Macromolecular Rapid Communications最新文献

Achieving both high strength and reprocessability in a single plastics material remains a fundamental challenge. Herein, we report the design and synthesis of novel supramolecular polydiketoenamine (PDK) network materials that were synergistically dual crosslinked by both the dynamic diketoenamine bonds and supramolecular cross-links (hydrogen-bonded benzene-1,3,5-tricarboxamide units). As a result, the PDK films exhibited a well-balanced combination of mechanical robustness and dynamic adaptability, achieving a high tensile strength of up to ∼77.21 MPa along with outstanding thermal reshaping and self-healing capabilities. Remarkably, beyond serving as strong structural films, the PDK plastic film exhibited superior performance as solid-state adhesives for diverse substrates-glass, metal, ceramic-exhibiting an enhanced lap-shear strength (up to ∼23.51 MPa) and retaining over 90% of its performance on glass after multiple reprocessing cycles. This work provides a promising strategy of integrating supramolecular cross-links into covalent adaptive network to construct high-performance, reprocessable network polymers that bridge the gap between the robustness of thermosets and the reprocessability of the thermoplastics.

The lithium-ion batteries increasingly require separators that combine high thermal stability, low swelling, and excellent electrolyte wettability, yet conventional ceramic coatings add weight and reduce porosity while acrylate-based polymer coatings often lack heat resistance. Here, we report a rationally engineered class of highly crosslinked, monodisperse polymeric microspheres synthesized via emulsion polymerization of styrene (St), methyl methacrylate (MMA), acrylonitrile (AN), and dipentaerythritol hexaacrylate (DPHA). The synergistic monomer design confers controlled particle nucleation, high thermal robustness (T₃ up to 370°C), and exceptional resistance to electrolyte swelling (<11%). When applied as thin (∼1.5 µm) separator coatings, the microspheres pack into uniform, porous, and strongly wettable architectures that significantly enhance separator performance. The coated separators exhibit minimal thermal shrinkage (5.6% at 150°C), more than double the electrolyte infiltration of ceramic-coated controls, and markedly improved ionic conductivity (0.80 mS cm^{- 1}). Pouch cells assembled with these separators deliver superior cycling stability and rate capability. This work establishes a high-performance, lightweight, and scalable alternative to ceramic coatings for next-generation lithium-ion battery separators.

In this work, the synthesis and structure/properties relationship of well-defined linear and branched copolymers composed of vinylbenzyl trimethylammonium chloride (VBTMA-C) and 2-(acryloyloxy)ethyl trimethylammonium chloride (AETMA-C) was investigated. Copolymers were obtained via reversible addition-fragmentation chain transfer (RAFT) polymerization in aqueous media at 70°C. Subsequently, chloride counterions were substituted by bis(trifluoromethanesulfonyl)imide (TFSI), and copolymers were characterized. Infrared (IR) and nuclear magnetic resonance (NMR) spectra confirm the chemical structure, while size exclusion chromatography (SEC) and rheological measurements highlight the influence of PAETMA moieties in electrostatic and inter-intramolecular interactions of copolymers. Thermogravimetric analysis (TGA) points out the thermal stability of materials. In addition, copolymers with TFSI exhibit a glass transition temperature (T_g) between 50°C and 87°C. X-ray diffraction tests demonstrate a physical rearrangement of amorphous copolymers contained TFSI. Mechanical behavior of copolymers was evaluated, and results demonstrated high modulus (8.406 GPa), tensile strength (25.035 MPa), and toughness (0.214 MJm^-3) of synthesized materials compared to values of polyvinylidene fluoride (PVDF) with modulus (0.605 GPa), tensile strength (1.10 MPa), and toughness (0.021 MJm^-3), respectively. These results confirm physicochemical features and great mechanical properties of the synthesized copolymers, opening the way for their uses as binders in cathodes for lithium-sulfur batteries.

It is promising but challenging to prepare poly(amino acid)s that directly bond to alcohols, especially saccharides. Herein, we report a novel method for the controlled ring-opening polymerization (ROP) of sarcosine N-carboxyanhydride (Sar-NCA) quantitatively initiated by hydroxyl groups using lutetium triflate (Lu(OTf)₃) as catalyst. Lu(OTf)₃ is devised to slow down the propagation by reducing the nucleophilicity of the amino group on the propagating chain end, thus realizing quantitative initiation efficiency (IE) of alcohol. Polysarcosine (PSar) samples with controlled molecular weights (M_n = 2.2-12.7 kg/mol) and low dispersities (Đ = 1.11-1.15) are obtained and full IE of the hydroxyl group is realized. Kinetic studies reveal that the propagation rate of Sar-NCA is significantly decreased in the presence of Lu(OTf)₃. The addition of Lu(OTf)₃ converts the characteristic of alcohol-initiated ROP of Sar-NCA from "slow initiation and fast propagation" to "fast initiation and slow propagation" which is essential of the polymerization control. Density functional theory (DFT) calculations provide mechanistic insights that Lu(OTf)₃ is prone to coordinate with the propagating chain end species of secondary amino and carbamate groups in the form of five- or eight-membered rings and retards the propagation. PSar products bearing glucose or mannose ester end groups, analogs of glycoproteins, are successfully synthesized by applying this protocol. The obtained mannose-functionalized PSar shows significantly accelerated ingestion by cancer cells.

The development of non-fullerene acceptors (NFAs) has driven significant advancements in organic solar cells (OSCs), resulting in power conversion efficiencies (PCEs) approaching 20% and positioning OSCs for practical applications. Notably, the recently introduced fused-ring A-DA'D-A type NFAs, especially those called Y-series NFAs, have propelled the field forward due to their strong near-infrared (NIR) absorption, adaptable structural features, and efficient molecular stacking, which collectively enhance charge transfer, minimize energy losses, and improve OSC performance. This review first summarizes the progression of Y-series NFAs from Y1 to the epoch-making acceptor Y6. Recent advances in fused-ring A-DA'D-A type NFAs are then discussed, with a focus on design strategies that modify structural parameters, such as side-chains, central cores, end-capping groups, and π-spacers. The advantages of each NFA are analyzed in relation to their corresponding polymer donors. The influence of molecular structure and optoelectronic properties of NFAs on the morphology of the donor/acceptor (D/A) active layer, charge transfer dynamics, and device performance is examined. Finally, the review identifies current challenges and outlines future directions for the development of Y-series NFAs in OSCs.

Liquid crystal elastomers (LCEs) are promising stimuli-responsive materials for applications in wearable devices, biomedical devices, and soft robotics owing to their thermotropic shape-changing behaviors. However, conventional LCEs exhibit high phase-transition temperatures, often exceeding 60°C, which limits their use in human-interfacing applications. Herein, we present body heat-responsive LCEs incorporating dynamic thiourea bonds. Body temperature actuation is achieved by introducing comonomers that weaken anisotropic intermolecular interactions among mesogens into these LCEs, while the dynamic thiourea bonds impart reprocessability to the cross-linked network. Systematic formulation study elucidates the influence of comonomer structure on the actuation performance and network malleability. Furthermore, the dynamic thiourea-based LCE demonstrates reprogrammability even at ambient temperature, enabling facile fabrication of mechanically programmed 3D structures. Finally, we showcase a bump-array actuator that reversibly changes its surface topography in response to body heat.

The development of polymer electrolytes is a promising strategy for increasing the safety and performance of lithium batteries. In particular, gel polymer electrolytes (GPEs) are closest to replacing conventional liquid electrolytes due to their properties from the incorporation of plasticizers and conductors into polymers. One family of these compounds, ionic liquids (IL), has the ideal range of properties for reducing the risk of fire, leaks, and toxic by-products. In this work, poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) copolymer was used to synthesize a GPE with lithium salt and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (IL), evaluating the effect of different solvents on the final properties of the material, such as thermal stability, crystallinity, microstructure and conductivity. The addition of IL was responsible for a reduction in the crystallinity of PVDF-HFP from an average of 31% to 11%, and a diminution in its thermal stability (T_2%) from 435°C to 350°C. Membrane microstructure was dependent on the solvent used, ranging from completely uniform with acetone to granular with dimethylformamide or dimethylacetamide. The dimethylacetamide electrolyte had the highest conductivity (0.43 mS cm^-1), while the N-methylpyrrolidone electrolyte showed better interaction with metallic lithium.

Polymer lipids (PLs) are an essential component for the stability of lipid nanoparticles (LNPs) for gene delivery. Poly(ethylene glycol) (PEG)-based lipids are the current gold standard. However, they are suspected to be responsible for rare adverse reactions to the LNP-based COVID-19 vaccines. Therefore, alternative PLs are being intensively investigated. A particularly promising alternative are poly(sarcosine) (PSar)-based lipids. However, one significant bottleneck of pSar-based biomaterials is the synthesis of the monomer sarcosine-N-carboxyanhydride (Sar-NCA). Current methods rely on highly toxic di- or triphosgene to obtain the monomer directly from the amino acid sarcosine. Herein, we present a phosgene-free, CO₂-based route to Sar-NCA in gram scale and excellent purity, suitable for the subsequent living polymerization to pSar. Furthermore, we used the obtained pSar for the synthesis of pSar lipids suitable for LNP preparation. Due to its low toxicity and simplicity, the CO₂-based Sar-NCA synthesis has great potential to become an attractive alternative to current monomer synthesis pathways.

Developing high-efficiency antifouling nanofiltration (NF) membranes is crucial to address the dual challenges of low separation selectivity and severe membrane fouling in lithium extraction from high Mg²⁺/Li⁺ ratio salt-lake brines. This study presents an efficient strategy based on one-step dip-coating surface modification. By grafting 1, 2-epoxy-3,3,3-trifluoropropane (TFO) molecules onto a PEI-TMC polyamide (PA) base membrane, a unique bipolar electrostatic potential reconstruction was triggered, simultaneously and significantly enhancing both the separation selectivity and antifouling performance of the membrane. In simulated high Mg²⁺/Li⁺ ratio brine (2000 ppm, Mg²⁺/Li⁺= 30:1), the PA-TFO_0.75 membrane demonstrated exceptional integrated performance by achieving a high Li⁺/Mg²⁺ selectivity of 20.5 (9.76 times higher than commercial NF membranes) while maintaining a high water permeance of 14.65 L m^-2 h^-2 bar^-1, and exhibiting an outstanding flux recovery ratio (FRR) approaching 100.6% (a 151% improvement over the pristine membrane), thereby meeting industrial fouling resistance standards. Critically, this strategy enabled the continuous fabrication of large-area membranes (60 m × 0.298 m). The assembled spiral-wound module (1812-type) retained a Li⁺/Mg²⁺ selectivity of 19.5 in the same simulated brine, providing an efficient, antifouling, and scalable industrial-scale solution for lithium extraction from high Mg²⁺/Li⁺ ratio salt lakes.

Conductive hydrogels (CHs), which integrate the biomimetic properties of hydrogels with the functionality of conductive components, have demonstrated distinctive advantages in biomedical engineering. By modulating cell-cell interactions, CHs provide an optimal microenvironment to facilitate cellular growth, proliferation, and migration, emerging as a promising platform for tissue engineering and regenerative medicine applications. This review systematically examines the intricate relationships among the composition, structure, and fabrication strategies of CHs, while highlighting their recent advancements in biomedical applications, including skin tissue regeneration, spinal cord injury repair, muscular tissue reconstruction, cardiac tissue engineering, and biosensing technologies. The design and synthesis of diverse CHs are introduced first, followed by a comprehensive summary of the common preparation methods. Furthermore, the current limitations of CHs in practical applications are critically analyzed, alongside perspectives on future developmental directions. By elucidating the interplay between material properties and biological functionality, this review aims to inspire interest in CHs and offer valuable insights for their rational design and application in next-generation biomedical innovations.