ACS Applied Polymer Materials最新文献

Triboelectric nanogenerators (TENGs) are promising candidates for powering next-generation wearable electronics by leveraging their self-powered capability, efficient low-frequency energy harvesting, and fast response. However, the widespread application of polymer-based TENGs remains limited by their poor environmental stability under harsh conditions. To overcome this limitation, we developed a durable aramid nanofiber/hydroxyapatite (ANF/HAP) composite film (denoted as AH film) through vacuum-assisted filtration. The design leverages a synergistic charge manipulation mechanism: ANFs serve as electron-trapping sites with low electrical potential, while HAP acts as a high-dielectric charge reservoir. This unique charge manipulation synergy concurrently enhances the mechanical robustness and triboelectric output. The optimized AH film demonstrates a remarkable tensile strength of 168.2 MPa and a toughness of 9.52 MJ·m^–3. When integrated into a TENG device (AH-T), the device achieves a superior power output of 26.45 V·cm^–2, a rapid response time of 16 ms, and excellent cyclic stability over 6000 cycles. Critically, the AH-T demonstrates exceptional environmental resilience, maintaining stable operation at high temperatures (up to 350 °C) and in acidic/alkaline environments. This work provides a practical and effective strategy for designing environmentally robust triboelectric materials, advancing the development of durable energy harvesters for wearable and harsh environment applications.

The controlled doping of organic semiconductors is a promising strategy for optimizing the charge transport and optoelectronic performance in organic devices. Herein, we report a Brønsted acid doping method using the tris(pentafluorophenyl)borane–water complex [B(C₆F₅)₃-H₂O] to modulate the molecular ordering and charge dynamics of PBTTT-C14/PCBM heterojunctions. The air-exposed B(C₆F₅)₃ (BCF) forms a stable Brønsted acid complex capable of protonating PBTTT-C14, leading to enhanced charge delocalization and reduced trap density. The optimized 2 wt % BCF-H₂O-doped PBTTT-C14/PCBM film exhibited a carrier mobility of 6.89 × 10^–2 cm²V^–1s^–1, a responsivity of 343.57 A/W, and a photocurrent-to-dark-current ratio of 2.3 × 10⁵, representing nearly a 3-fold improvement over the pristine film. Spectroscopic analysis (¹¹B NMR, EPR, and UV–vis-NIR) confirms successful doping, while transient absorption and GIXRD measurements reveal a prolonged exciton lifetime, enhanced crystallinity, and improved molecular orientation. This work provides a straightforward approach to high-performance phototransistors via Brønsted acid doping of conjugated polymers.

Cyanate ester (CE) resins are high-performance matrix materials extensively utilized in extreme environments owing to their exceptional thermal stability and superior dielectric properties. However, the highly cross-linked network based on triazine rings also leads to intrinsic brittleness, severely limiting their broader applicability. The molecular-scale failure mechanisms remain insufficiently understood, partly due to the challenge of constructing accurate molecular models. This study overcomes these limitations by integrating molecular dynamics simulations with experimental validation. We developed a high-precision cross-linking algorithm incorporating reversible dimer metastable intermediates to form stable triazine rings and innovatively combined the polymer consistent force field with a Morse potential to simulate bond rupture during network failure. The resulting model predicts key performance parameters with less than a 3% error. Network formation is shown to proceed through three distinct kinetic stages: rapid oligomer formation, competitive network growth, and network integration/densification. More importantly, this work reveals a failure mechanism: although fracture is macroscopically brittle, it involves significant “microplasticity” at the molecular scale. The process is deconstructed into five characteristic stages with energy evolution analysis uncovering a dynamic equilibrium between elastic storage and dissipation via chain slippage, topological reorganization, and bond rupture/reformation. We conclude that macroscopic brittleness fundamentally results from the concentrated release of energy accumulated through numerous localized microplastic dissipation events.

Formaldehyde (HCHO), a hazardous volatile organic compound (VOC) in indoor environments, urgently requires efficient abatement strategies. MnO₂ is renowned for its excellent catalytic activity and enables effective degradation of HCHO at low temperatures. In this study, MnO₂ nanorods (NRs) were successfully grown on polypropylene (PP) nonwoven fabric via hydrothermal synthesis, yielding MnO₂ NRs @ PP composite material with integrated HCHO removal, antibacterial, and photocatalytic functions. pH value and temperature critically regulated MnO₂ morphology. Increasing pH raised the aspect ratio of MnO₂ NRs, which transitioned to MnO₂ nanoparticles (NPs) when the pH value was above pH 3.5. Higher temperatures promoted MnO₂ NRs formation, yet beyond 150 °C, excessive refinement led to MnO₂ NRs agglomeration and partial PP fiber melting. Optimal performance was achieved at pH 3.5 and 150 °C, where the composite exhibited a high HCHO removal efficiency of 55.1% along with notable antibacterial and photocatalytic properties. This work provides a feasible synthesis strategy for multifunctional composites that can be applied in indoor air purification and environmental remediation.

Excess free radicals cause oxidative stress, which damages cells and triggers inflammation. Inflammation generates more radicals, creating a self-perpetuating cycle that contributes to many human diseases. Antioxidants can neutralize radicals and prevent inflammation. Two unique amphiphilic dendritic antioxidants, Generation 1 (G1) and Generation 2 (G2), were developed, each featuring an equal ratio of hydrophobic syringaldehyde to water-soluble pyridoxal on their surfaces. G1 carries six units of each component, whereas G2 contains 12 units of each. In the 2,2-diphenyl-1-picrylhydrazyl radical-scavenging assay, G2 and G1 exhibited IC50 values of 1.28 and 2.6 μM, respectively. In comparison, syringaldehyde and pyridoxal exhibited significantly higher IC50 values of 200 and 16500 μM, respectively. G2 and G1 are 156 and 77 times more effective than syringaldehyde and 12890 and 6346 times more potent than pyridoxal, highlighting the benefits of building antioxidants within dendritic frameworks. In cell viability assays with RAW 264.7 macrophages, G1 only reduced cell viability at the highest tested concentration (323 μM), while G2 induced a statistically significant decrease starting at 11.3 μM. In lipopolysaccharide-stimulated macrophages, G1 at 32.3 μM showed strong anti-inflammatory effects, lowering NO levels by 76% and IL-6 levels by 100%, indicating that G1 can produce its potent anti-inflammatory effects via dual mechanisms: scavenging reactive oxygen species and reducing pro-inflammatory cytokine production. G2 had limited effects at its nontoxic concentrations.

Psoriasis is a chronic, immune-mediated inflammatory skin disease marked by recurrent lesions, which severely impact the quality of life of patients. While conventional treatments such as topical corticosteroids and immunosuppressants can relieve symptoms, prolonged use frequently leads to adverse effects, including skin irritation, liver toxicity, and bacterial infections. The colonization of S. aureus and its exotoxins play a key role in psoriasis pathogenesis, complicating treatment. Thus, controlling bacterial infections and toxin production is critical for improving therapeutic outcomes. In response to concerns over bacterial resistance, pyrimidine derivatives have gained significant attention due to their antibacterial, anti-inflammatory, and immunomodulatory properties. This study synthesized a series of poly tetrahydropyrimidine (PTHP) derivatives with various functional groups and backbone structures, identifying P-T-3 as the most promising candidate with excellent antimicrobial, anti-inflammatory, and biocompatible properties. Results show that P-T-3 effectively eliminates S. aureus and reduces toxin production, alleviating recurrent infections. Additionally, P-T-3 demonstrates antioxidant and anti-inflammatory effects, scavenging free radicals and reducing oxidative stress damage, enhancing psoriasis treatment. It also offers potential protection for patients on long-term immunosuppressive therapy. This presents a promising therapeutic approach for psoriasis, with the potential to enhance clinical outcomes and reduce the risk of complications.

Nickel-rich Li[Ni_xCo_yMn_1–x–y]O₂ (NCM) is critical for high-energy-density lithium-ion batteries but suffers from severe capacity fading and short cycle life, especially in high-nickel compositions such as NCM811, due to structural and interfacial instability. To address this, we develop an in situ-formed, thermoset cross-linked polyurethane acrylate (PUA) binder that acts synergistically as a robust binder and an artificial cathode–electrolyte interphase (CEI). This multifunctional PUA layer effectively shields active material from electrolyte corrosion, mitigates mechanical stress from volume change, and suppresses microcrack formation. As a result, the PUA-modified NCM811 cathode exhibits significantly improved cycling stability with 88.9% capacity retention after 200 cycles and superior rate capability (91 mAh g^–1 at 5 C). Furthermore, mechanistic investigations confirm the suppression of irreversible phase transitions and metal dissolution. This work demonstrates a practical electrode engineering strategy for stabilizing nickel-rich cathodes through interfacial control.

Covalent organic frameworks (COFs) have shown great potential in the field of photocatalysis. In this study, two amine monomers, 4,4’-(benzo[c][1,2,5]thiadiazole-4,7-diyl)dianiline (BTD) and 4,4’-(5,6-dimethyl-4,7-dihydrobenzo [c][1,2,5]thiadiazole-4,7-diyl)dianiline (CTD), with different electron-withdrawing capabilities, were selected to couple with 2,4,6-triformylphloroglucinol (Tp) to construct COFs. The 2BTD/1CTD COF synthesized by the blending strategy significantly enhanced the photocatalytic hydrogen evolution activity compared with the symmetrical two-component TpBTD and TpCTD COFs. The characterization results indicate that the 2BTD/1CTD COF with a D–A structure possesses the lowest exciton binding energy and higher photogenerated carrier separation and transport efficiency. These features collectively contribute to an enhanced charge separation efficiency. The blending strategy effectively improves the photocatalytic performance and provides an idea for designing more efficient COF photocatalysts.

With the rapid advancement of 5G communication and electronic technologies, electromagnetic interference issues have become increasingly severe, making the development of efficient, flexible, and self-healing electromagnetic shielding materials an urgent necessity. This study innovatively prepared a PVP/SA/CaCO₃/rGO (PSCG) dual-network hydrogel via biomimetic mineralization. Utilizing rGO as a conductive filler and CaCO₃ as a cross-linking agent, this material constructs a unique dual-cross-linked structure. At a thickness of 2 mm, it achieves an electromagnetic shielding effectiveness of 43 dB, surpassing most hydrogels. The PSCG hydrogel exhibits excellent electromagnetic shielding performance within a skin depth of 4 mm. It simultaneously exhibits the ability to self-repair conductivity and structural integrity within 3 s, along with excellent thermal insulation performance that maintains internal temperatures below 80 °C even at 400 °C. This significantly outperforms traditional metal-based materials and recently reported similar hydrogels, providing a high-performance solution for protecting electronic devices in extreme environments.

Leaching of incorporated silicone oil (SO) from poly(dimethyl-methylphenyl-methyltrifluoropropyl)siloxane (PDPFS) coatings has been proven to be the main driving force of their excellent fouling-release efficacy against marine bacteria and Navicula tenera, surpassing the effects of surface free energy or roughness. This study proposes an approach to control the SO leaching behavior of PDPFS coatings by altering their internal filler structure, thereby modulating their antifouling performance. Five anatase titanium dioxide (TiO₂) structures (microparticles, nanoparticles, photocatalytic particles, nanofibers, and nanotubes) were incorporated alongside methyl or phenylmethyl SO (MSO/PSO) into PDPFS-based coatings. The findings of the study establish distinct filler structure–property relationships. High-aspect-ratio TiO₂ (nanofibers/nanotubes) yielded a lower Young’s modulus and created continuous interfacial channels, which synergistically accelerated SO leaching and maximized its dynamic surface coverage–a process quantitatively described by the Higuchi model. A multistage leaching mechanism of “Homogeneous dispersion–Interfacial enrichment–Channelized migration–Surface leaching” is proposed. The results of the study support a fundamental shift in design strategy, highlighting that control of the internal filler structure can modulate SO leaching kinetics, providing a powerful paradigm for developing high-performance, sustainable fouling-release coatings.