelMA network, an MXene electronic conductive network, an NaCl-mediatedion transport network, and a glycerol–water hydrogen bond network,thereby establishing a synergistic electronic–ionic conductiveinterface with enhanced water retention and long-term stability. Therationally engineered multiscale network simultaneously improves mechanicalrobustness, electrical conductivity, and interfacial conformity whileeffectively suppressing conductivity decay induced by dehydration.The optimized hydrogel exhibits a compressive strength of 680.1 kPa,an electrical conductivity of 0.304 S m^–1 (10 Hz),a low skin–electrode impedance of 6.501 kΩ, and retains88.35% of its initial water content after 72 h under ambient conditions.Benefiting from the synergistic electron–ion transport mechanismand stable hydrated interface, the hydrogel electrode enables reliableacquisition of resting-state EEG and steady-state visual evoked potentialsignals, achieving a signal-to-noise ratio of 15.05 dB and maintainingstable electrophysiological performance after 12 h of continuous wear.This work demonstrates a general strategy for constructing long-termstable bioelectronic interfaces through the synergistic regulationof mechanical networks, electron transport, ion migration, and waterretention, providing a promising platform for next-generation wearableEEG electrodes and continuous brain–computer interface applications.