最新刊期
卷 53 ， 期 7 ， 2022
- 摘要：Covalent polymers are robust but not adaptive, while supramolecular polymers have fantastic dynamic properties but lack good mechanical properties, which limit their applications in specific fields. Inspired by the working mechanism of the supramolecular polymers in living organisms, covalent polymers and supramolecular polymers are integrated into one system and connect with each other by effective interactions to afford a new fashion of polymeric system named as synergistic covalent-and-supramolecular polymers (CSPs), which can combine and even amplify the merits of the two kinds of polymers. This article first introduces the definition and features of CSPs. Then we summarize the current synthetic strategies for the synergistic CSPs. Further, the structures and properties of synergistic CSPs are emphasized to establish their relationships and elucidate property advantages of synergistic CSPs. Finally, the key scientific issues and challenges in the field of synergistic CSPs are discussed. Synergistic CSPs are beneficial to remedy the deficiencies of individual polymer, and thus prompt the practical applications of supramolecular polymers. Furthermore, it also provides a new approach to preparing polymeric materials with mechanically robust yet dynamic properties.关键词：Synergistic effect;Supramolecular polymers;Non-covalent interactions;Mechanical properties;Dynamic materials
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发布时间：2024-10-08 - 摘要：Wearable and implantable fiber bioelectronics can continuously collect physiological information and accurately modulate physiological environment, which have revolutionized the conventional way of health monitoring, disease diagnosis and treatment. However, most of the fiber bioelectronics reported so far have insufficient flexibility. They do not match the soft tissues mechanically and cannot form stable device/tissue interface, limiting their long-term use. In this feature article, we mainly introduced our recent progress on flexible fiber bioelectronic composite materials and devices, aiming to solve the problem above. We first introduced the fabrication of flexible polymer composite fibers with hybrid or core-sheath structure, which possess good electrical and mechanical properties as well as biocompatibility. Based on the high-performance flexible polymer composite fibers, a series of fiber bioelectronics with functions of biosensing, energy-harvesting and storage, and electrochemical modulating were constructed for wearable and implantable applications, which showed promising prospects in healthcare and medicine. Finally, we discussed the future development direction of flexible fiber bioelectronics.关键词：Polymer composite fiber;Carbon nanotube;Flexible;Fiber bioelectronics
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发布时间：2024-10-08 - 摘要：Holographic polymer materials usually refer to structurally ordered polymer materials, which can store the whole information of light including the amplitude and phase upon laser interference. They have exhibited transformative potential for high-tech applications such as naked-eye recognizable three-dimensional display, augmented reality, high-security level anticounterfeiting and high-density data storage. With the development of these high-tech fields, it is highly desired to boost the performance and functionalities of holographic polymer materials. Toward this end, mediating reaction orthogonality can be an effective approach. Starting from the concept and design principle of orthogonal reactions, in this minireview, recent progresses of advanced manufacturing based on orthogonal reactions are highlighted. Furthermore, the significance of orthogonal reactions in holographic polymer materials are discussed in detail, for instances, to optimize material processing, to increase the refractive index modulation and grating diffraction efficiency, to decrease haze, to reduce volumetric shrinkage during polymerization, to increase the data storage capacity, and to non-interferingly integrate holographic and emissive dual images. Yet, new orthogonal reaction systems are still highly awaited to design high performance and multifunctional holographic polymer materials.关键词：Holography;photopolymer;orthogonal reactions;advanced manufacturing
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发布时间：2024-10-08 - 摘要：In the past few years, the performance of laboratory-scale organic solar cells (OSCs) have experienced very fast development, especially with the development of non-fullerene acceptor. However, there are still challenges on the way to realizing efficient module devices, such as the low compatibility of the thickness-sensitive interlayer and active layer with large area coating techniques, the tremendous power loss on enlarged electrode, the frequent need for toxic solvents, tedious optimization processes used during device fabrication, etc. To achieve high-performance large area PSC modules, we have carried out a series of studies. For the interlayer, we have developed simple and efficient approaches to achieving large area cathode interlayer using electrostatic layer-by-layer self-assembly and in situ self-assembly processes. N-type doping was also developed to obtain printable large area cathode interlayer. In terms of active layer, one of the main obstacles for printing ideal active layer comes from the excessive aggregation of film during printing. In this case, we have employed solvent engineering, third component strategy, molecular engineering and device structure engineering to overcome the excessive aggregation of active layer during printing and obtained high performance modules. On the basis of these results, non-halogen solvent dimethylbenzene processed large-area module with an active area of 18 cm2 and efficiency over 14% was obtained. Finally, the existing problems and development directions of this field are discussed and forecasted.关键词：Organic solar cell;Large-area module;Interlayer;Active layer aggregation;Device structure
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发布时间：2024-10-08 - 摘要：Two-dimensional macromolecules, a new family of polymer with 2D topology, have expanded to include hundreds of members from insulator and semiconductor to metal and superconductor, rapidly promising potential breakthroughs in extensive applications. Two-dimensional macromolecules are posed to rapidly extend the polymer science and technologies and indispensably shape our future lives. The great expectations of 2D macromolecules urgently call a unified understanding of their macromolecular behaviors but also a general methodology to guide the precise fabrication with rational structural design, in order to achieve disruptive performances of their macroscopic materials. This principal development philosophy has been self-evidenced by the classic 1D polymer science, engineering and industry. Motivated by this philosophy, we need to establish the conformation principle of 2D macromolecules and a systematic routine for macroscopically assembled materials. In this monograph, we give a systematic review to researches of fundamental conformation behaviors of 2D macromolecules and the emerged conceptual researches of modulating their condensed structures. In the experimental model of graphene oxide, we conclude the advances in fundamental scaling relationship between conformation and molecular size of 2D macromolecules, their conformation transition rules, the spontaneous and artificial liquid crystalline phases and the methods for modulating the multiscale condensed structures in their macroscopic materials. The research advances extend from the conformation transition diagram of individual and multiple 2D macromolecules to the exotic liquid crystal behaviors and the condensed structures of their macroscopic materials. An important analogy between 1D and 2D polymers has been proposed and the conformation principle of 2D macromolecules is clearly establish, laying the foundation of the unified polymer theory. We hope that the monograph can help complete the systematic understanding of polymer science by including the new 2D molecular topology. The developing system of 2D macromolecules will generally guide the precise control and versatile design of macroscopic materials of 2D polymers and realize wide applications.关键词：Two dimensional macromolecules;Conformation;Condensed state;Two dimensional materials
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发布时间：2024-10-08 - 摘要：Controlling dye molecules into a highly ordered J-type sliding arrangement/packing induces exciton coupling to enable new photophysical properties, which makes J-aggregation a powerful tool to construct efficient photoactive materials for disease diagnosis and treatment. In particular, the significant red-shift of absorption and emission peak, enhanced absorbance, and narrowed spectral lines enable deep tissue penetration of photons, high photon utilization, and multi-channels optical diagnosis and therapy, respectively. However, J-aggregates have difficulty in maintaining the necessary dye alignment in complex living settings, impeding their biomedical applications. Furthermore, the difficulty in forming nanostructures with appropriate morphology and size is another obstacle to the in vivo applications of J-aggregates. Polymeric nanoassemblies formed by self-assembly of amphiphilic block copolymers have been widely used as drug delivery vehicles due to their intriguing properties, such as stimuli responsiveness, multifunctional integration, and biocompatibility. Therefore, covalent conjugation with polymers and/or encapsulation by polymer assemblies provide an efficient strategy for constructing optical and colloidal stable J-aggregate materials for biological applications. In this review, we summarize recent advances in polymeric materials with J-stacked dyes for disease diagnosis and therapy, including: (i) establishing facile strategies to construct water-stable polymeric or supramolecular J-aggregate nanomaterials to maintain the necessary J-type arrangement in complex living systems, (ii) developing robust methods to remodel J-aggregates nanoassemblies with the assistance of polymers to obtain nano J-aggregates with desired morphology and size to improve their in vivo performances in tumor diagnosis and therapy, and (iii) devising and constructing novel polymeric nano-J-aggregates with remarkable performances in cancer diagnostic and therapeutic applications, such as near-infrared-Ⅱ imaging agents with high tissue penetration depth, non-photobleaching photothermal agents for cancer photothermal therapy, and activatable photosensitizers in response to disease biomarkers for precise photodynamic therapy. In light of the unique photophysical and photochemical properties of J-aggregates and fascinating properties of polymers, this new type of polymeric materials with J-stacked photo-functional moieties bring new design principles and preparation methods for the development of phototherapeutic materials, and opens a gateway to the explore polymer/supramolecular phototherapeutic materials with higher performance.关键词：Photoactive functional polymer;Diagnostic and therapeutic polymer material;Noncovalent interaction;J-aggregation;Molecular self-assembly
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发布时间：2024-10-08 - 摘要：Through-space charge transfer polymer fluorescent materials are a kind of luminescent polymers that utilize non-conjugated polymer skeleton to realize through-space π-stacking of electron donors and acceptors, and then emit light by through-space charge transfer, which become a new way for developing luminescent polymers beyond the classical fluorescent polymers based on conjugated polymer backbone and through-bond charge transfer emission. This review summarizes the research progress of through-space charge transfer polymers in our group from the perspective of material design and device performance, and disscusses the realization, regulation and application of through-space charge transfer polymers. Meanwhile, molecular design strategies for tuning spatial interactions between donors and acceptors by modulating their strength, planarity, distance and alignment patterns, and effect of multiple donor/acceptor structures on through-space charge transfer effect, thermal activation delayed fluorescence property and electroluminescent performance, are illustrated. Finally, opportunities and challenges for the future development of through-space charge transfer polymers are also discussed.关键词：Through-space charge transfer;Luminescent polymer;Donor/acceptor structure;Organic electroluminescence
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发布时间：2024-10-08 - 摘要："Adhesion" is essentially the formation of chemical bonds, hydrogen bonds or van der Waals forces at the interface, which is considered as a universal multi-scale interaction. In recent years, on the basis of mussel biomimetic, incorporation of catechol groups into the dynamic boronate ester polymers, has become an important developing direction of functional polymer adhesives. This feature article focuses on the molecular adhesion, micro/nano surface adhesion and macroscopic surface adhesion, as well as introduces the research progress in the functionalization of polymer materials related to the manipulation of catechol groups by using boronate ester bonds. For molecular adhesion, the interaction between catechol groups and guest molecules or ions in the boronate ester polymers, and the corresponding material morphology control and stimuli-responsive behavior are discussed. For micro/nano surface adhesion, the supramolecular driving forces and self-assembly mechanism of boronate ester polymers are analyzed, and the related application in the modification of micro/nano materials is introduced. For macroscopic surface adhesion, the relationship between the manipulation of catechol groups by using boronate ester bonds and the control of adhesion performance is discussed, and the application of boronate ester polymer adhesives in the field of macro-assembly and climbing robot is introduced. Finally, the future and development trend of this field are prospected from the perspective of new boronate ester polymers, precise control over dynamic bonds, and device design and applications.关键词：Boronate ester polymer;Catechol-based polymer;Mussel-inspired bionics;Surface and interface control;Intelligent polymer
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发布时间：2024-10-08 - 摘要：Carbonized polymer dots (CPDs) is a kind of carbon-based nanomaterial with a new hybrid structure of carbon core and polymer shell, which is formed by polymerization, crosslinking and carbonization of small molecules, polymers or biomass through bottom-up methods. This special hybrid structure endows CPDs with many unique optical, electrical and other physical and chemical properties. For example, high fluorescence quantum yield, easy surface functionalization, high chemical stability, photobleaching resistance, low toxicity, etc., make CPDs show great application potential in biomedicine, catalysis, photoelectric devices, sensing, anti-counterfeiting and other fields. As an emerging kind of zero-dimensional carbon nanomaterials, CPDs has received extensive research attentions. Here, through the summary and analysis of the relevant literature, we emphasize the importance of polymerization and carbonization on the structure and properties of CPDs, and it is seen as a new type of single-particle organic inorganic hybrid system. We summarize the research progress of CPDs from four perspectives: the structural characteristics, preparation, photoelectric properties and their applications in the fields of optics and catalysis. The emphasis of this review is especially focused on our research work on the fields of controllable preparation, luminescence mechanism, optical and catalytic applications, and discusses the problems and important development direction of CPDs in the future.关键词：Carbonized polymer dots;Core-shell structure;Inorganic-organic hybrid;Controllable preparation;Photoelectric properties
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发布时间：2024-10-08
Feature Article
- 摘要：Cationic polymers have been widely used as biomedical materials in recent years. Cationic polymers possess an outstanding capability to bind to cell membranes owing to their positive charge, following which they can penetrate the cell membranes. Among such polymers, nitrogenous cations, such as primary amines, secondary amines, and tertiary amines, are obtained through the ring-opening reaction of amine groups with epoxy functionalities. Moreover, abundant hydroxyl groups can be generated because of such reaction, endowing the obtained polymers with good biocompatibility. This article introduces three strategies for the construction of cationic polymers based on the ring-opening reaction of amine groups with epoxy groups and verifies the applicability of the strategies in bio-based applications (e.g., gene delivery and antibacterial activity): (1) Poly-(glycidyl methacrylate) (PGMA), which is rich in the epoxy functionality, is synthesized by atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer polymerization (RAFT) reactions and reacts with amine groups for further modification. A series of functional and hydroxy-rich ethanolamine-functionalized PGMA (denoted by PGEA) were synthesized by the ATRP polymerization of glycidyl methacrylate using designed small functional molecules as initiators or introducing functional molecules using amine groups to conduct ring-opening reactions with PGMA. (2) Based on the host-guest assembly, hydrophilic and hydrophobic assembly, and electrostatic assembly, a series of cationic polymers coupled with macromolecules were designed by assembling PGEA-based cationic polymers with native polysaccharides or native proteins. (3) By designing degradable monomers with multiple amine or epoxy groups, reducible branched cationic polymers with abundant hydroxyl groups were synthesized via the “one-pot” ring-opening reaction of amine groups and epoxy groups. These biodegradable branched cationic polymers can be responsively and tunably degraded in specific microenvironments, which is favorable for gene release and biosafety. These findings are greatly significant for the future development of biomaterials.关键词：Cationic polymers;Ring-opening reaction;Hydroxyl-rich;Nucleic acid delivery vector;Antibacterial materials
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发布时间：2024-10-08 - 摘要：Polyurethane foams (PUFs) with a porous-cell structure and low density, including rigid polyurethane foam (RPUF) and flexible polyurethane foam (FPUF), have a wide range of applications and can meet multifarious requirements in daily life. However, PUFs are easy to ignite owing to their high contents of hydrocarbon chain segments, large specific surface area, and low limiting oxygen index (LOI) of 17%-19%. When PUFs are ignited and burned, the fire spreads rapidly, and large volumes of toxic fumes will be released concomitantly, which bring serious negative influences on the human body and the environment. Flame retardants assuage the threat of fire from inherently flammable PUF materials. Driven by global environmental concerns, halogen-free flame retardants of PUFs have grabbed extensive attention. This review summarizes the combustion characteristics and flame-retardant mechanism of polyurethane foams, and enumerates the recent progress of the reactive, additive, and surface flame-retardant strategies, focusing on an in-depth analysis of the different contributions and mechanisms of these studies. The difference and similarities of the combustion behaviors and flame-retardant methods for RPUF and FPUF are analyzed in detail. Finally, crucial objections correlated with flame-retardant PUFs are discussed, and prospects and new development strategies for flame retardancy are proposed. How to maintain the comprehensive performance of the foam and achieve high-efficiency flame retardancy is the key and difficult point in the practical research and application of PUF. To tackle the above problems, highly efficient flame-retardant reactive molecules or nanoscale additives can be designed to improve the compatibility of flame retardants with the matrix. The durability of flame-retardant coatings can be enhanced by high-adhesion coating component regulation, surface modification pretreatment, and biomimetic design. Breaking through the conceptual limitations of traditional flame-retardant methods, a variety of flame-retardant methods can be combined reasonably and complement each other to achieve the best effect. Environmental friendliness, high efficiency, high flame-retardant and smoke suppression, and recyclability are important directions for the future development of flame-retardant PUFs.关键词：Polyurethane foam;Halogen-free flame retardancy;flame-retardant mechanism;flame-retardant method
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发布时间：2024-10-08 - 摘要：Phototheranostics, as an emerging treatment integrating the functions of light-driven diagnostic imaging and therapy, has aroused extensive attention for both fundamental research and clinical application in recent years because of its advantages of high temporal and spatial selectivity, low side effects, small trauma and high controllability. The conjugated polymers have distinct advantages including excellent optical properties, easy chemical structure regulation, good biocompatibility and solution processability, showing great potential application in the field of phototheranostics. However, traditional fluorescent molecules including the conjugated polymers suffer from the phenomenon of aggregation-caused quenching (ACQ) in aggregate state resulted from their rigid planar structures, thus hindering their biological applications. Luminogens with aggregation-induced emission (AIE) characteristics have attracted much attention because of their high fluorescence quantum efficiency in aggregate. This review is aimed to summarize the state-of-the-art advancements of AIE polymers in phototheranostics, especially the D-A type conjugated polymers, involving the construction strategies of AIE polymers and their applications in three aspects of biological imaging, tumor diagnosis and therapy, and bacterial eradication. According to the practical applications, the different requirements of construction strategies for AIE polymers, as well as the comparisons of the structure and properties advantages between the small molecules and polymers are also discussed. For biological imaging, the review is mainly focused on the development of AIE polymers with NIR-II fluorescence emission and high brightness to achieve high-resolution fluorescence imaging in deep tissues. In the aspect of tumor diagnosis and treatment, the review illustrates the AIE polymers with great advantages compared with small molecules in photon absorption and photosensitization performance, and their applications in photodynamic therapy, photothermal therapy and combined therapy. Also, the applications of AIE polymers for photodynamic therapy of bacterial infections are illustrated. Although the development of AIE polymers have lagged behind that of small molecules mainly due to their complex molecular structures and more difficult AIE mechanism studies, it is necessary to pay more attention to pushing forward the studies on AIE polymers and having in-depth understanding about structure-properties relationship. Additionally, the future development in the field of AIE polymers is prospected at the end of this review.关键词：Aggregation-induced emission;Polymer;Phototheranostics
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发布时间：2024-10-08
Review
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