Circularly polarized luminescence (CPL) materials have attracted considerable attention because of their unique chiroptical properties and promising applications. However, the simultaneous achievement of a high luminescence dissymmetry factor (g_lum), high photoluminescence quantum yield, excellent processability, and environmental stability remains challenging. Chiral helical polymers, featuring single-handed helical conformations, have emerged as versatile and powerful platforms for constructing high-performance CPL systems by utilizing their inherent chiral amplification effects, tunable conformational dynamics, and ability to form hierarchically ordered structures. This review systematically summarizes recent advances in CPL materials based on chiral helical polymers, focusing on the regulation of chiroptical properties through polymer conformation, mesoscopic ordered structures, and photophysical pathways. CPL systems are categorized into three main classes: monocomponent chiral helical polymers, multi-component organic composites, and organic-inorganic hybrids. For each category, representative molecular design strategies, fabrication methodologies, and CPL performance were elaborated, emphasizing the underlying structure-property relationships. The key mechanisms governing CPL generation and amplification are discussed in depth, including chirality transfer, solvent- and state-dependent chiral inversion, selective absorption/filtering, and cholesteric liquid-crystal-mediated photonic amplification. Furthermore, representative breakthroughs, such as near-infrared CPL, room-temperature phosphorescence, and long-persistent CPL, are highlighted. Finally, the current challenges and future directions are outlined, providing a guideline for the rational design and practical application of next-generation helical polymer-based CPL materials.

Recently circularly polarized luminescence (CPL) generated by chiral materials have attracted tremendous attention due to its potential applications such as 3D displays, quantum communication, and information storage. Polymers have emerged as particularly promising platforms for generating and amplifying CPL, owing to their structural designability, inherent helical architectures, and excellent processability. Hence, this review provides a comprehensive overview of recent advances in polymer-based CPL materials, with a central focus on the rational construction of polymer chiral superstructures, including helical polymers bearing chiral centers on side chains for chiral transfer and amplification, helical polymers with chiral centers integrated into the main chain, achiral polymers complexed with small-molecule inducers through non-covalent interactions; and achiral polymers utilizing macromolecular inducers. By discussing representative examples, we elucidate the underlying mechanisms of chirality transfer, amplification, and luminescence that govern CPL. The review concludes by highlighting the key challenges and promising future perspectives in this field, aiming to guide further research and accelerate the practical application of polymer-based CPL materials.

Poly(phenylacetylene)s (PPAs) are one kind of important helical polymers with tunable main chain conformations. However, the preparation of near-infrared optically active helical PPAs remains a challenge. Here, we report a novel helical poly(m-terphenyl acetylene)s (PTPAs) bearing two chiral alkylamide pendants, which showed a stretched cis-transoid helix in solution or poly(methyl methacrylate) matrix with a broad optical activity range from the ultraviolet-visible (UV-Vis) to near-infrared regions. The effects of substituents, solvents, temperature, and acid/base additions on the helical conformation were carefully investigated. The substituent structure had little effect on the elongation but remarkably affected the main chain screw sense. The stability of this extended cis-transoid helix depends on the solvent applied and the temperature. Reversible conformational transitions between the one-handed cis-transoid helices and frustrated coil conformations can be achieved by the addition of trifluoroacetic acid and triethylamine. Furthermore, full-color circularly polarized luminescent materials can be prepared by virtue of their broad Cotton effects and chirality-selective absorption.

Stereochemical control in ring-opening metathesis polymerization (ROMP) is essential for tailoring polymer properties. While several existing studies have achieved tunable regioselectivity with asymmetric monomers through catalyst design, yet achieving high trans-selectivity alongside defined regiochemistry remains challenging. Here we report the ROMP of a chiral aza-norbornene monomer derived from Vince lactam using a readily prepared phenylimido tungsten catalyst. The resulting polymer exhibited high head-to-head regioselectivity and high trans-selectivity, which stands in stark contrast to our previous work where Ru-based catalysts afforded predominantly cis-selective polymers from the same monomer. Moreover, together with our previously reported polymers, specific rotation measurements and circular dichroism spectra demonstrated that varied stereochemical configurations significantly influenced the optical activity and chiral expression of polymers derived from the same chiral monomer. This work provides a complementary approach to stereochemical control in ROMP, offering valuable insights for design and synthesis of structurally well-defined chiral polymers.

Polymer crosslinked networks often face a fundamental trade-off between the mechanical robustness of covalent systems and the dynamic reversibility of supramolecular assemblies. Inspired by the hierarchical organization of biological extracellular matrix, where fibrous structures are reinforced by covalent crosslinking, we report a squaramide-directed cooperative assembly strategy that integrates one-dimensional (1D) supramolecular nanofiber formation with covalent macromolecular architecture to construct hierarchical polymer networks. Telechelic macromolecules were designed by tethering orthogonally arranged squaramide–amide hydrogen-bonding motifs to polydimethylsiloxane (PDMS) spacers. In the model system, these motifs undergo cooperative nucleation-elongation assembly into long-range nanofibers, while comparison with a urea analogue reveals enhanced intermolecular binding and assembly stability arising from the squaramide motif. Covalent integration of the assembling units transforms discrete nanofibers into microphase-separated networks with increased thermal stability and storage modulus. This work establishes a molecular design principle linking cooperative self-assembly with hierarchical polymer network formation and macroscopic mechanical performance.

Incorporating different structural units into the polyester backbone constitutes a powerful strategy to tailor material performances. The integration of ether and ester moieties affords poly(ether-alt-ester)s with enhanced mechanical flexibility and tunable thermal properties. Nevertheless, the substrate scope available for the alternating copolymerization of epoxides with lactones remains considerably restricted, and the resulting polymers still suffer from inferior thermal resistance. Herein, we design a typical Bringmann’s lactone bearing a conformationally constrained biaryl axis and a helically distorted six-membered bridging scaffold. A binary catalyst system composed of simple Salen-Cr(III)-Cl and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD) enables strictly alternating and controlled copolymerization with meso-epoxides, effectively suppressing the formation of ether-ether or ester-ester linked homopolymer sequences. This protocol yields alternating poly(ether-alt-ester)s with a high glass transition temperature of 114 °C, an enhancement of 57 °C relative to alternating copolymer derived from the flexible 3,4-dihydrocoumarin monomer. This approach provides a facile and practical strategy for advancing the performance of alternating poly(ether-alt-ester)s.

Chiral hydrogels derived from helical polymers are attractive as intelligent chiral materials due to the combination of polymer helicity and hydrogel characteristics. Here, we report the synthesis and characterization of chiral hydrogels from helical thermoresponsive dendronized poly(phenylacetylene)s via dynamic covalent acylhydrazone crosslinking, which are responsive to temperature, pH and redox. Two types of helical copolymers, featuring dendritic oligoethylene glycol (OEG) units terminated with either methoxyl or ethoxyl groups, were employed as precursors to afford distinct overall hydrophilicity. These precursors exhibited unprecedented thermoresponsive behavior attributed to the densely grafted dendritic OEGs, with cloud points (T_cps) primarily governed by the terminal groups (methoxyl versus ethoxyl). To impart multi-responsiveness, a disulfide-containing crosslinker was selected for hydrogel formation. Gelation was conducted at three different temperatures—freezing temperature, room temperature (below T_cp), and elevated temperature (above T_cp)—yielding hydrogels with tunable responsiveness to temperature, pH, and redox conditions. The resulting hydrogels displayed stabilized helicity, along with good self-healing properties, excellent compressibility and robust mechanical performance. Preliminary biocompatibility assays indicated low cytotoxicity, underscoring their potential for biomedical applications.

As one of the most popular polysaccharide derivatives with high chiral recognition ability, cellulose tris(3,5-dimethylphenylcarbamate) (CDMPC) has been successfully applied in the enantioseparation of a wide range of racemates for various purposes. However, the derivative is usually synthesized with an amorphous structure, and its effect on enantioseparation ability remains obscure. To obtain a better understanding of the correlation between its structure and enantioseparation ability, in this study, CDMPC derivatives with crystalline and amorphous structures were prepared through carbamoylation followed by anti-solvent precipitation. Their chiral recognition abilities were evaluated using high-performance liquid chromatography (HPLC) with chiral stationary phases (CSPs). Interestingly, the ordered arrangement of the helical polymer chains of CDMPC was effectively induced by the aromatic solvent after derivatization, forming a crystalline derivative (c-CDMPC) with a uniform and compact worm-like morphology, whereas the amorphous derivative (a-CDMPC) was obtained by regular treatment with a polar alcoholic solvent. The c-CDMPC–based CSP exhibited higher chiral recognition abilities with much shorter retention times for most racemates in this study, compared to the a-CDMPC–based CSP. In particular, flavanone (Rac-7), an important chiral drug with anti-inflammatory, anti-tumor, and cardiovascular protective activities, was even better resolved with higher enantioselectivity on crystalline c-CDMPC than on Chiralcel OD, a commercialized chiral column based on CDMPC. This indicates that the crystalline ordered arrangement played a critical role in the chiral recognition ability of the cellulose derivative.

The helical structures found in biological systems, such as DNA, have inspired significant research interest in artificial helical polymers, owing to their strong potential for applications including chiral recognition and resolution, asymmetric catalysis, and other related areas. However, the preparation of single-handed helices from achiral starting materials, as well as the exploration of their chiral resolution behavior, continues to represent a considerable challenge. In this work, we present the rational design and synthesis of optically active helical poly(phenyl isocyanide)s through helix-sense selective polymerization (HSSP) of achiral phenyl isocyanide monomers, catalyzed by enantiopure Pd(II) complexes bearing S- or R-configured ligands (Pd(II)/L^S or L^R). The polymerization exhibits living and controlled characteristics, allowing for the precise modulation of molecular weights (M_n) with exceptionally narrow distributions (M_w/M_n). The resulting polymers exhibit intense optical activity and demonstrate outstanding performance in chiral recognition. Specifically, these chiral materials are utilized as a chiral stationary phase (CSP), which can separate various racemates including α-methylbenzylamine, cobaltic acetylacetonate, and 2-hydroxy-2-phenylacetophenone. Additionally, when applied as a chiral crystallization agent, the polymer enabled the resolution of racemic Z-Alanine via enantioselective crystallization, yielding an enantiomeric excess (ee) as high as 81%.

Intrinsically emissive helical poly(phenylacetylene)s (PPAs) are attractive circularly polarized luminescence (CPL) materials, yet their color tunability and light-harvesting capability remain limited because the emission mainly originates from the backbone excited states. Herein, we construct side-chain/backbone bichromophoric PPA systems to investigate Förster resonance energy transfer (FRET) and its effect on CPL performance. Using a pentafluorophenyl ester-functionalized PPA-PFP as a common precursor, planar aromatic donors, pyrene (Py) and naphthalene (Nap), and a non-coplanar donor, triphenylamine (TPA), were systematically introduced through activated-ester amidation. Py-PPA and Nap-PPA both underwent efficient donor-to-backbone energy transfer to the emissive cis-cisoid helical backbone, while Py-PPA showed a higher FRET efficiency and a much more pronounced solid-state CPL enhancement, with a |g_lum| value of 7×10⁻² in the film. In contrast, TPA-PPA exhibited conformation-coupled FRET attenuation and emission color switching because the bulky twisted donor destabilized the cis-cisoid backbone. Further spectroscopic and diffraction studies revealed that the superior CPL performance of Py-PPA originated from the synergistic combination of stronger pendant chiral ordering and more efficient side-chain-to-backbone energy transfer during solution aging and film formation. These results show that donor-pendant modification is an effective way to regulate FRET and CPL in intrinsically emissive PPA systems.

Hydrogen peroxide (H₂O₂) is a green chemical with extensive applications in chemical synthesis and environmental remediation. While the industrial anthraquinone process remains the dominant production method, solar-driven photocatalytic H₂O₂ production has emerged as a promising strategy to complement or optimize current production models, particularly for on-site applications. Among various porous organic polymers (POPs), covalent organic frameworks (COFs), and covalent triazine frameworks (CTFs) have attracted significant attention as a premier platform due to their modular construction and precise molecular-level tunability. Here, we systematically summarize recent progress in POPs-based photocatalysts, with a primary focus on the structural and functional modification of COFs and CTFs. We first elucidate the fundamental principles and existing challenges of photocatalytic H₂O₂ production. Subsequently, the research landscape of various POPs materials in photocatalysis is discussed. Taking COFs and CTFs as representative examples, we then highlight advanced modification strategies, including the design of donor-acceptor (D-A) structures, functional group engineering, and the construction of heterostructures. These strategies effectively facilitate efficient charge separation, extend carrier lifetimes, and improve mass transport, thereby enhancing solar-to-chemical conversion efficiency. Finally, we summarize the current state of the field and offer perspectives on future research directions for POPs-based photocatalytic H₂O₂ production.

Although near-infrared (NIR)-absorbing acceptors tend to capture more photons to boost the photocurrent (J_SC) of polymer solar cells (PSCs), they often suffer from significant energy loss (E_loss), resulting in a low photovoltage (V_OC), which limits further improvement of the power conversion efficiency (PCE). Herein, we developed four selenium-fused NIR-absorbing acceptors (Y-SeNF, Y-SeNF-2ClO, Y-SeBNF, and Y-SeBNF-2ClO) by regulating the molecular photoelectric properties via end-group and side-chain dual-engineering. Among them, Y-SeNF-2ClO with linear side-chains and asymmetric end-groups showed favorable molecular packing and energy levels, achieving an optimized active layer morphology and suppressed energy loss. Therefore, among the binary PSCs with a polymer donor D18, the Y-SeNF-2ClO device achieved the minimized E_loss and the highest product of V_OC×J_SC, leading to a champion PCE of 17.41%, outperforming other devices based on acceptors with branched side-chains and/or symmetric end-groups. Encouraged by the above success, NIR-absorbing Y-SeNF-2ClO was also introduced into the classic D18:L8-BO host system to fabricate efficient ternary PSCs. Notably, the D18:L8-BO:Y-SeNF-2ClO device offered a further improved PCE of 20.08%, ranking among the highest values reported for asymmetric acceptors. This work provides a feasible molecular design strategy for end-group and side-chain dual-engineering to develop NIR-absorbing acceptors for constructing efficient PSCs.

Organic electrochemical transistors (OECTs) enable high-performance bioelectronics through their efficient ionic-electronic coupling, yet realizing a complete neuronal signal pathway that transduces environmental stimuli into spiking activity and synaptic memory remains a persistent system-level challenge. Here we demonstrate a neuron-inspired signal transduction pathway constructed entirely from OECTs, comprising a signal receptor, a spiking axonal module and a synaptic memory unit. System-level functionality is examined using a hardware-in-the-loop configuration based on direct analog signal transfer. The raw output photocurrent generated by the receptor drives the axonal oscillator, and the resulting voltage spikes subsequently modulate the synaptic device, without any algorithmic scaling or software-based amplification. This direct-drive regime preserves physical signal causality and reveals that the intrinsic signal levels of each functional block are naturally matched to the input requirements of the subsequent stage. Experimentally, receptor-induced spiking activity reliably gives rise to short-term synaptic plasticity under these unassisted conditions. Together, these results demonstrate the inherent inter-stage electrical compatibility of OECT-based devices and establish a rigorous experimental foundation for the future monolithic integration of fully organic neuromorphic systems.

The non-equilibrium dynamics of solvent evaporation and polymer diffusion induce vertical crystallization differences in the donor film, which pose great challenges to the precise control of the ideal vertical phase morphology in pseudo-planar heterojunction (PPHJ) organic photovoltaics (OPVs). In this study, the Peclet number (Pe) was first proposed as a predictive parameter to evaluate the correlation between solvent evaporation and the vertical gradient distribution morphology of the active layer during the film-forming process. This further directs the regulation of the hierarchical aggregation structure and vertical crystallization behavior of the polymer donor, thereby inducing ordered donor/acceptor interpenetration and ultimately achieving the construction of active layers with controllable heterojunction architectures. Depth-dependent light absorption spectroscopy and in situ depth-dependent fluorescence intensity measurements confirmed that Pe is about 1 can induce vertical crystallization differences in various polymer donors to form a PPHJ active layer with an ideal vertical gradient distribution morphology. Consequently, the toluene-processed PPHJ device achieved competitive power conversion efficiencies of 20.07%/16.86% (0.04/16.94 cm²) via blade coating technology.

Two pyrimidoisoindigo-based polymers were synthesized by copolymerizing thiophene-flanked pyrimidoisoindigo (T-PymII) with thiophene (T) or 3,4-difluorothiophene (2FT), and their structure–property correlations were investigated. Although both polymers exhibited ambipolar transport properties, P(PymII-TTT) was dominated by hole transport, while P(PymII-T-2FT-T) was dominated by electron transport. Among them, the highest hole mobility up to 1.66×10⁻² cm²·V⁻¹·s⁻¹ was observed for P(PymII-TTT), while the highest electron mobility of 6.37×10⁻³ cm²·V⁻¹·s⁻¹ was observed for P(PymII-T-2FT-T). AFM and GIWAXS analyses revealed that their poor morphology and crystallinity may account for their inferior performance. Therefore, further side-chain engineering is needed to improve the crystallinity of PymII-based polymers.

Polymer co-assembly provides a versatile route to hierarchical nanostructures, yet achieving precise structural control remains a significant challenge. In particular, understanding how topological differences in polymer building blocks influence co-assembly behavior is important for expanding the design of complex polymer materials. In this work, a co-assembly system of amphiphilic block copolymers (BCPs) and single chain polymer nanoparticles (SCPs) was designed to investigate the effect of topological variations. At certain SCP/BCP mass ratios, BCPs and SCPs co-assembled to form a hierarchical composite structure with vesicles growing on the surface of micelles, following a path-dependent stepwise co-assembly mechanism, where SCPs co-assembled with BCP to form core micelles and self-assembled into vesicles from the micelle surface into hierarchical micelle@vesicle (M@V) composite structure. The SCP/BCP mass ratio significantly influences the morphology and size of the M@V composite structure, and the strategy is applicable to copolymer systems with wide range of hydrophobic/hydrophilic volume ratios. This work provides new insights into topology-regulated polymer co-assembly and offers a useful strategy for the design of hierarchical and multifunctional polymer materials.

Non-metallic cationic polymerization of low-reactivity styrene (St) derivatives remains challenging due to broad molecular weight distributions and rapid deactivation of active species. Here we show that adding only a minor amount of CH₃CN (V/V, 3/97) to the conventional BF₃·OEt₂/COH/CH₂Cl₂/St system affords polystyrene with narrow dispersity (M_w/M_n, Đ ≈ 1.3). Notably, the M_n increases linearly with conversion and closely matches the M_n.calcd. ¹H-nuclear magnetic resonance (¹H-NMR) analysis and comparative experiments with the BF₃·CH₃CN co-initiation system indicate CH₃CN does not coordinate strongly with BF₃ compared to diethyl ether (OEt₂); however, it stabilizes the propagating carbocation and decreases the the propagation rate constant (k_p), which leads to a narrower dispersity in the product. Lowering the temperature to −25 °C further extends the active-chain lifetime. This strategy is also effective for other low-reactivity styrene monomers, including p-chlorostyrene (pClSt) and p-chloromethylstyrene (pCMSt), and is even applicable to the relatively more reactive p-methylstyrene (pMeSt), offering a versatile metal-free route to the synthesis of styrenic polymers with a narrow dispersity.

Advanced aerospace technologies demand polymer-based wave-transparent materials with low dielectric constant (D_k), low dissipation factor (D_f), and high heat resistance for hypersonic vehicles. Thermosetting polyimides (PIs) from phenylethynyl-terminated imide (PETI) oligomers are promising candidates due to their excellent thermal stability; however, their application is limited by high D_k and D_f at high frequencies and processing difficulties. Here, a series of PETI oligomers were designed and synthesized by polycondensation of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride containing a Cardo structure, and six diamine monomers, respectively. The diamines were divided into three pairs by backbone flexibility, with each pair comprising a non-fluorinated diamine and its trifluoromethyl (―CF₃) substituted analog. The effects of chain segment flexibility and ―CF₃ substitution on the processability of the oligomers and the properties of the cured PIs were systematically investigated. Results show that oligomers with ―CF₃ groups exhibit enhanced solubility and improved viscosity stability at 270 °C compared to their non-fluorinated counterparts. Moreover, the corresponding cured resins show lower D_k and D_f values while maintaining good thermal stability and mechanical properties. Notably, the BPAF-FA system exhibits favorable properties: an oligomer solubility of 40 wt% in NMP, and a minimum melt viscosity of 5.61 Pa·s; D_k=2.953, D_f=0.0098 (at 50% RH), T_g=403 °C. Mechanistic analysis indicates that these improvements result from the synergistic effects of the intrinsic characteristics of ―CF₃ groups (steric hindrance, electron-withdrawing effect, low polarizability, and hydrophobicity) and their role in influencing chain flexibility, symmetry, and molecular packing. These findings provide valuable guidance for the design of high-temperature-resistant, low-dielectric wave-transparent composite materials.

Bone defects remain a major clinical challenge due to the slow rate of recovery, complex surgical procedures, and great impact on the lives of patients. Therefore, the development of biocompatible, durable, degradable artificial bone grafts is highly desirable. Inspired by the natural composition of human bone, this study reports the fabrication of poly(lactic acid) (PLA)/zinc-doped hydroxyapatite (Zn-HA) composite materials via the melt blending method. The chemical properties, mechanical performance, degradability, and biocompatibility of the composites were evaluated systematically. Among them, the 10 wt% PLA/Zn-HA composite exhibited optimal performance, including high tensile and flexural strengths, superior thermal stability, and the lowest degradation rate. Controlled degradation and sustained release of zinc ions further enhance osteoblast activity with low cytotoxicity. Furthermore, Alkaline Phosphatase (ALP) activity and Alizarin Red S (ARS) staining confirmed that the 10 wt% PLA/Zn-HA composite significantly promoted osteogenic differentiation. By simultaneously achieving mechanical reliability and enhanced biological properties, this study provides promising design criteria for next-generation artificial bone grafts for bone defect repair.

Biodegradable polymeric nanocarriers demonstrate significant potential for the controlled release of pesticides, offering a sustainable and efficient approach for agriculture. This study involves the synthesis of novel pH-responsive L-cysteine-conjugated polydopamine (PDC) nanospheres for the controlled release of emamectin benzoate (EMB). Using sustainable in situ polymerization, hydrophobic EMB was encapsulated within biodegradable polydopamine (PDA), which was further conjugated with L-cysteine. The functionalized and encapsulated carriers were characterized using UV-visible spectroscopy, Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), zeta potential, field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), and X-ray photoelectron spectroscopy (XPS). Both EMB@PDA and EMB@PDC nanospheres were assessed for their encapsulation efficiency and pH-responsive release of EMB. Under varying pH and temperature conditions, the maximum cumulative release of EMB was achieved at pH=3 and was further enhanced by temperature. Various kinetic models have shown that Fick’s diffusion controls the release process. EMB@PDC nanospheres exhibited excellent adhesion to plant surfaces and effectively protected against UV radiation, which reduced EMB loss through rainfall washout and photolytic degradation. In addition, EMB@PDC exhibited high insecticidal potency against Pieris brassicae. Hence, this integrative platform exemplifies an effective pesticide delivery system for promoting agricultural sustainability.

Semi-crystalline polymers can obtain a broad melting transition by copolymerization or blending and show a two-way shape memory effect (2W-SME) under stress-free conditions. However, intricate interactions between polymers are not easily controlled. It is still challenging for semi-crystalline polymers to obtain a two-way shape memory effect by broadening the melting transition. Here, we prepared polycaprolactone (PCL)-based cross-linked polyurethane by using malic acid as a side chain, thereby exploring the relationship between malic acid and the crystallinity of PCL or 2W-SME. The results showed that the incorporation of malic acid broadened the melting transition and improved the two-way shape memory behavior of the PCL-based cross-linked polyurethane. The influence of malic acid on the dynamic response mechanism of polyurethane was studied using in situ polarized optical microscopy (POM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectroscopy. The investigation revealed that the malic acid side chain plays a dual role by adjusting the crystallization behavior and strengthening the hydrogen-bonding network in the two-way shape memory process. This work provides a versatile strategy for the structural design of two-way shape memory polymers.

On-demand peelable adhesives represent a pivotal green chemistry research avenue; however, they confront a critical challenge in reconciling robust interfacial bonding strength with efficient peelability. Herein, a cohesion-adhesion synergy-guided molecular engineering strategy was developed to fabricate UV-curable adhesives with the integrated properties of superior bonding strength and hot water-triggered peelability. The adhesive was formulated with custom-synthesized difunctional polyurethane acrylate (PM1) as the crosslinker, which was blended with complementary acrylate monomers. PM1 constructed a robust yet adaptable crosslinking network to ensure high cohesive strength; its polytetrahydrofuran diol- and polyester diol-derived soft segments endowed the network with superior molecular chain mobility and stress dissipation capacity. Additionally, the incorporation and compositional optimization of polar acrylate monomers modulate the cohesive energy, surface wettability, and interfacial adhesion of the substrate, thus realizing synergistic enhancement of the cohesive and adhesive properties. Systematic experimental investigations and molecular dynamics simulations were conducted to determine the structure-property relationships governing the composition, bonding performance, and mechanical properties of UV-curable adhesives. The optimized formulation achieved high shear strength (>5 MPa, glass substrates), excellent mechanical properties (tensile strength: 12.80 MPa, elongation at break: 313.70%), and good thermal stability (5 wt% weight-loss temperature > 240 °C). Notably, the developed adhesives realize rapid, complete, and residue-free debonding within 3 min of immersion in 60 °C water, where hydration-induced disruption of adhesive-substrate contact attenuates interfacial interactions. Additionally, the peeled adhesive can be recycled repeatedly after drying while retaining its excellent interfacial bonding performance. This study provides a versatile and scalable strategy for the rational design of high-performance functional adhesives, thereby paving the way for recycling electronic products and sustainable manufacturing.

Protein stability is a critical factor that limits its application in biopharmaceuticals, clinical diagnostics, and industrial production. The inherent instability of proteins renders them susceptible to loss of activity and function under external environmental stresses, thus necessitating the development of novel stabilizers to improve protein stability. Inspired by sericin, we developed heterochiral poly-β-homoserine (β-HS) that combines resistance to enzymatic degradation, straightforward synthesis, and precise composition control, while exhibiting favorable in vitro safety profile. The β-HS exhibits remarkable stabilizing effects on horseradish peroxidase (HRP) and β-galactosidase (β-Gal) when subjected to elevated temperature and lyophilization, respectively. Our research indicates that β-HS stabilizes proteins by assisting in the maintenance of their conformation and preventing aggregation. Additionally, β-HS demonstrates stabilizing effects on proteins with diverse physicochemical properties. Therefore, this study suggests that the β-HS is a promising candidate for enhancing protein stability.

The molecular design of bio-based plasticizers often involves a trade-off between key performance and sustainability. Herein, we propose a novel molecular design strategy that breaks this contradiction by integrating a flexible backbone derived from non-edible sources, sustainable alicyclic rigid core, and epoxy groups. A series of epoxy-functionalized cyclohexane-based ricinoleate plasticizers, epoxyacetyl ricinoleic acid cyclohexanol ester (EACHR), epoxyacetyl ricinoleic acid cyclohexanediol ester (EACHDR), and epoxyacetyl ricinoleic acid cyclohexanedimethanol ester (EACHDMR), were synthesized. When evaluated in poly(vinyl chloride) (PVC) as a demanding validation platform, the optimal plasticizer (EACHDMR) achieved comprehensive performance, which reduced the glass transition temperature (T_g) by 30%, increased the elongation at break by more than 50-fold, and enhanced the notched impact strength by over 35-fold compared to an unplasticized PVC sample. Importantly, EACHDMR exhibited lower migration and 20.7% higher plasticizing efficiency than the commercial benchmark dioctyl terephthalate (DOTP). This study demonstrated that by rationally integrating rigid cores, flexible fatty acid chains, and polar groups, it is possible to successfully balance performance and sustainability, providing a new design strategy for developing high-performance and sustainable alternatives to traditional plasticizers.

Molecular chain defect engineering is a pivotal strategy for tailoring the macroscopic properties of polymeric materials. However, establishing a definitive relationship between molecular-level defects and bulk material performance remains challenging, due to the difficulty in precisely controlling not only the molecular architecture but also the subsequent chain packing, which critically governs material performance. In this work, we demonstrate that introducing ethylene units as chain defects into poly(vinyl alcohol) (PVA) enables precise modulation of the dichroism in iodine-doped PVA polarizers. This approach allows for concurrent control over the iodine-PVA complexation, the crystalline network and the mechanical properties. The dichroic behavior originates from the formation of oriented I₃⁻ and I₅⁻ species, with I₃⁻ absorbing between 400–520 nm and I₅⁻ between 520–780 nm. Therefore, optimizing optical performance—namely transmittance and polarization efficiency—requires careful tuning of the I₃⁻/I₅⁻ ratio and their overall concentration. The incorporation of ethylene defects addresses this need through three synergistic effects: (1) It increases the I₃⁻/I₅⁻ ratio by shortening the vinyl-alcohol sequence length in the amorphous regions, given that ethylene unit does not complex with iodine; (2) It reduces the overall crystallinity, as ethylene units are excluded from the crystalline domains; (3) It weakens intermolecular interactions (reflected by an increased Flory-Huggins parameter), which lowers the modulus but enhances drawability. This study illustrates how molecular-level defect engineering can be effectively translated into precise control over both chemical complexation and physical networks, thereby enabling the simultaneous manipulation of optical and mechanical properties in polymer materials.

In polymer processing, low-molecular-weight chemically identical oligomers are typically added to a polymer to improve its processability and mechanical properties by manipulating its entanglement concentration. However, the complicated semi-crystalline morphologies and melt memory effect of less entangled bimodal dispersed mixtures cannot be overlooked. In this study, we systematically examined the crystallization and self-nucleation behavior of poly(ε-caprolactone) (PCL) mixtures composed of a relatively high-molecular-weight (83 kg/mol) fraction and a low-molecular-weight PCL with a mid-chain defect (2 kg/mol). The entanglement concentrations were quantified by linear rheological measurements. Both thermal analysis and small-angle X-ray scattering (SAXS) investigations revealed that pronounced crystallization-induced phase separation (i.e., molecular segregation) occurs because of the different nucleation energy barriers. In contrast to our previous investigation using a long chain fraction with a higher molecular weight (200 kg/mol) (Macromolecules 2024, 57, 1632−1641), the low-molecular-weight oligomer tends to crystallize between adjacent crystalline lamellae composed of long PCL chains due to the lack of intra-crystalline links, for example, entanglements and tie-molecules. The correlation between the melt memory effect and the entanglement concentration was evaluated using self-nucleation experiments. The 2 kg/mol PCL oligomer (with a central defect) did not exhibit melt memory. However, the introduction of high-molecular-weight components, even below the critical entanglement concentration, leads to a wider temperature range, preserving the ordered structure. Our results provide solid evidence that the melt memory effect in polar semi-crystalline polymers originates from the intramolecular interactions of adjacent chain folding rather than entanglements or chain overlaps.

Passive thermal regulation materials offer a promising route toward energy-efficient building and smart devices. However, achieving both passive radiative cooling and solar-driven heating within a single polymeric system remains a significant challenge due to trade-offs in optical transparency, solar reflectivity, and environmental durability. Herein, we report a molecularly engineered polyimide (PI) film platform with switchable cavitation (realized through controlled cross-linking) that enables bidirectional thermal regulation. By tuning the molecular architecture, the PI films can be fabricated into either a highly porous, white reflective film for passive cooling (about 90% solar reflectivity, ΔT is about –6 °C) or a transparent solid film for passive heating (about 88.7% solar transmittance, ΔT is about +8 °C). The films exhibit excellent flame retardancy (PHRR is about 7.98 W·g^–1), thermal stability (T_max > 500 °C), and environmental resistance to UV and acidic conditions. Comprehensive outdoor and simulated tests confirm their dual-mode thermal regulation capabilities. This work presents a versatile strategy for designing robust, multifunctional PI materials for year-round thermal management in extreme environments, paving the way for next-generation energy-saving polymers.

To address the brittleness of epoxy resin (EP) caused by high crosslinking density, the modification of epoxy resin with flexible rubber segments was proposed in this work. Bisphenol A-type epoxy resin (E51) was reacted with isocyanate-terminated groups via an addition reaction to prepare a prepolymer (E51-TDI). Subsequently, E51-TDI was grafted with hydroxyl-terminated fluororubber (HTFR) to synthesize a high-toughness fluorinated epoxy resin (E51-TDI-HTFR) with side chains. A mixture of E51-TDI-HTFR and curing agent (D230) was used to fabricate the coating. The chemical structure of the modified epoxy resin and the thermal, hydrophobic, mechanical, and cavitation erosion resistance of the coatings were investigated. When the HTFR concentration was 25%, the epoxy coating exhibited the best hydrophobicity, mechanical properties, and cavitation resistance. The contact angle of the modified epoxy resin was increased to 110°. Meanwhile, the elongation at break increased to 46.40%, which was approximately four times that of the unmodified coatings. The fracture surface gradually became rougher as the HTFR content increased, indicating a ductile fracture characteristic. Although the addition of HTFR slightly reduced the glass transition temperature, it maintained good thermal stability. In addition, the cavitation erosion resistance of the epoxy coatings was enhanced. This study provides theoretical support for the development of high-toughness and hydrophobic epoxy coatings.

This study investigates the mechanical performance of hybrid fiber-metal laminates (FMLs) fabricated using a poly(vinyl alcohol) (PVA) matrix reinforced with woven glass and carbon fibers, further enhanced with titanium dioxide (TiO₂) and graphene fillers. The composites were fabricated using the vacuum bag molding process, and to optimize the mechanical behavior, different filler loadings were incorporated as graphene at (0.5 wt%, 1 wt%, and 3 wt%), and TiO₂ (0.5 wt%, 1 wt%, 2 wt%, and 3 wt%). Mechanical tests revealed that the inclusion of filler particles significantly enhanced tensile, flexural, and toughness properties. The optimal graphene loading was found to be 0.5 wt%, resulting in an 83.4% increase in Young’s modulus and a 127% improvement in tensile strength compared to PVA composites without filler. Optimal loading for TiO₂ was 2% by weight, which resulted in a 102.3% increase in Young's modulus and an 81.5% increase in ultimate tensile strength. The maximum flexural properties were achieved for 0.5 wt% graphene-loaded composites, with a flexural strength of 56.6 MPa and a flexural modulus of 19.3 GPa, while the highest toughness value of 4.2 MPa was also observed at this loading. Density analysis showed a slight increase in composite density with filler addition and minimum porosity at 0.5 wt% graphene and 2 wt% TiO₂, consistent with improved mechanical performance. XRD and FTIR analysis confirmed successful filler incorporation, enhanced crystallinity for TiO₂-filled composites, and the SEM analysis confirmed the strong interfacial interactions without altering the PVA matrix chemistry, while higher filler loadings led to property degradation due to particle agglomeration and stress concentration effects.

Achieving long-term anti-fogging performance while maintaining high visible-light transmittance is of critical importance for transparent substrates. However, challenges remain in achieving satisfactory abrasion resistance and weatherability of anti-fogging coatings across different substrates. In this work, an organic-inorganic hybrid anti-fogging coating was developed by integrating a highly adhesive hydrophilic polymer resin with polyoxometalates (POMs). The hydroxyl groups along the polymer chains provide excellent adhesion, while the presence of hydrophilic ionic groups facilitates the rapid formation of a continuous water film upon exposure to water vapor. Moreover, the multiple protons carried by the POMs not only form interfacial bonding with the substrate to further enhance adhesion, but also form multiple hydrogen bonding interactions with the polymer chains to strengthen the coating's cohesion and reduce its surface roughness. As a result, the coating exhibits outstanding abrasion resistance, maintaining excellent anti-fogging performance even after 1200 abrasion cycles under a 500 g load. Furthermore, the strong UV absorption of POMs prevents photoaging of the polymer resin in outdoor environments, imparting remarkable weather resistance. After 240 h of accelerated UV aging (0.68 W/m², 60 °C), the coating still delivers effective anti-fogging functionality. This study provides a generalizable strategy for designing environmentally friendly, long-lasting anti-fogging coatings with promising applications in glass, optical devices, and agricultural films.

A fundamental prerequisite to effectively regulate the content of stereocomplex crystals (SCs) in poly(lactic acid) (PLA) is to elucidate the underlying mechanisms governing their formation. In this study, we established polymer blend systems with different chain segment mobility but similar initial segment miscibility based on dynamic Monte Carlo (MC) simulations. The SC fraction was found to be closely related to segment mobility in polymer blend systems during the crystallization process. The simulation results further indicated that polymer blend systems with stronger segment mobility exhibited higher segment miscibility during crystallization, resulting in the formation of more SCs. Therefore, it can be concluded that by increasing the segment mobility, segment miscibility can be enhanced, thereby improving the stereocomplexation ability.

Deciphering how molecular sequences of block copolymers program their self-assembly pathways is a pivotal pursuit in polymer science. To this end, we integrated viscoelastic constitutive relations into dynamic self-consistent field theory (DSCFT) to probe the spatiotemporally coupled evolution of nanostructures and chain conformations in sequence-defined multiblock copolymers during viscoelastic microphase separation. The DSCFT simulations reveal that the linear sequence of slow-relaxing “hard” and fast-relaxing “soft” blocks encodes two programmable kinetic motifs: a hard-soft-hard sequence drives a sharp, droplet-coalescence-triggered conversion from loop to bridge conformations during viscoelasticity-mediated phase inversion, whereas a soft-hard-soft sequence governs a gradual, network-contraction-driven relaxation of chain conformations. Serving as modular kinetic codes identified in the system of triblock copolymers, these kinetic motifs were shown to operate concurrently within tetrablock chains and generalize to penta- and hexa-block architectures, demonstrating the scalability and robustness of sequence-encoded dynamics. This work establishes the paradigm of sequence-encoded viscoelastic kinetics, providing a mechanism for controlling pathway-dependent self-assembly at the molecular level.

The interfacial structure at the electrode-electrolyte interface is a critical determinant of the performance of electrochemical supercapacitors. Although grafting polyelectrolyte (PE) brushes onto electrodes is a promising strategy to enhance charge storage, the role of dielectric contrast and its coupling with PE microstructure remains to be studied. In this work, a classical density functional theory (cDFT) is employed to elucidate the synergistic effects of dielectric contrast and PE microstructure on supercapacitor performance. The theory explicitly accounts for image-charge interaction induced by dielectric discontinuity, chain correlation of the PE, excluded volume effect, and electrostatic correlation. The results reveal that increasing the grafting density and chain length of the PE brushes significantly enhances the capacitance by providing more immobile charge sites and expanding the effective double-layer region, which facilitates stronger counterion adsorption. It is found that the dielectric contrast between the electrode substrate and solvent, which is often oversimplified in idealized models, plays a decisive role. A higher dielectric permittivity of the substrate weakens the shielding effect of the polarization field within the electrode. Consequently, the external electric field provides a stronger influence on the electrolyte, promoting a denser accumulation of counterions at the interface. Crucially, a high-dielectric substrate mitigates the repulsive image-charge interaction, effectively transforming it into an attractive force that further adsorbs charge near the electrode. This effect becomes particularly pronounced at high surface potentials. These results provide fundamental insights into the optimization of high-performance SCs using PE coatings.

Rotaxanes are a class of mechanically interlocked polymers characterized by the sliding motion of ring molecules along a linear backbone. The dynamic behavior of a ring plays a critical role in determining its material properties. In this study, molecular dynamics simulations were performed to investigate the sliding dynamics of a ring on a rod-coil copolymer in rotaxane. We find that both the mean square displacement $ {g}_{3} \left(t\right) $ and the diffusion coefficient D of the rings are influenced by the rod-to-coil length ratio α, the stretching degree μ of the coil block, and the ring size $ {N}_{\mathrm{ring}} $. The mean square displacement $ {g}_{3} \left(t\right) $ shows sub-diffusive behavior at intermediate time scales owing to the heterogeneous backbone. The diffusion coefficient exhibits nonmonotonic dependence on α and μ. D first decreased and then increased as α increased, indicating that the ring diffused faster on more homogeneous copolymer chains. D increases with μ under a moderate stretching degree of the coil block, but decreases under near full extension, which demonstrates that the dynamics of the ring are governed by a competition between the chain flattening and the coil block’s fluctuation. Similarly, ring size $ {N}_{\mathrm{ring}} $ has a nonmonotonic influence on the diffusion coefficient D. This study provides molecular-level insights into the manipulation of sliding dynamics in rod-coil-based rotaxanes, thereby offering a theoretical basis for the design of functional slide-ring materials through topological control.

Upgrading commercially available polyethylene to have both higher mechanical properties and surface hydrophilicity is of fundamental interest and practical importance, but the actual results usually suffer from a trade-off between mechanical performance and surface hydrophilicity. Herein, we report the preparation of eighteen high-density polyethylene (HDPE) blend materials via the simple physical blending with hydrophilic ethylene/meta-methoxystyrene (E-mMOS) copolymers (P1, P2, and P3) used as macromolecular additives. After adding low blend ratios of the E-mMOS copolymers (2 wt%, 5 wt% and 10 wt%), the tensile strength, toughness and hydrophilicity of the resultant HDPE blends simultaneously increased. HDPE(SABIC)/P3 blend showed the optimal comprehensive improvement in tensile strength (41.2 MPa versus 31.1 MPa), elongation at break (1601% versus1083%), and hydrophilicity (water contact angle, 96.2° versus 106.4°) compared with commercial HDPE. SEM tests exhibited the HDPE/E-mMOS blends had good compatibilities. These HDPE materials also exhibited good processability, as evidenced by DSC and rheological measurements.