最新刊期
卷 55 ， 期 5 ， 2024
- 摘要：Structured liquids are a new type of non-equilibrium soft materials constructed by the assembly and jamming of solid particles at the liquid/liquid interface, combining the structural stability of solids with the fluidity of liquids. However, the preparation of smart structured liquids and derived functional materials with precise structures is still challenging, due to the lacking of suitable building blocks and manufacturing methods. Our group has carried out a great deal of research work in this field, and has achieved a series of significant results in the development of new self-assembly mechanism at the interface, the preparation of new liquid/solid materials, and the construction of novel devices with advanced functions. In this review, we highlight a generalized strategy for the preparation of structured liquids by using the formation, assembly and jamming of nanoparticle surfactants, in which nanoparticle surfactants are generated by the co-assembly between nanoparticles and polymeric ligands at the liquid/liquid interface. We first introduce the self-assembly mechanism of solid particles at the liquid/liquid interface. Then we summarize the progress in the construction of structured liquids and derived materials. Finally, we provide an outlook of the opportunities and challenges in this field.关键词：Structured liquids;Nanoparticle surfactants;Liquid/liquid interface;Self-assembly
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发布时间：2024-05-07 - 摘要：Nanofiber composites have been widely used in new energy storage systems like lithium-metal batteries (LMBs, including lithium-sulfur batteries, lithium-air batteries, etc.) due to their high porosity, high specific surface area, diversified compositions and structural designability. The electrochemical performance of the batteries largely depends on the ion transfer process during charging and discharging, while the structural morphology and surface/interface properties of nanofiber composites have an important influence on the ion transport kinetics in batteries. Therefore, focusing on the key scientific and technical issues of sluggish ion transport dynamics and the shuttling of intermediate lithium polysulfides faced by LMBs, this review firstly introduces different new designs and preparation methods of nanofiber composites. Then, the effects of composition and structure of nanofiber composites on the regulation and optimization of ion transport kinetics in lithium batteries are discussed in detail by combining the recent works of our team. Following, the applications of nanofiber composites in different fields of lithium batteries are summarized, such as anodes, cathodes, separators, and solid-state electrolytes, etc. The challenges and prospects of nanofiber composites are finally proposed in future applications of high-performance energy storage equipment.关键词：Nanofibers;Nanocomposites;Electrospinning;Ion transport dynamics;Electrochemical performance
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发布时间：2024-05-07
Feature Article
- 摘要：Two-dimensional sp2c-conjugated polymers (2D sp2c-CPs) refer to layered materials constructed by C＝C. 2D sp2c-CPs have shown great potential in photocatalytic conversion of high-value-added products, osmotic energy generation, fluorescence sensing, proton conduction, organic semiconductor devices, and the extraction of radioactive nuclides, due to their designable periodic porous structures, high surface area, excellent structural stability, and high charge transfer. This review primarily elucidates the research endeavors of our research group concerning 2D sp2c-CPs. Firstly, the structural design and synthesis methods of 2D sp2c-CPs are presented. Subsequently, the preparation strategies for 2D sp2c-CP films, primarily conducted by our research group are introduced. Moreover, the applications of 2D sp2c-CPs in seawater uranium extraction, osmotic energy generation, fluorescence sensing, proton conduction, and photocatalysis are summarized in detail. Finally, the review offers a perspective on the research of 2D sp2c-CPs, encompassing modulation of crystal structure, exploration of novel synthesis methods, design of universal film synthesis strategies, and the expansion of related applications.关键词：2D sp2c-conjugated polymers;topology;thin film synthesis;photocatalytic energy conversion
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发布时间：2024-05-07 - 摘要：The cell membrane, the outer protective structure of a cell, serves to shield its internal components from external disruptions. By manipulating the cell membrane and incorporating specific molecules or structures, one can exert control over the fate and functionality of cells, thereby imbuing them with specialized functions. In recent years, the strategy of using biomacromolecules to self-assemble on cell membranes has been widely studied for functionalizing the surface of cell membranes. This paper reviews that the self-assembly of different biomacromolecules on the cell membrane surface can change the biological effects of cells and produce positive effects in tumor immunotherapy. It is elaborated that when biomacromolecular materials are self-assembled on the cell membrane, it can cause biological effects of cells, such as oligomerization of cell membrane receptor proteins to activate immune cells, changing cell membrane permeability to promote endocytosis, etc. At the same time, its application in tumor treatment is briefly introduced, and the future development of self-assembly technology modified cell membrane surface is prospected.关键词：Cell membrane;Self-assembly;Polymer materials;Peptide;Cancer treatment
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发布时间：2024-05-07
Review
- 摘要：Stretchable ionically conductive fibers hold great promise in the fields of flexible electronic devices, smart textiles, and human-machine interfaces. However, the scalable production of stretchable fibers with both high conductivity and elasticity remains a significant challenge. In recent years, pultrusion spinning has emerged as a promising technique for the continuous fabrication of ultrathin gel fibers at ambient conditions. Nevertheless, the reduction in fiber diameter often comes at the cost of significantly increased resistance, hampering their applications in smart sensing. To overcome this limitation, in this study, we introduce a one-step pultrusion spinning approach for the continuous production of highly elastic ionogel fibers. Our ionogel fiber is derived from a spinning dope containing poly(2-(dimethylamino)ethylacrylate) methyl chloride quarternary salt (PDMAEA-Q), poly(methacrylic acid) (PMAA), and an ionic liquid, 1-ethyl-3-methylimidazolium ethyl sulfate (EMI ES). Upon water evaporation, PMAA chains undergo nanoconfinement through hydrogen bonding, forming numerous clusters dispersed within the ductile PDMAEA-Q matrix. Moreover, the employed ionic liquid, EMI ES, interacts with polymer matrix through various physical interactions, further modulating the mechanical and electric properties of the resulting fiber. Owing to its hierarchical phase-separated structure formed by spontaneous nanoconfinement, the ionogel fiber exhibits exceptional stretchability (707% elongation), remarkable transparency (98%), high elasticity (~9% residual strain), high ionic conductivity (0.12 S·m-1), and anti-freezing properties. Furthermore, the ionogel fiber is sensitive to humidity, temperature, and strain changes, enabling its high-resolution detection of different stimuli via electrical signals. This work paves the way for the design of advanced ionically conductive fibers, unlocking a myriad of possibilities in smart sensing applications.关键词：Spinning;Conductive fiber;Ionogel;Smart sensing
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发布时间：2024-05-07 - 摘要：It is of significance to develop renewable and biodegradable aliphatic thermoplastic elastomers, which are promising replacement of the widely used polystyrene-based thermoplastic elastomer materials and are expected to partially address the end-of-life issue of plastics. Poly(lactic acid)-b-poly(δ-caprolactone)-b-poly(lactic acid) triblock copolymer was successfully prepared by sequential ring-opening copolymerization of commercial bio-based δ-caprolactone and L-lactide in the presence of an organobase (t-BuP2)/urea as binary catalytic system. These triblock copolymers exhibited different microphase separation structures and mechanical properties depending on the composition of soft and hard segments. As the volume fraction of the hard segment (fhard) increased from 0.22 to 0.34, the microphase separation structure of the sample gradually changed from spheres to hexagonally packed cylinders, and finally to lamella. When fhard was in the range of 0.30‒0.45, the triblock copolymers behaved as thermoplastic elastomers (TPEs) with high elongation at break (εb=600%‒1000%) and good tensile strength (σb=10-20 MPa). The samples with fhard~0.35 exhibited high elastic recovery (ER~90%), high resilience (~70%) and low residual strain (<10%). When the samples possessed comparable molecular weight of soft segment, the elastic recovery and resilience gradually decreased while the residual strain increased as fhard decreased from 0.34 to 0.22. The triblock copolymers that possessed a relatively lower volume fraction of the hard segment (fhard<0.22) can be used as pressure-sensitive adhesives after mixing with epoxy soybean oil (ESO). The 180° peel strength of PSA can be further adjusted by changing the composing triblock copolymers and the ratio of copolymers to ESO. The 180° peel adhesion tests showed that the peel strength of PSA-1 was (3.0±0.4) N/cm, and that of PSA-2 was (0.3±0.05) N/cm, which can be used as kraft paper tape and post-it note, respectively.关键词：Thermoplastic elastomers;Pressure-sensitive adhesives;Triblock copolymer;Ring-opening polymerization;Aliphatic polyester
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发布时间：2024-05-07 - 摘要：Designing novel copolymerization methods for preparing new copolymers is of significance to synthesize high-value polymer materials. Vinyl and heterocyclic compounds are the most important types of monomers in polymer chemistry, but the controlled copolymerization of the two is a great challenge due to the distinct polymerization mechanisms and reactive centers, which limits the development and application of new copolymer materials. Based on the thionolactone monomers which are studied widely, the cationic ring-opening polymerization of a seven-membered biphenyl-fused thionolactone (DOT) via using common cationic catalyst BF3·Et2O was studied. The structure of this newly synthesized polythioester was confirmed using 1H nuclear magnetic resonance (1H-NMR) and 13C-NMR. Differential scanning calorimeter method (DSC) and thermogravimetric analysis (TGA) indicated that the polythioester exhibits good thermal stability and a high Tg (98 ℃). Subsequently, cationic hybrid copolymerization of DOT and vinyl ether was explored. According to the effects of three types of cationic catalysts on the copolymerization of DOT and isobutyl vinyl ether (IBVE) without a chain transfer reagent (CTA), trifluoromethanesulfonic acid (CF3SO3H) was selected for further investigation. Subsequently, with the use of a scalable and green cationic CTA and the catalyst CF3SO3H, the controlled cationic hybrid copolymerization of DOT and IBVE was developed, producing a new poly(vinyl ether)-block-poly(thioester) copolymer (Mn=7.6-8.0 kg/mol, PDI<1.40). The block structure of the polymer was further confirmed by diffusion ordered spectroscopy (DOSY) NMR. This study provides design ideas for the development of new methods of hybrid copolymerization and the preparation of new copolymer materials.关键词：Cationic;Hybrid polymerization;Thionolactone;Vinyl ether
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发布时间：2024-05-07 - 摘要：Hollow mesoporous microparticles have attracted much attention because of their unique internal cavity structure and functional shell, which combines the physical and chemical properties of mesoporous materials. It is therefore of great interest to develop facile, effective, and controllable methods for the preparation of hollow mesoporous microspheres. This research proposes a new strategy for creating silica/carbon composite hollow mesoporous microparticles via the combination of three-dimensional confined self-assembly (3D-CSA) of block copolymer (BCP) and a self-template carbonization strategy. Firstly, using the 3D-CSA method, the BCP and perfluorooctane (PFO) underwent hierarchical self-assembly into core-shell microparticles. Notably, the shell was composed of BCP with mesostructures via microphase separation. Then, the continuous phase of the shell was selectively composited with silicon oxide on purpose of loading of the inorganic frame and cross-linking. Ultimately, the silica/carbon composite hollow mesoporous microspheres were generated by calcining the composite microparticles to selectively carbonize the continuous phase of the shell. The formation mechanism and necessary conditions of core-shell microparticles were systematically described. Additionally, the effects of the amount of precursors and the molecular weight of BCP on the morphology of hollow mesoporous microspheres were studied. This research provides a simple yet controllable method for the creation of novel hollow mesoporous microparticles.关键词：Block copolymers;3D Confinement;Self-assembly;Hollow microparticles;Mesoporous microparticles
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发布时间：2024-05-07 -
Sequentially Autonomous Rolling of Liquid Crystalline Elastomers with Tunable Actuation Temperatures 增强出版
摘要：The autonomous liquid crystalline elastomer (LCE) actuators have garnered increasing attention owing to their ability to sustain continuous motion without the need for external manual control. However, most autonomous LCEs are only capable of achieving self-sustained locomotion under specific single conditions (or within a small temperature range) due to their simplistic chemical design. This study begins with a twisted ribbon-shaped autonomous LCE, wherein precise control over the working temperature is attained by manipulating the network cross-linking density and incorporating non-liquid crystal co-monomers. The result shows that the cross-linking density has a significant impact on both the actuation performance and mechanical properties of LCEs, thereby influencing working temperature range and actuation speed. Specifically, as the amount of crosslinkers decreases, the actuation strain increases from 60% to 90% while the Young's modulus decreases from 21 MPa to 6 MPa. Due to the compromise of these two properties, the self-rolling capability would be constrained by either excessively high or low levels of cross-linking densities. The optimal performance is observed when the cross-linker ratio is in a moderate state, resulting in a wider range of actuation temperatures and faster moving speed. Beyond that, the incorporation of non-liquid crystal co-monomers also plays an important role in the actuation of LCEs. Different from the cross-linking density, both actuation performance and mechanical properties decrease significantly as the content of co-monomers increases, leading to a notable reduction in the temperature range required for actuation. The phase transition temperature of LCE even disappears when the co-monomer content exceeds 25 wt%, resulting in a loss of autonomous motion. Overall, the aforementioned methods enable the easy achievement of autonomous LCE actuators with diverse working temperature ranges. Sequential autonomous rolling can be accomplished during both the heating and cooling processes, owing to the distinct actuation temperatures exhibited by different LCE actuators. This tunable working temperature of autonomous LCE actuators will significantly broaden the scope of material design for soft robots.关键词：liquid crystalline elastomer;soft actuator;autonomous locomotion- 217
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发布时间：2024-05-07 - 摘要：Poly(lipoic acid)-based functional hydrogels incorporated with silver nanoparticles (AgNPs) are developed for bacteria-infected skin wound healing in this work. Owing to the reducibility of α-lipoic acid (LA), AgNO3 can be converted into AgNPs in the local hydrogel network (PLAS@AgNPs hydrogels), which are synthesized by concentration- and thermo-induced ring-opening polymerization of LA in the presence of NaHCO3. Benefiting from the dynamic nature of hydrogen bonds formed by －COOH groups, PLAS@AgNPs hydrogels feature facile injectability and self-healing ability, and exhibit stable adhesion behavior with porcine skin tissues (36 kPa). The resulting hydrogels show promising photothermal efficiency due to the in situ formation of AgNPs, and the temperature of the hydrogels can be elevated by 38 oC with the irradiation of near-infrared (NIR) light for 10 min, which can effectively inhibit the proliferation of escherichia coli and staphylococcus aureus. Moreover, the PLAS@AgNPs hydrogels can also clear the intracellular reactive oxygen species (ROS) inherited from the antioxidant nature of LA. In a rat full-thickness skin injury model with bacterial infection, the PLAS@AgNPs hydrogel dressing can accelerate the skin wound healing with the assistance of NIR light irradiation through the synergistic effect of anti-bacteria and ROS scavenging.关键词：Hydrogel;Hydrogen bond;α-Lipoic acid;Photothermal effect;Skin wound healing
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发布时间：2024-05-07
Research Article
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