最新刊期
卷 55 ， 期 7 ， 2024
- 摘要：Polymer self-assembly is an important branch of the self-assembly field, and research on the precise control of its assembly process and function is necessary to further broaden its application scope. Gas, as a "green" stimulus, different from conventional physical or chemical signals, is of great significance for the regulation of the self-assembly process of polymers. Combining the work of our research group, this paper systematically introduces two types of new gas-regulated polymer assembly systems: "gas-responsive polymers" and "gas-constructed polymers". Gas-responsive polymers can respond to external gas signal stimulation, change their amphiphilicity or aggregation state by reacting with gas molecules and specific chemical moieties in the polymer, thereby affecting their self-assembly behavior and outputting functions. The progress of research on the design and controllable assembly of gas-sensitive polymers is summarized, focusing on the three major gas signal molecules in living organisms—hydrogen sulfide (H2S), carbon monoxide (CO), and nitric oxide (NO) as stimuli sources. Gas-constructed polymers use gas molecules as assembly units to construct polymer materials. Then introduces the "dynamic gas bridge" formed between boron/phosphorus frustrated Lewis acid-base pairs and gas molecules such as carbon dioxide (CO2), as well as research on the structure design, dynamic self-assembly, and functional applications of gas-constructed polymers. Finally, the future development of these two types of gas regulated polymers was discussed. Gas-responsive polymers can be used in the design of multi-signal molecule-programmed responsive systems, achieving intelligent intracellular targeted release and carrier transport functions. Gas-constructed polymers, while having universality for a broad spectrum of gas molecules, lack selectivity for single gas molecules and have poor chemical tolerance in the design of complex functions. The solution to this problem will lay the foundation for the development of a wider range of functional gas-constructed assembly materials.关键词：Polymer self-assembly;Gas;Gas-responsive polymer;Gas-constructed polymer;Functional assemblies
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发布时间：2024-09-25 - 摘要：In the field of molecular assembly, photocontrolled self-assembly is an intelligent strategy to regulate molecular ordering, multiscale structure and optoelectronic properties. However, conventional photocontrolled self-assembly is implemented through a photochemical process in which photochemical reactions induce structural changes in molecules. The nanostructures and morphologies formed by photocontrolled self-assembly are often unpredictable due to the presence of side reactions and limited conversion rates. On the contrary, assembly by photophysical processes that only utilize the conformational changes of molecules from the ground state to the excited state can avoid the above drawbacks and can further promote the synergistic assembly or phase transition of the whole material system. In this paper, we focus on the photoexcitation-induced assembly (PEIA) strategy using polysulfide aromatic hydrocarbons (PAHs) as the building blocks. PAHs are capable of generating significant molecular conformational transitions from the ground state to the excited state, which are favorable for the formation of intermolecular interactions that drive molecular motions, aggregation, and assembly. In this paper, we systematically introduce the progress of exploring PEIA of polysulfide aromatics at the molecular level, further demonstrate that PEIA of polysulfide aromatics can synergistically drive molecular motions and phase transitions in polymer systems, and provide an outlook on the key issues and important challenges for the future development of PEIA.关键词：Excited-state conformation;Persulfurated arenes;Photoinduced self-assembly;Phosphorescence
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发布时间：2024-09-25 - 摘要：The properties and applications of crystalline polymer materials largely depend on their crystallinity. Rapid preparation of high crystalline or single crystal polymer materials is not only beneficial for studying their structure-property relationship, but can also expand their practical applications. However, efficiently and accurately assembling organic molecules into polymer single crystals through polymerization is a challenging task. To address this issue, our group has developed a supercritically-solvothermal method for achieving ultra-fast preparation of polymer single crystals. This method uses supercritical carbon dioxide as the reaction medium, which greatly improves the growth rate of polymer crystals due to its high diffusion rate and low viscosity. This feature article reviews the commonly used synthesis methods for covalent organic frameworks (COFs), as well as the challenges faced in single crystal preparation. Then, the basic properties and applications of supercritical fluids, the advantages of supercritically-solvothermal method, and the structural characterization of the prepared COF single crystals are systematically discussed. Finally, the challenges and development directions faced in the synthesis of polymer single crystals by supercritically-solvothermal method are prospected.关键词：Supercritically-solvothermal method;Polymer;Single crystal;Covalent organic frameworks;Fast synthesis
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发布时间：2024-09-25 - 摘要：As a main-chain liquid crystalline polyelectrolyte, poly(2,2'-disulfonyl-4,4'-benzidine terephthalamide) (PBDT) is characterized by its fully aromatic architecture, ultra-high density of sulfonate groups, intramolecular and intermolecular hydrogen bond networks formed by the amide groups. Here we describe a series of distinctive characteristics of PBDT solutions, including the self-assembled double helical conformations, formation of nematic liquid crystalline phases, and anisotropic ion transport along polymer chains. Based on the multi-scale molecular conformation of PBDT and its selective ion transport properties, composite materials with various functions can be designed, such as PBDT-based hydrogels, ionogels and nanocomposites. By emphasizing the rigid rod architecture and the anisotropic ion transport mechanism of counter ions in PBDT, the applications of PBDT composites in solid-state electrolytes and lithium battery electrode binders have been highlighted; meanwhile, indicating potential significance for the development of other rigid-rod polyelectrolyte materials similar as PBDT for the field of new energy storage and conversion and other related areas.关键词：Rigid rod polyelectrolytes;Double helical conformation;Liquid crystalline phase;Anisotropic ion transportation;Lithium batteries
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发布时间：2024-09-25
Feature Article
- 摘要：Fluoropolymers possess many outstanding physical and chemical properties, allowing applications in aerospace, defense, chemicals, new energy, biomedicine, etc. Reversible deactivation radical polymerization (RDRP) is among the important methods for realizing precise synthesis of polymers. However, compared with the (methyl)acrylate and styrene derivatives, RDRPs of fluorinated monomers are very limited. Recently, a growing number of research reports demonstrated that the precise regulation of polymer structures contributes to improving properties of polymers, promoting the development of high-end materials. Herein, this review focuses on RDRPs of fluorinated monomers, introduces the research advancements of the controlled synthesis of side-chain and main-chain fluorinated polymers, and summarizes the RDRP reports of fluorinated acrylates, fluorinated styrene, chlorotrifluoroethylene, tetrafluoroethylene, vinylidene fluoride, hexafluoropropylene, and perfluoroalkyl vinyl ethers. Given the urgent need for customized synthesis of fluorinated polymers in many frontier fields, the development of controlled synthesis methods for fluorinated polymers will not only contribute to regulating the structural scope of fluorinated polymers but also facilitate the production of high-performance fluorinated polymer materials. This review serves as a valuable resource for researchers working in the field of fluorinated polymers, providing an overview of the current state of the art and briefly illustrating the prospects and challenges for the RDRP of fluorinated monomers.关键词：fluoropolymers;fluoroalkenes;reversible deactivation radical polymerization (RDRP);Living polymerization
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发布时间：2024-09-25 - 摘要：Soft matter science is an important branch in the fields of physics, chemistry, and material science. However, the complexity of soft matter systems, especially their multi-scale structures and rich dynamic behaviors, poses significant challenges to researchers. To address these challenges, simulation methods based on field theory demonstrate unique advantages in simulation techniques. By introducing continuous field variables, they provide a more efficient and macroscopic perspective for describing and handling complex interactions in soft matter systems. This article first introduces the basic principles of polymer field theory and elaborates on their applications in soft matter physics, such as the structure prediction of protein HP models, the static topological entanglement problems of polymer chains, chemical reaction/light induced microphase separation, etc. It then explores the application of modern computational technologies like deep learning in soft matter research, and finally looks forward to the future research trends and developments in the field of soft matter, pointing out that field theory remains a powerful tool for soft matter study.关键词：Soft matter;Simulation methods based on field theory;Self-consistent field theory;Deep learning
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发布时间：2024-09-25
Review
- 摘要：Real-time monitoring of glucose concentration in vivo holds significant importance for disease diagnosis and treatment. The enzyme-based electrochemical glucose sensor has garnered considerable attention in the realm of real-time glucose monitoring due to its outstanding selectivity and sensitivity. Despite the development of first and second generation electrochemical glucose sensors, they encounter numerous challenges derived from their sensing principles, including interference from oxygen concentration, instability of electronic mediators, and leaching toxicity. The third generation of glucose sensor based on direct electron transfer between enzyme and electrode is anticipated to address these challenges. Here, we report an all-polymer-based flexible fiber glucose sensor (FGS) based on direct electron transfer, leveraging poly(3,4-vinyldioxythiophene):polystyrene sulfonate (PEDOT:PSS) and glucose dehydrogenase (GDH) as its constituents. The FGS exhibits commendable linearity (R2=0.9968) within the range of 10-500 μmol/L and demonstrates a sensitivity of 62.53 μA/(mmol·L-1·cm2). The FGS is seamlessly integrated into fabric, enabling continuous real-time monitoring of glucose levels in human sweat during exercise. This work presents a novel approach for developing the third-generation glucose sensors to cater to the requirements of wearable technology.关键词：Flexible fiber;Glucose sensor;Direct electron transfer;Sweat monitoring;Poly(3,4-vinyldioxythiophene):polystyrene sulfonate
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发布时间：2024-09-25 - 摘要：Polymers with precise structures possess important roles in biomedicine, information storage, hierarchical assembly, etc., while their preparation has always been a challenge in the field of polymer synthesis. N-Methyliminodiacetic acid (MIDA) boronates, employed as tags in liquid-phase iterative synthesis, were widely utilized in Suzuki-Miyaura coupling reactions as stable boronic acid precursors for the construction of a variety of organic molecules. In this study, four monomers with different structures of thiophene-phenyl side chains were prepared based on MIDA boronates tags. Precise aryl side-chain linkages were created through several coupling reactions between boronic acids and aryl bromides containing MIDA boronates. Further MIDA boronates can be converted into hydroxyl functional groups, allowing for further modification and introduction of vinyl functional groups to synthesize polymerizable monomers. Different monomers were employed in the controlled radical polymerization to yield polymers with precisely controlled side-chain structures. UV-Vis and fluorescence spectra of the polymers revealed distinct optical properties based on different side-chain structures, while similarities in thermal and crystalline properties were observed due to their identical main-chain structures and similar side-chain compositions. This work establishes a methodology for synthesizing precisely controlled side-chain monomers using MIDA boronate labels, providing insights and feasible approaches for the accurate modulation of polymer side chains.关键词：Sequence-defined polymers;boronic acid ester;Controlled/Living polymerization
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发布时间：2024-09-25 - 摘要：Carbon nanotubes (CNT) can be assembled into carbon nanotube fibers (CNTF) by floating catalytic chemical vapor deposition, but it remains challenging to effectively enhance the interaction force between carbon nanotubes and their bundles inside carbon nanotube fibers to effectively improve mechanical and electrical properties. In this study, we proposed to introduce aramid nanofibers into carbon nanotube fibers through solvent protonation to obtain high-performance carbon nanotube composite fibers. The composite fibers exhibited tensile strength of 1.23 GPa and the Young's modulus of 26.97 GPa, which were improved by 92.1% and 133.5% compared with the original carbon nanotube fibers, respectively. The specific strength and specific modulus of the composite fibers were 28.67 and 628.67 cN/dtex, which were comparable to those of high-performance fibers such as aramid fiber. In addition, the composite fibers showed good flexibility and electrical conductivity, which can be directly used as the electrode material in fiber electronic devices, showing good application potential.关键词：Carbon nanotube fiber;Aramid nanofiber;Hydrogen bond;Polymer composite fiber
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发布时间：2024-09-25 - 摘要：Based on the synergistic non-covalent interaction of tadpole-like single-chain particles with multiple sites on the wafer surface, a PEG brush grafting strategy has been developed that combines ease of handling and excellent "biofouling" properties. Specifically, the block copolymer poly(ethylene glycol)-b-poly(4-vinylpyridine) (PEG-b-P4VP) was synthesized by atom transfer radical polymerization (ATRP). The P4VP block was then intra-chain cross-linked using the "electrostatic-mediated" strategy, and the P4VP "head" was completely quaternized by further addition of excess ethyl iodide, yielding tadpole-like single-chain particles with completely quaternized "heads" (TSCP-Q). By simple solution immersion grafting method, the completely cross-linked and collapsed "head" significantly reduces its adsorption area on the silicon wafer through multi-site non-covalent synergistic interaction, while the extended PEG "tail" ensures grafting uniformity of TSCP-Q brushes on the surface through volume repulsion effect. As a result, the obtained TSCP-Q brushes achieve stable and uniform grafting on the silicon wafer, with PEG "tail" overlying the P4VP "head" anchoring layer and effectively masking the charge of the anchoring layer. The TSCP-Q brushes were shown to have excellent anti-bovine serum albumin (BSA) adsorption (4.8 ng/cm2) and could effectively inhibit the colonization of Staphylococcus aureus (S. aureus) (killing efficacy up to 81%).关键词：Tadpole-like single-chain particle;Polymer brush;Poly(ethylene glycol);Anti-protein adsorption;Antibacterial
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发布时间：2024-09-25 - 摘要：Conjugated polymers have been widely applied in various optoelectronic devices because of their special mechanical, electric, and optoelectronic properties. Usually, the fabrication of conjugated polymers is based on solution processing, and the conformation and solution aggregation state of conjugated polymers can be transferred to the solid state due to the memory effect. Therefore, the solution-state aggregation of conjugated polymers has an important impact on their crystalline structure and thus property in the film state. In this work, the concentration of poly(3-butylthiophene) (P3BT) solution was adjusted to control the chain aggregation in the solution, which in turn influenced the crystalline structure including form and crystal orientation of P3BT in thin films. Moreover, the correlation between different crystalline structures of P3BT and their charge transport properties based on organic field-effect transistors (OFET) was revealed. It showed P3BT aggregated weakly in low concentrations of solutions and thus produced form I crystals in edge-on orientation in the films, which had non-interdigitated packing of alkyl side chains and a larger side-chain stacking distance. In contrast, stronger aggregation of P3BT chains was observed in the solutions with high concentrations and form Ⅱ crystals in the mixed flat-on and edge-on orientations were produced in the films. These P3BT form Ⅱ crystals had interdigitated side chains and a smaller side-chain stacking distance than that of form Ⅰ. These P3BT films with different forms and crystal orientations were closely related to their charge transport characteristics.关键词：Polythiophenes;Solution-state aggregation;Form;Crystal orientation;Organic field-effect transistors
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发布时间：2024-09-25
Research Article
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