Metal-backboned polymers, featuring one-dimensional atomic chains held together by metal–metal bonds, represent a highly promising class of functional materials. However, current synthetic methods rely on solution-phase multidentate bridging ligands, which severely limit the degree of polymerization. Herein, we report a pressure-driven solid-phase polymerization strategy that directly forms intermolecular Au―Au bonds from a dinuclear gold precursor at a pressure of 25 GPa, yielding a gold-backboned polymer (GBP). This method produces a continuous one-dimensional gold chain comprising more than 100 gold atoms. The peripheral ligands coordinate around the backbone, stabilizing the chain and endowing the polymer with high solution processability. The resulting GBP exhibited high thermal stability, well-defined glass transition temperature, and broad-spectrum photoluminescence spanning from the visible to near-infrared regions. This study opens a new synthetic route to long-chain metal-backboned polymers and provides a structurally well-defined model system for investigating the intrinsic photophysical properties of one-dimensional metal–metal bonds.

Conventional chemotherapy and radiotherapy damage normal tissues due to off-target toxicity, impairing patient prognosis. Chemoradiotherapy (CRT)—the concurrent use of chemotherapy and radiotherapy—has gained considerable attention, as it suppresses primary tumors and reduces metastasis. However, dose-limiting drug toxicity remains a major barrier to clinical CRT. To mitigate adverse effects and improve drug bioavailability, nano-sensitizer (NS)-mediated CRT has become a research focus. Nonetheless, unique tumor microenvironmental features, including hypoxia, abnormal vasculature, elevated reactive oxygen species, mild acidity, dense extracellular matrix, and immunosuppression, severely compromise NS efficacy. Accordingly, smart NS designed to surmount these microenvironmental barriers represent a key direction in drug development. This review summarizes recent advances in tumor microenvironment-targeted NS and their preclinical and clinical applications, aiming to deepen understanding of microenvironmental challenges in CRT and facilitate the development of potent NS.

Lithium-ion battery liquid electrolytes serve as the "blood" of the battery, undertaking the critical mission of transporting lithium ions between the cathode and anode. Consequently, the market demand for performance continues to escalate. However, lithium-ion batteries still face substantial challenges in terms of specific energy, safety, and cycle life, with the degradation of ester-based electrolytes being particularly prominent. Therefore, research on multifunctional electrolyte additives has become a focal area, offering promising avenues for effectively addressing these challenges. This study systematically analyzed the degradation mechanisms of ester-based lithium hexafluorophosphate (LiPF₆) electrolytes, emphasizing the pivotal role of the inevitably generated hydrogen fluoride and phosphorus pentafluoride (HF and PF₅) in electrolyte breakdown. This elucidates the crucial contribution of mechanism-oriented functional groups in stabilizing electrolytes, scavenging HF/PF₅, modulating solvation structures, and engineering robust solid electrolyte interphase (SEI) and cathode electrolyte interphase (CEI). Furthermore, we developed a high-throughput computational workflow utilizing Gaussian 09, Multiwfn, and VMD to rationally design multifunctional additives through synergistic integration of functional groups and density functional theory (DFT)-guided screening. This approach evaluates HF/PF₅ binding energies, frontier orbital energies (HOMO/LUMO) levels (redox activity), chemical hardness, and electrostatic potential interactions. Unlike previous reviews that primarily rely on empirical data summaries, this work innovatively bridges the gap between macroscale electrolyte failure behaviors and the microscale rational design of additives. By establishing a unified framework from HF/PF₅ evolution to DFT-driven multi-functional molecular engineering, our study provides a predictive and systematic design guideline to minimize experimental trial and error, thereby accelerating the development of wide-temperature, high-voltage electrolytes with enhanced cycle life and safety.

Metal-backboned polymers have been proposed as a new class of materials with remarkable physical and chemical properties for applications in optoelectronics, magnetism, and energy. However, the number of metal atoms in their backbones is limited to less than 30 to date. This has prevented the systematic investigation of their properties. Herein, we report the synthesis of metal-backboned polymers with a polymerization degree of 169. Using gold as a model system, we identified that the controlled release of Ag⁺, an electron-donating imidazole co-ligand, ligand steric/electronic effects, and elevated reaction temperature are key to achieving such long chains. The resulting metal-backboned polymers display hallmark polymer behaviors such as glass transition, together with a unique electronic structure featuring pronounced electron delocalization along the Au backbone and efficient room-temperature phosphorescence. This work provides an effective route to long-chain metal-backboned polymers and deepens the understanding of the electronic structures in one-dimensional metal backbones.

Fully π-conjugated polymers are promising for flexible optoelectronics; however, their inherent brittleness poses a challenge for achieving high-performance flexible electronic devices. In this study, we developed a carbazole-based semiconductor fluid plasticizer, TODPFCZ, to simultaneously enhance the stretchability and optoelectronic properties of poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) films using an external plasticizing strategy. The fluid TODPFCZ molecules incorporated into the F8BT matrix disrupted interchain π-π stacking and crystallinity, which significantly enhanced the stretchability, increasing the fracture strain from 18% to 44% and the crack-onset strain from 5% to 35%. Owing to the efficient energy transfer from TODPFCZ to F8BT, polymer light-emitting diodes (PLEDs) based on the optimized blend films showed stable electroluminescence and maintained efficiency even after being pre-strained up to 15%, revealing outstanding stress tolerance. The blended films also exhibited excellent recoverability and thermoplasticity. This study demonstrates that carbazole-based semiconductor fluid plasticizers provide a versatile and effective pathway for designing high-performance, intrinsically stretchable, fully π-conjugated polymers for durable flexible electronics.

Intrinsically stretchable organic photodetectors (IS-OPDs) are highly attractive for applications such as skin-mounted wearables, soft robotics, and electronic textiles. However, simultaneously achieving mechanical robustness and stable optoelectronic functionality under high strain remains a challenge. Here, we demonstrate that the fibrillar network morphology formed by high-molecular-weight conjugated polymer blends provides an effective pathway to overcome this limitation. The entangled, interconnected polymer fibrils establish a mechanically percolated network that efficiently dissipates strain energy and suppresses crack propagation, enabling a high fracture strain of about 80% and enhanced toughness. The fibrillar network also forms continuous charge transport pathways, resulting in improved carrier mobility and reduced trap density. Therefore, the IS-OPDs exhibit outstanding performance stability under large deformations, maintaining a high detectivity of about 10¹² Jones at strains above 40%, while enabling reliable optical communication and clear imaging capability even at 100% strain. Our study identifies a high-molecular-weight-driven fibrillar morphology as a key structural motif for mechanically robust IS-OPDs.

Conjugated polymers are indispensable materials in organic optoelectronics. Living chain-growth polymerization has emerged as a promising strategy for synthesizing conjugated polymers with narrow polydispersity indices. To date, the majority of living chain-growth polymerization protocols have relied on Kumada-type cross-coupling reactions using aryl halides as monomers. Herein, we developed a nickel-catalyzed living chain-growth polymerization method based on carbon–sulfur bond activation, employing aryl sulfides as monomers, which enabled the synthesis of poly(3-hexylthiophene) (P3HT) with a regioregularity exceeding 95%. Kinetic studies confirmed the chain-growth mechanism of the polymerization, while steric hindrance and electronic effects were found to play important roles in regulating the polymerization behavior.

Hydrogel actuators with intrinsic softness, biocompatibility and large deformability hold great promise for extensive applications in intelligent autonomous soft robotics. However, achieving directionally controllable autonomous motion under constant stimulation remains a key challenge, primarily due to the isotropic and densely crosslinked nature of conventional hydrogel networks, which limits both directional driving forces and efficient mass transport pathways. Here, we report a simple method for the fabrication of curved cylindrical hydrogels with aligned porous channels that enable autonomous rolling under constant light irradiation via directional freezing assembly-assisted in situ photopolymerization. Benefiting from the oriented open-cell network, the hydrogel exhibited fast light-responsive deformation with bending and recovery speeds of 16.5 (°)·s^–1 and 24 (°)·s^–1, respectively. Notably, the hydrogel achieved self-sustained rolling under constant light irradiation at a speed of 0.77 mm·s^–1, arising from the synergy of structural anisotropy and geometric curvature. By spatially modulating the irradiation region, the photo-guided direction-steerable rolling could be realized. Additionally, the hydrogel implemented multiple tasks including obstacle crossing, stair climbing and cargo transport, highlighting its potential in biomimetic soft robotic systems.

The deswelling of microgels is governed by solvent characteristics and particle concentration. Soft nanoparticles have been synthesized and dispersed in small molecular solvents or oligomeric polystyrenes. Coarse-grained molecular dynamics simulations were performed to quantify particle dimensions. The linear viscoelasticity of these solutions was experimentally characterized. In good solvents, increasing the particle concentration induces deswelling because of the enhanced crowding-induced osmotic compression. Increasing the molecular mass of the solvent could also enhance deswelling by suppressing solvent penetration into the nanoparticle network. Equilibrium relations derived from the osmotic-pressure balance are developed to describe these two mechanisms and are shown to capture the simulation results. A single unified framework can describe the deswelling over a broad range of solvent masses and particle concentrations. In addition, varying the solvent mass shifts the fragility transition observed experimentally in solutions of soft nanoparticles, thereby linking deswelling to changes in the glassy dynamics. This work establishes a unified framework for understanding microgel deswelling across concentration- and solvent-controlled regimes.

Liquid crystal elastomers (LCEs) are compelling smart materials for soft robotics and flexible electronics. However, both conventional and dynamically crosslinked LCE systems fundamentally rely on chemically crosslinked networks, which has long been regarded as a prerequisite for their reversible actuation. While thermoplastic elastomers based on block copolymers offer a structural model for constructing robust physically crosslinked networks, it remains a significant challenge to transplant this design strategy into LCEs to realize reversible actuation in non-covalently crosslinked system. Herein, we develop a physically crosslinked thermoplastic LCE system based on ABA-type triblock copolymers (PS-b-MCLCP-b-PS). Polystyrene (PS) hard-block aggregates act as reversible physical crosslinking sites, effectively replacing permanent covalent bonds. We systematically investigated the regulatory effect of the PS block content on the microstructure, mechanical properties, and thermally responsive actuation of the materials. By achieving an optimal balance between physical network confinement and the segment mobility of the liquid crystal phase, the resultant elastomer exhibits excellent reversible thermally driven actuation, well-balanced mechanical properties and solvent recyclability with high mechanical retention. Furthermore, the material demonstrates prominent wide-temperature-range damping performance attributed to the synergistic energy dissipation of the physical network and mesogen rotation. This work offers a feasible molecular design strategy for sustainable and multifunctional LCEs to break the dependence on chemical crosslinking for reversible actuation.

This study explored the chemical recycling of polyurethane (PU) elastomers via acidolysis using itaconic acid and dimethylformamide (DMF) as the solvent without the use of glycol. The depolymerization process was optimized by varying the reaction parameters, and the resulting oligomers were analyzed using end-group analysis. PU coatings were formulated using recovered oligomers and isocyanates derived from isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and toluene diisocyanate (TDI). Analytical techniques including differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FTIR), electrochemical impedance spectroscopy (EIS), and gel permeation chromatography (GPC) were used for characterization. TDI based coatings exhibited superior optical, mechanical, chemical, thermal, and anticorrosive performance over the HDI and IPDIbased coatings. This study successfully showcased a facile method for recycling of PU waste along with PU coating formulations from 100% recycled oligomers, showcasing the use of recycled polyols in high performance applications.

Vascular closure devices (VCDs) play a critical role in preventing bleeding and hematoma formation after percutaneous interventions. Despite effective mechanical hemostasis, the current collagen-based VCDs lack anti-inflammatory and regenerative capabilities. Herein, we report the development of a polydopamine (PDA)-modified collagen sponge (Col@PDA) to enhance the anti-inflammatory and pro-regenerative potential of collagen-based materials. PDA modification not only preserved the sponges’ inherent porosity and swelling behavior but also endowed them with immunomodulatory functions. In vitro, the modified sponges exhibited superior anti-inflammatory and antioxidant activities in RAW 264.7 macrophages and L929 fibroblasts. In a rat subcutaneous implantation model, Col@PDA attenuated local inflammation, promoted dermal regeneration, and enhanced collagen deposition and angiogenic factor expression. Collectively, PDA modification enables collagen sponges to actively modulate the healing microenvironment, resulting in faster tissue repair than unmodified collagen sponges.

As plastic pollution has become increasingly severe, the development of recyclable and rapidly degradable polyesters has significant practical value and significance. In this study, seven-membered cyclic 1,3-propylene glycol oxalate (POx) was successfully synthesized through a two-step polycondensation-depolymerization method using dimethyl oxalate (a low-cost and readily accessible bulk chemical) and bio-based 1,3-propylene glycol as the starting materials. Using Sn(Oct)₂ as the catalyst, high-molecular-weight poly(1,3-propylene oxalate) (PPOx) was efficiently prepared via ring-opening polymerization (ROP) of POx. This ROP demonstrated excellent reactivity, attaining a monomer conversion up to 95% within 10 min, and PPOx had a maximum intrinsic viscosity (η) of 1.06 dL/g. Furthermore, the prepared PPOx could be catalytically depolymerized to enable efficient recovery of the POx monomer, with a yield of 60% and a purity of 98%. The degradation performance tests indicated that PPOx exhibited rapid degradation, reaching a degradation rate of up to 99% within 50 days. Owing to the innovative selection of raw materials and the design of a closed-loop process, this study provides a new economical and sustainable strategy for reducing dependence on petroleum resources, offering valuable insights into the development of recyclable and rapidly degradable polyesters.

Self-assembly of block copolymers (BCP) with quantum dots (QDs) in a three-dimensional confined emulsion system is an effective method for preparing advanced QD/polymer composite particles with diverse morphologies and functionalities. However, the obtained particles normally exhibit sub-micrometer sizes and contain residual toxic surfactants, which hinders their potential application in fluorescent bio-imaging. In this study, we designed and synthesized a rod-coil-type amphiphilic block copolymer bearing a rigid hydrophobic poly(arylene ether nitrile) (PEN) block end-capped with a flexible hydrophilic poly(ethylene glycol) (PEG) segment for the first time. Subsequently, the synthesized amphiphilic block copolymer, abbreviated as PENG, was employed as both the macromolecular surfactant and polymeric matrix to encapsulate the green-emitting oleophilic QD via emulsion confinement self-assembly. This process ultimately results in the generation of surfactant-free QD@PENG nanoparticles showing robust fluorescence emission over a wide pH and salt concentration range. Meanwhile, both the fine morphology and fluorescence emission of the QD@PENG nanoparticles were well preserved even after steam sterilization at 121 °C for 2 h, which is attributed to the high-temperature resistance of the rigid PEN segment. Owing to their robust fluorescence, biocompatibility, and nanoscale size (about 100 nm), the optimized QD@PENG nanoparticles exhibited good performance in fluorescent imaging of macrophage cells. The current work proves that the emerging rod-coil amphiphilic block copolymers could serve as a promising matrix for the preparation of reliable bio-imaging probes.

With growing global focus on plastic circular recycling and sustainable development, chemical upcycling is gaining importance. It converts waste plastics into high-value products, avoiding the performance degradation and downcycling associated with conventional physical recycling processes. Polyimide (PI) is a high-performance polymer material, particularly valued in the field of lithium-ion batteries as a separator due to its high-temperature resistance, favorable mechanical strength, and good electrolyte wettability. However, its broader application has been limited by the high cost of its monomers and the energy consumption of its preparation process compared to conventional lithium-ion battery separators such as polyethylene/polypropylene. Here, we propose an effective strategy for the high-value application of recycled polyimide (PMDA/ODA-type) films through chemical catalysis: using lithium hydroxide to catalyze the partial ring-opening of the imide rings in recycled polyimide, transforming the insoluble and infusible recycled polyimide into a soluble poly(amic acid)-polyimide system (PAA-PI). This system is further processed via electrospinning to fabricate polyimide nanofiber membranes, which are applied as separators in lithium-ion batteries. They exhibit similar structural, thermal properties, and mechanical properties to the PI separators prepared by the traditional method, while also possessing good porosity, electrolyte wettability, and electrolyte uptake. Furthermore, batteries prepared using this recovered PI separator (RPI) exhibit excellent high-rate performance (135.55 mAh·g^–1 at 5 C current) and long-term cycle stability (118.01 mAh·g^–1 after 100 cycles at 0.5 C current, and 87.10 mAh·g^–1 after 100 cycles at 2.0 C current), showing no significant difference compared to batteries prepared with conventional PI separators, while outperforming batteries prepared with commercial Celgard 2500 separators, essentially meeting the performance requirements of next-generation lithium-ion batteries. This work presents a strategy for the low-cost production of high-safety polyimide-based separators in lithium-ion batteries, enabling the high-value reuse of polyimide waste and thereby establishing a process consistent with green chemistry and sustainable development.

The synthesis of bottlebrush block copolymers (BBCPs) via ring-opening metathesis polymerization (ROMP) typically relies on exo-norbornene-terminated macromonomers to achieve high polymerization rates. However, norbornene derivatives synthesized via the Diels-Alder reaction were obtained as mixtures of exo and endo isomers, with the endo isomer predominating. This presents a significant challenge for the preparation of well-defined BBCPs from such mixtures because of the inherently low ROMP reactivity of endo-norbornene. Here, we demonstrate that polymerization kinetics are strongly influenced by the solvent, temperature, and configuration of the norbornene end group. By optimizing these parameters, the complete conversion of endo/exo macromonomer mixtures can be achieved within a short time, enabling the efficient synthesis of well-defined BBCPs. The resulting BBCPs exhibited self-assembly behavior comparable to those prepared from purely exo-norbornene-terminated macromonomers, forming structurally colored polymer microspheres that function as eco-friendly photonic pigments. This study provides an efficient and cost-effective strategy for the synthesis of BBCPs using commercially available norbornene derivatives.

Co-assembly of different block copolymers has emerged as a versatile strategy for constructing stimuli-responsive polymer nanostructures with broad applications in biomedicine. However, the spatial distribution of functional blocks and the structural transition of mixed assemblies under external stimuli remain insufficiently explored, limiting the rational design of efficient delivery systems with on-demand cargo loading and release. Here, we systematically investigated the self-assembly behaviors of AB/BC mixture in solution using the dissipative particle dynamics (DPD) method. By varying the interaction parameters between different components, several classic morphologies were obtained, including vesicles (V), multicompartment vesicles (MCV), and large compound micelles (LCM). Most importantly, the distinct hydrophilic blocks (A/C) underwent microphase separation during the co-assembly process, yielding aggregates with patterns having different internal A/C distributions, such as mixed, Janus (J), and A- or C-dominated (A/C) vesicles. Upon applying external stimuli, we tracked the dynamic rearrangement process of blocks A and C, focusing on the inversion of the dominant internal block. The results revealed that kinetic factors significantly influence the inversion process, either accelerating, decelerating, or even freezing the structure. A kinetic-control mechanism for the inversion was proposed, wherein the mobility of the hydrophilic blocks and the barrier effect of the hydrophobic layer can be tuned by adjusting the interaction parameters (such as a_BC and a_BS), thereby governing the occurrence and kinetics of inversion. These findings can provide valuable insights into the precise modulation of block distribution and rearrangement in stimuli-responsive aggregates, offering applications in controlled drug delivery and release processes.

Invasive fungal infections remain a significant global health threat, and the development of antifungal agents that selectively target fungi remains a critical challenge. This study investigates hyperbranched polylysine (HPL) with tunable molecular weight and charge density as a potential selective antifungal candidate. HPL1, with the lowest molecular weight, showed negligible antimicrobial activities, while HPL3, with the highest molecular weight, exhibited broad-spectrum antimicrobial effects against both bacteria and fungi. Notably, HPL2, the mediate molecular weight, demonstrated selective antifungal activities against clinically relevant Candida species, including C. albicans, C. krusei, C. parapsilosis, C. tropicalis, and C. glabrata. This selectivity is mainly ascribed to its optimal zeta potential and appropriate hydrodynamic size, enabling HPL2 to penetrate through the fungal cell wall while stuck in bacterial cell envelopes. Mechanistic studies revealed that HPL2 initially adheres to the fungal surfaces induced via electrostatic interactions, then passively penetrates the fungal cell wall, disrupts membrane integrity, induces intracellular damage, and ultimately leads to cell death. Furthermore, HPL2 exhibited excellent biocompatibility and in vivo therapy efficacy with minimal disruption to host gut microbiota. These results highlight HPL2 as a promising antifungal agent with potent efficacy and favorable safety, which can be easily synthesized at kilogram scale.

In this study, unique conductive gratings were constructed in polyurethane (PU) foams to achieve tunable electromagnetic shielding. First, a mold enabling region-selective silver plating was fabricated through model design and 3D printing technology. Second, PU foam was placed inside the mold to create controllable exposure regions. Third, a region-selective silver plating process was achieved by exploiting this localized exposure, thereby successfully constructing conductive grating composite foams (grating-Ag/PDA@PU). The effects of the grating number, arrangement pattern, spacing, and incident angle of electromagnetic waves on the electromagnetic interference shielding effectiveness (EMI SE) were systematically investigated, revealing the structure-property relationship between shielding performance and grating geometric parameters. The results indicate that the EMI SE values of a single-layer conductive grating are positively correlated with the number of gratings. For a multilayer conductive grating, staggered parallel arrangements exhibit superior shielding performance compared to simple parallel arrangements. Appropriately increasing the spacing between gratings helps reduce mutual electromagnetic coupling, thereby enhancing the overall EMI SE values. It was also found that a nondestructive electromagnetic shielding switch could be realized simply by flipping the sample. Specifically, the EMI SE values changing from 3.53 dB to 34.04 dB can be achieved by simply flipping the foams. This study provides new insights into the design and fabrication of tunable conductive gratings for use in electromagnetic shielding switches.

Information leakage and forgery continue to threaten the security of the information storage and transmission. However, most existing physical encryption materials rely on single and predictable stimulus-response mechanisms, resulting in limited security, programmability, and service life. Herein, a high-security sequential 4D encryption system is developed based on a dynamic covalent polyurethane network that integrates shape memory, self-healing, and photochromism in one system. Arylboronic acid was incorporated into the polyurethane framework to form a dynamic boron carbamate network. The resulting boroxine crosslinks act as reversible junctions, enabling thermally triggered shape memory behavior, while simultaneously providing efficient self-healing through reversible hydrolysis and reformation. The optimized polyurethane exhibited a tensile strength of about 35 MPa, a shape-fixity ratio of >99%, and a shape-recovery ratio of up to 83% while achieving a self-healing efficiency of about 81% after thermal treatment. In parallel, the incorporation of a photochromic dye enables precise time-dependent color evolution under ultraviolet irradiation. The synergistic coupling of thermal and photonic responses allows sequential and time-gated information decoding, significantly increasing the encryption complexity and resistance to unauthorized access. The resulting films function as dynamic 4D encryption carriers from which correct information can be retrieved only through a predefined sequence of shape recovery and color transformation. This study provides a versatile strategy for next-generation physical encryption materials with intrinsic damage tolerance, long-term reliability, and storage potential in optical data storage and advanced anti-counterfeiting applications.

Traditional acrylate reactive diluents, which are derived from fossil resources, are known to exhibit significant irritation and allergenic potential, leading to their prohibition in high-end electronics, particularly in wearable devices. To address these limitations, four bio-based acrylate reactive diluents (BRDs) were synthesized via the reaction of alcohols derived from renewable sources, piperitol, vanillin, eugenol, and isosorbide, with methacrylic anhydride. The viscosity of the synthesized BRDs and the T_g of their corresponding polymers were systematically evaluated and compared with those of the petroleum-based diluent isobornyl acrylate (IBOA). The BRDs were then blended with acrylate-terminated polyurethane (APU) to formulate a series of UV-curable polyurethane adhesives (APU-BRDs). The results suggest that BRDs effectively reduce the viscosity of APU. By selecting and combining BRDs, the bonding strength of APU-BRDs to polar substrates such as PC and glass can reach 20 MPa. Even for non-polar substrates like PE, the strength is close to 5 MPa. The values obtained in this study exceed those of adhesives prepared using the conventional petroleum-based diluent IBOA. Furthermore, the study explored the potential application of APU-BRDs in smart wearable devices, confirming their suitability for next-generation wearable technology.

Long-lived room-temperature phosphorescent (RTP) films are attractive for information encryption, yet binary host-guest polymer systems often suffer from weak afterglow and limited operational reliability. In this study, we developed a ternary RTP system using poly(vinyl alcohol) (PVA) as the host matrix, coumarin derivatives as the emissive guests, and a third component, boric acids (BA/3-BBA), tannic acid (TA), or metal salts (Ca²⁺, Mn²⁺, Zn²⁺), to regulate triplet-state generation and stabilization. Structural analysis confirmed the guest incorporation and borate network formation. Guest loading decreased the visible transmittance, whereas borate crosslinking partially restored the transparency and improved the thermal integrity (main decomposition near 430 °C). The films exhibit good mechanical performance (for PVA-A: 32.70 MPa tensile strength; 245.60 MPa modulus; and 63.82 MJ·m^–3 toughness), while crosslinking/coordination increases stiffness (up to 1479.55 MPa modulus for PVA-A-TA). The introduction of the third component enhanced the RTP and photoluminescence quantum yield (PLQY), except for Mn²⁺, which induced quenching. The materials also demonstrated reversible moisture response and good UV stability. Leveraging time-gated afterglow, multi-level information encryption is achieved using dynamic digit displays and an ASCII matrix with decoy and delayed outputs. This ternary strategy enables the practical optimization of PVA-based flexible RTP materials for high-security anti-counterfeiting and information encryption applications.

Bioinspired smart surfaces enable reversible regulation of surface wettability, which is increasingly important for the advancement of surface and interface science. Herein, a novel fluorine-free photoresponsive azo-copolymer was rationally designed and synthesized via a molecular engineering strategy involving the synergistic integration of photoresponsive azobenzene moieties and low-surface-energy organosilicon segments. A facile solution dip-coating method was employed to construct photoresponsive smart fabric surfaces. Benefiting from the excellent reversible trans-cis isomerization of the azobenzene moieties within the azo-copolymer, the resulting coating achieved a notable surface energy variation of up to 32.75 mN·m^–1. The as-prepared smart fabrics exhibited rapid, reversible wettability switching between high hydrophobicity (water contact angle of about 135°) and superhydrophilicity (0°) within 120 s under alternating UV and visible light irradiation. Meanwhile, the smart fabric surfaces exhibited outstanding chemical and mechanical robustness, enabling resistance to harsh environmental conditions, repeated abrasion tests, and various mechanical deformations, such as stretching, curling, and folding. More importantly, as a proof-of-concept demonstration, diverse rewritable wettability patterns were conveniently fabricated on a smart fabric surface via selective light exposure. This simple and effective strategy, together with the as-developed smart surfaces, holds great promise for application in information storage, biosensors, and microreactors.

Acrylonitrile butadiene styrene (ABS) is widely used owing to its excellent mechanical properties, thermal stability, and processability; however, its poor inherent flame retardancy limits its applications, which require higher safety. Conventional flame-retardant ABS systems mainly rely on a bromine-antimony synergistic system, in which antimony trioxide (ATO) is costly and environmentally concerning. In this study, decabromodiphenylethane (DBDPE) and ATO were first selected as the flame-retardant systems and combined at a mass ratio of 3:1. The results showed that the ABS/12DBDPE/4ATO composite achieved a UL-94 V-0 rating with a limiting oxygen index (LOI) of 24.0%. Subsequently, zinc ferrite (ZF) nanoparticles were synthesized via a co-precipitation method and employed as partial substitutes for ATO in ABS composites. When 50 wt% ATO was replaced by ZF, the ABS/12DBDPE/2ATO/2ZF composite exhibited an increased LOI value of 26.9%, while still achieving a UL-94 V-0 rating. Compared with neat ABS, the peak heat release rate (PHRR) and total heat release (THR) were reduced by 62.1% and 46.3%, respectively. Furthermore, incorporating 5 wt% nitrile butadiene rubber (NBR) significantly improved the toughness of the composite, increasing the impact strength from 3.8 kJ/m² to 13.2 kJ/m², without compromising flame retardancy. Overall, this study demonstrates an effective and practical strategy to reduce ATO usage while simultaneously enhancing the fire safety and mechanical performance of ABS.

Composite solid-state electrolytes (CSEs) with excellent flexibility and high safety hold great potential for high performance lithium batteries. However, its low room temperature ionic conductivity and transfer number have plagued its practical application. In this work, local Li diffusion was tailored by the synergetic effect of halloysite nanotubes (HNTs) and high-entropy ZIF in a polyvinylidene fluoride/LITFSI/Li_6.85La_2.95Yb_0.05Zr_1.85Ta_0.15O₁₂ matrix. The anchoring of TFSI^– anions by the rich open metal sites in HE-ZIF and the inner positively wall in HNT, combined with the continuous diffusion pathway of Li⁺ built by the negatively surface of HNT, distinctly enhances the ionic conductivity and transfer number of the electrolyte. A high ionic conductivity (1.06×10^–3 S·cm^–1 at 30 °C) and high Li⁺ transference number (0.86) were achieved in PLLH-HE. The lithium symmetric battery (Li//PLLH-HE//Li) exhibited excellent interfacial compatibility and a high critical current density (CCD, 2.38 mA·cm^–2). A lithium metal battery assembled with LiFePO₄ (LFP) cathodes exhibited a high discharge specific capacity of 141 mAh·g^–1 after 400 cycles at 0.5 C, while the cell assembled with LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) also delivered a high discharge specific capacity of 140.1 mAh·g^–1 at 1 C after 600 cycles. This work reveals the critical role of local Li diffusion and provides a general method for enhancing the electrochemical properties of CSEs for solid state batteries.

The precise microstructural origin of cavitation in semicrystalline polymers remains a subject of persistent controversial. Consequently, the exact spatial initiation of voids within a single spherulite remains under debate. Resolving this ambiguity has long been hindered by the spatial resolution limits of the conventional characterization techniques. To overcome this limitation, we employ an integrated approach of in situ synchrotron microfocus X-ray scattering and ultrasmall-angle X-ray scattering to investigate the cavitation behavior within individual isotactic polybutene-1 spherulite during uniaxial stretching. It turns out that early-stage voiding exhibits a distinct spatial sequence. Structural damage preferentially initiates at the spherulitic center, subsequently emerges in the equatorial region, and ultimately propagates to polar regions. By reconstructing the three-dimensional lamellar orientation within the undeformed spherulite, we revealed that lamellae oriented parallel to the stretching direction are extensively distributed across all spherulitic regions. Based on these findings, we propose a micro-mechanical cavitation model. In this framework, parallel lamellae undergo direct mechanical fragmentation under stress, with microvoids nucleating within the interstitial gaps between adjacent crystalline blocks.

Silicon-based anodes are promising candidates for next-generation lithium-ion owing to their high theoretical specific capacity. However, their practical application is limited by their severe volume expansion and poor electronic conductivity during cycling, which results in rapid capacity fading. To address these challenges, a novel polymer-derived ceramic (PDC) precursor, PSZ/PAN, was designed and synthesized by integrating polysilazane (PSZ) with polyacrylonitrile (PAN). The synthesis involved an initial free-radical polymerization of PSZ to form a crosslinked network, followed by in situ introduction and polymerization of acrylonitrile, yielding a PSZ/PAN hybrid with an interpenetrating network structure at the molecular level. Upon pyrolysis, the resulting SiCNO/C hybrid anode exhibited a high reversible specific capacity of 1050.1 mAh·g^–1 at 500 mA·g^–1 and excellent cycling stability, retaining 73.2% of its initial capacity after 600 cycles. This molecular-level interpenetrating design of polymer-derived ceramics provides a promising strategy for the development of high-performance anode materials for lithium-ion batteries.

The rapid advancement of communication technologies and wearable applications has increased the demand for high-performance flexible electromagnetic wave absorption materials. Conventional conductive fibers are often constrained by their poor wearability, weak interfacial stability, and limited absorption efficiency, which restrict their reliability and practical applicability in dynamic environments. Herein, a flexible and robust electromagnetic-absorbing fiber was successfully fabricated via wet spinning techniques, which integrates multi-walled carbon nanotubes (MWCNTs), polyaniline (PANI), and aramid nanofibers (ANFs). Polymerization of PANI on the MWCNTs surface is employed to optimize impedance matching and enhance interfacial compatibility, while ANFs serve as a continuous structural skeleton, improving the mechanical strength and spinnability. The resulting composite fibers exhibited a tensile strength of (202.0±8.0) MPa and an elongation at break of 13.6%±0.9%, stable electrical conductivity under mechanical deformation, and ultrasonic cleaning. Notably, the fiber architecture enables superior electromagnetic wave absorption, achieving a minimum reflection loss of −62.07 dB and an effective bandwidth of 3.24 GHz compared to the powder counterparts, owing to the extended propagation path and multiple scattering within the aligned fiber network. In addition, the composite fibers demonstrated self-extinguishing behavior during combustion, reflecting their inherent flame-retardant characteristics. This study provides a feasible strategy for developing flexible, high-performance electromagnetic wave (EMW)-absorbing fibers for next-generation protective textile materials.

The reprocessing and recycling of vulcanized rubbers remain challenging because conventional vulcanization networks are irreversible. Here, we designed a modified sulfur crosslinker via inverse vulcanization to regulate the exchange kinetics of vulcanization networks, thereby governing the mechanical recovery behavior of reprocessed rubbers. Copolymers of sulfur and thioctic acid (CSTA), synthesized via inverse vulcanization, were employed to crosslink butadiene-styrene rubber. After vulcanization, thioctic acid (TA) introduces dynamic disulfide bonds into the conventional vulcanization networks, enabling thermally activated network rearrangement while preserving the overall crosslinked structure. Kinetic analysis revealed that increasing the TA content accelerated network exchange and significantly lowered the apparent activation energy for network rearrangements. Correspondingly, the recovery of the mechanical properties after reprocessing improved with increasing TA content. These results establish a clear correlation between vulcanization network exchange kinetics and macroscopic mechanical performance, providing a kinetic basis for the design of reprocessable vulcanization networks and offering a promising route toward recyclable high-performance rubber materials.

Understanding the film formation mechanism of waterborne latex is crucial for developing high-performance, eco-friendly coatings. However, the influence of various enviromental factors, i.e. temperature and wind, on spatiotemporal structure heterogeneity induced during drying complicates the establishment of the structure-process-property of coating. Here, we track a polyacrylate latex film formation using a custom-built single-sided nuclear magnetic resonance (NMR) hyphenated instrument. Two-dimensional correlation spectra reveal highly restricted water dynamics within the latex suspension, evidenced by a decreased self-diffusion coefficient D from 2.00×10^–9 m²/s of pure water to 1.39×10^–9 m²/s in suspension with a plummeted T₁/T₂ of 30, which is about 111 for pure water. For film drying under mild conditon (24 °C without airflow), dense particle packing induces strong capillary forces, generating anomalous fast-diffusion channels (D up to 31.05×10^–9 m²/s) to accelerate water evaporation resulting in homogeneous structure along the thickness direction. Conversely, after introducing airflow, i.e. 35 °C with 10 L/min airflow, the accelerated drying rate (3.72 μm/min) drastically amplifies the spatiotemporal heterogeneity and triggers premature surface skinning. Such skin-core structure traps residual water inside and inhibit further coalescing of latex particles. The uncoalesced bottom layer thicknesses quantitatively predicted by non-destructive single-sided NMR (about 100, 200, and 400 μm), which is well consistent with SEM measurements (93, 240, and 409 μm, respectively). This work provides direct physical insights and theoretical guidance for the formulation and application of waterborne coatings during real service condition.

Photo-induced reaction-diffusion systems provide a valuable theoretical framework for exploring nonequilibrium self-organization under external energy input. Most existing studies have focused on binary mixtures subjected to globally uniform driving, whereas realistic chemical and biological systems are typically multicomponent and experience strongly localized energy supply. In this work, we extend photo-induced reaction-diffusion models to a multicomponent setting and systematically investigate pattern formation in a minimal three-component system. By combining numerical simulations with linear stability analysis, we find illumination can induce periodic nonequilibrium structures, whose characteristic length scales can be tuned by the input energy density and intrinsic molecular energetic parameters. We further introduce localized illumination to capture the effects of spatially heterogeneous energy input. Under such conditions, a theoretical phase diagram for pattern formation is constructed, revealing distinct spatial morphologies, including dot patterns and target-like structures. In addition, we explicitly examine the nonnegativity of entropy production for both globally and locally illuminated systems. These results provide a unified and physically consistent framework for understanding photo-induced pattern formation in multicomponent nonequilibrium systems and are also applicable to photoexcitation-controlled supramolecular systems such as persulfurated-arene/block-copolymer assemblies.

Polymer compositions based on plasticized poly(vinyl chloride) (PVC) are extremely widely used in engineering and everyday life. Diester plasticizers based on aliphatic dicarboxylic acids are currently considered as new, environmentally friendly, and less toxic plasticizers for poly(vinyl chloride). In the present work, the structural organization of polymer compositions based on poly(vinyl chloride) plasticized with dicarboxylic acid diesters—dibutoxyethyl glutarate, dibutoxyethyl adipate, octyl butoxyethyl adipate, dibutoxyethyl azelate, and dibutoxyethyl sebacate—was studied using molecular dynamics modeling methods. The methodology of fragment condensation was used to obtain three-dimensional models of the dense polymer phase. It is shown that the intensity of intermolecular interactions between PVC chains and plasticizer molecules, as well as the degree of uniformity of the plasticizer’s spatial distribution, directly affect the characteristics of the temperature dependence of the mechanical loss tangent. Thereby, the heterogeneity of the plasticizer distribution at the nanoscale level, determined by its tendency to associate, significantly affects the width of the glass transition. The data suggest a possible transition from a plasticization mechanism characteristic of short-chain diesters (associated with a higher number of directional Cl···O contacts) to a mechanism of bulk dispersion spacing of PVC chains for long-chain esters. This interpretation is consistent with the observed differences in thermal stability and low-temperature flexibility. These conclusions are based on a limited set of five plasticizers and a specific MD/fragment-condensation framework; therefore, they should be considered as preliminary and model-dependent.

High-temperature polymer dielectrics are critically needed for advanced power electronics; however, their performance is often compromised by charge-transfer complexes (CTC) in aromatic polyimides. To overcome this limitation, we introduced an ultra-low loading of 5,10,15,20-tetra(4-aminophenyl) porphyrin (TAPP) as a multifunctional crosslinker into a polyimide (PI) matrix. TAPP simultaneously establishes covalent crosslinking and trap engineering, and its amino groups form a robust network with PI chains, whereas the porphyrin cycle acts as an efficient deep-level charge trap, effectively suppressing CTC formation and charge migration. The optimized PCPI films exhibited a tunable non-monotonic dielectric constant while maintaining a low loss. The PCPI-0.1 sample shows a significantly enhanced breakdown strength and achieves high discharge energy densities of 8.78, 6.09, and 4.97 J·cm⁻³ at 25, 150, 200 °C, respectively, while maintaining an efficiency above 85%. Remarkably, PCPI-0.1 delivered superior energy density compared to most high-temperature polymer dielectrics reported in the literature, coupled with excellent cycling stability and aging resistance. This work presents a strategy based on ultra-low-loading crosslinking that integrates structural modulation with deep-trap engineering, offering a viable pathway to high-performance all-organic dielectrics for extreme-condition applications.