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Self-healing covalent adaptable networks (CANs) are not only of fundamental interest but also of practical importance for achieving carbon neutrality and sustainable development. However, there is a trade-off between the mobility and cross-linking structure of CANs, making it challenging to develop CANs with excellent mechanical properties and high self-healing efficiency. Here, we report the utilization of a highly dynamic four-arm cross-linking unit with an internally catalyzed oxime-urethane group to obtain CAN-based ionogel with both high self-healing efficiency (>92.1%) at room temperature and superior mechanical properties (tensile strength 4.55 MPa and toughness 13.49 MJ m-3). This work demonstrates the significant potential of utilizing the synergistic electronic, spatial, and topological effects as a design strategy for developing high-performance materials.
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Fibers, originating from nature and mastered by human, have woven their way throughout the entire history of human civilization. Recent developments in semiconducting polymer materials have further endowed fibers and textiles with various electronic functions, which are attractive in applications such as information interfacing, personalized medicine, and clean energy. Owing to their ability to be easily integrated into daily life, soft fiber electronics based on semiconducting polymers have gained popularity recently for wearable and implantable applications. Herein, we present a review of the previous and current progress in semiconducting polymer-based fiber electronics, particularly focusing on smart-wearable and implantable areas. First, we provide a brief overview of semiconducting polymers from the viewpoint of materials based on the basic concepts and functionality requirements of different devices. Then we analyze the existing applications and associated devices such as information interfaces, healthcare and medicine, and energy conversion and storage. The working principle and performance of semiconducting polymer-based fiber devices are summarized. Furthermore, we focus on the fabrication techniques of fiber devices. Based on the continuous fabrication of one-dimensional fiber and yarn, we introduce two- and three-dimensional fabric fabricating methods. Finally, we review challenges and relevant perspectives and potential solutions to address the related problems.
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Global population growth and industrialization have exacerbated the nonrenewable energy crises and environmental issues, thereby stimulating an enormous demand for producing environmentally friendly materials. Typically, biomass-based aerogels (BAs), which are mainly composed of biomass materials, show great application prospects in various fields because of their exceptional properties such as biocompatibility, degradability, and renewability. To improve the performance of BAs to meet the usage requirements of different scenarios, a large number of innovative works in the past few decades have emphasized the importance of micro-structural design in regulating macroscopic functions. Inspired by the ubiquitous random or regularly arranged structures of materials in nature ranging from micro to meso and macro scales, constructing different microstructures often corresponds to completely different functions even with similar biomolecular compositions. This review focuses on the preparation process, design concepts, regulation methods, and the synergistic combination of chemical compositions and microstructures of BAs with different porous structures from the perspective of gel skeleton and pore structure. It not only comprehensively introduces the effect of various microstructures on the physical properties of BAs, but also analyzes their potential applications in the corresponding fields of thermal management, water treatment, atmospheric water harvesting, CO2 absorption, energy storage and conversion, electromagnetic interference (EMI) shielding, biological applications, etc. Finally, we provide our perspectives regarding the challenges and future opportunities of BAs. Overall, our goal is to provide researchers with a thorough understanding of the relationship between the microstructures and properties of BAs, supported by a comprehensive analysis of the available data.
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Soft actuators, pivotal for converting external energy into mechanical motion, have become increasingly vital in a wide range of applications, from the subtle engineering of soft robotics to the demanding environments of aerospace exploration. Among these, electrochemically-driven actuators (EC actuators), are particularly distinguished by their operation through ion diffusion or intercalation-induced volume changes. These actuators feature notable advantages, including precise deformation control under electrical stimuli, freedom from Carnot efficiency limitations, and the ability to maintain their actuated state with minimal energy use, akin to the latching state in skeletal muscles. This review extensively examines EC actuators, emphasizing their classification based on diverse material types, driving mechanisms, actuator configurations, and potential applications. It aims to illuminate the complicated driving mechanisms of different categories, uncover their underlying connections, and reveal the interdependencies among materials, mechanisms, and performances. We conduct an in-depth analysis of both conventional and emerging EC actuator materials, casting a forward-looking lens on their trajectories and pinpointing areas ready for innovation and performance enhancement strategies. We also navigate through the challenges and opportunities within the field, including optimizing current materials, exploring new materials, and scaling up production processes. Overall, this review aims to provide a scientifically robust narrative that captures the current state of EC actuators and sets a trajectory for future innovation in this rapidly advancing field.
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Fabrics represent a unique platform for seamlessly integrating electronics into everyday experiences. The advancements in functionalizing fabrics at both the single fibre level and within constructed fabrics have fundamentally altered their utility. The revolution in materials, structures, and functionality at the fibre level enables intimate and imperceptible integration, rapidly transforming fibres and fabrics into next-generation wearable devices and systems. In this review, we explore recent scientific and technological breakthroughs in smart fibre-enabled fabrics. We examine common challenges and bottlenecks in fibre materials, physics, chemistry, fabrication strategies, and applications that shape the future of wearable electronics. We propose a closed-loop smart fibre-enabled fabric ecosystem encompassing proactive sensing, interactive communication, data storage and processing, real-time feedback, and energy storage and harvesting, intended to tackle significant challenges in wearable technology. Finally, we envision computing fabrics as sophisticated wearable platforms with system-level attributes for data management, machine learning, artificial intelligence, and closed-loop intelligent networks.
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Herein, a bioinspired metal-organic framework (MOF) cocrystal produced from the co-assembly of a MOF [Ni3(hexaiminobenzene)2, Ni3(HIB)2] and p-chloranils (CHLs) is reported. Because of the 2D conjugation nature and the formation of persistent anion radicals, this cocrystal shows an excellent photothermal property, and is further used as an absorber in solar-driven interfacial water evaporation. The solar-driven interfacial water evaporation rate (4.04 kg m-2 h-1) is among the best compared with those of previously reported photothermal materials. Molecular dynamics simulation results suggested that the rotating of the CHL molecules relative to the MOF planes tuned the pore size to enable the ultra-fast water transporting, and thus ultra-high water transporting rates (1.11 × 1011 and 3.21 × 1011 H2O s-1 channel-1 at 298.2 and 323.0 K, respectively) for layered cocrystal structures, that are much higher than that of aquaporins (≈1.1 × 1010 H2O s-1 channel-1 at 298.2 K), are observed. The superior solar-driven water evaporation performance is thus attributed to the synergistic effect of the ultra-fast water transporting pores together with the excellent photothermal property of the cocrystal. This research provided a biomimetic strategy of rational design and production of charge transfer cocrystals to modulate their pores and photothermal properties for solar-driven interfacial water evaporation.
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Targeted photodynamic therapy (PDT) offers advantages over nontargeted approaches, including improved selectivity, efficacy, and reduced side effects. This study developed star-shaped glycopolymeric photosensitizers using porphyrin-based initiators via ATRP. Incorporating a porphyrin core gave the polymers fluorescence and ROS generation, while adding fructose improved solubility and targeting capabilities. The photosensitizers had high light absorption, singlet oxygen production, specificity, low dark toxicity, and biocompatibility. The glycopolymers with longer sugar arms and higher density showed better uptake on MCF-7 and MDA-MB-468 cells compared to HeLa cells, indicating enhanced targeting capabilities. Inhibition of endocytosis confirmed the importance of the GLUT5 receptor. The resulting polymers exhibited good cytocompatibility under dark conditions and satisfactory PDT under light irradiation. Interestingly, the polymers containing fructose have a GLUT5-dependent elimination effect on the MCF-7 and MDA-MB-468 cells. The intracellular ROS production followed a similar pattern, indicating that the fructose polymer exhibits specific targeting toward cells with GLUT5 receptors.
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Fotoquimioterapia , Porfirinas , Humanos , Fármacos Fotosensibilizantes/farmacología , Fármacos Fotosensibilizantes/uso terapéutico , Fotoquimioterapia/métodos , Células HeLa , Especies Reactivas de Oxígeno , Porfirinas/farmacología , Polímeros/farmacología , Fructosa/farmacologíaRESUMEN
The emergence of photoinduced energy/electron transfer-reversible addition-fragmentation chain transfer polymerization (PET-RAFT) not only revolutionized the field of photopolymerization but also accelerated the development of porphyrin-based photocatalysts and their analogues. The continual expansion of the monomer family compatible with PET-RAFT polymerization enhances the range of light radiation that can be harnessed, providing increased flexibility in polymerization processes. Furthermore, the versatility of PET-RAFT polymerization extends beyond its inherent capabilities, enabling its integration with various technologies in diverse fields. This integration holds considerable promise for the advancement of biomaterials with satisfactory bioapplications. As researchers delve deeper into the possibilities afforded by PET-RAFT polymerization, the collaborative efforts of individuals from diverse disciplines will prove invaluable in unleashing its full potential. This Review presents a concise introduction to the fundamental principles of PET-RAFT, outlines the progress in photocatalyst development, highlights its primary applications, and offers insights for future advancements in this technique, paving the way for exciting innovations and applications.
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Porfirinas , Humanos , Polimerizacion , Tomografía de Emisión de PositronesRESUMEN
Polyamide 6 (PA6) fiber has the advantages of high strength and good wear resistance. However, it is still challenging to effectively load inorganic antibacterial agents into polymer substrates without antimicrobial activity. In this work, graphene oxide is used as a carrier, which is modified with an aminosilane coupling agent (AEAPTMS) to enhance the compatibility and antimicrobial properties of the inorganic material, as well as to improve its thermal stability in a high-temperature melting environment. Cuprous oxide-loaded aminated grapheme (Cu2O-GO-NH2) is constructed by in situ growth method, and further PA6/Cu2O-GO-NH2 fibers are prepared by in situ polymerization. The composite fiber has excellent washing resistance. After 50 times of washing, its bactericidal rates against Bacillus subtilis and Escherichia coli are 98.85% and 99.99%, respectively. In addition, the enhanced compatibility of Cu2O-GO-NH2 with the PA6 matrix improves the orientation and crystallinity of the composite fibers. Compared with PA6/Cu2O-GO fibers, the fracture strength of PA6/Cu2O-GO-NH2 fibers increases from 3.0 to 4.2 cN/dtex when the addition of Cu2O-GO-NH2 is 0.2 wt%. Chemical modification and in situ concepts help to improve the compatibility of inorganic antimicrobial agents with organic polymers, which can be applied to the development of medical textiles.
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Antibacterianos , Bacillus subtilis , Caprolactama , Cobre , Escherichia coli , Grafito , Pruebas de Sensibilidad Microbiana , Polímeros , Antibacterianos/química , Antibacterianos/farmacología , Antibacterianos/síntesis química , Cobre/química , Escherichia coli/efectos de los fármacos , Bacillus subtilis/efectos de los fármacos , Caprolactama/química , Caprolactama/análogos & derivados , Grafito/química , Polímeros/química , Polímeros/farmacología , Polímeros/síntesis químicaRESUMEN
This study sheds light on the exploration of photoresponsive host-guest systems, highlighting the intricate interplay between confined spaces and photosensitive guest molecules. Conducting nonadiabatic molecular dynamics (NAMD) simulations based on electronic structure calculations for such large systems remains a formidable challenge. By leveraging machine learning (ML) as an accelerator for NAMD simulations, we analytically constructed excited-state potential energy surfaces along relevant collective variables to investigate photoisomerization processes efficiently. Combining the quantum mechanics/molecular mechanics (QM/MM) methodology with ML-based NAMD simulations, we elucidated the reaction pathways and identified the key degrees of freedom as reaction coordinates leading to conical intersections. A machine learning-based nonadiabatic dynamics model has been developed to compare the excited-state dynamics of the guest molecule, benzopyran, in both the gas phase and its behavior within the confined space of cucurbit[5]uril. This comparative analysis was designed to determine the influence of the environment on the photoisomerization rate of the guest molecule. The results underscore the effectiveness of ML models in simulating trajectory evolution in a cost-effective manner. This research offers a practical approach to accelerate NAMD simulations in large-scale systems of photochemical reactions, with potential applications in other host-guest complex systems.
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Room temperature phosphorescence (RTP) materials have garnered significant attention owing to its distinctive optical characteristics and broad range of potential applications. However, the challenge remains in producing RTP materials with more simplicity, versatility, and practicality on a large scale, particularly in achieving chiral signals within a single system. Herein, we show that a straightforward and effective combination of wet spinning and twisting technique enables continuously fabricating RTP fibers with twisting-induced helical chirality. By leveraging the hydrogen bonding interactions between polyvinyl alcohol (PVA) and quinoline derivatives, along with the rigid microenvironment provided by PVA chains, typically, Q-NH2@PVA fiber demonstrates outstanding phosphorescent characteristics with RTP lifetime of 1.08â s and phosphorescence quantum yield of 24.6 %, and the improved tensile strength being 1.7 times than pure PVA fiber (172±5.82 vs 100±5.65â MPa). Impressively, the transformation from RTP to circularly polarized room temperature phosphorescence (CP-RTP) is readily achieved by imparting left- or right-hand helical structure through simply twisting, enabling large-scale production of chiral Q-NH2@PVA fiber with dissymmetry factor of 10-2. Besides, an array of displays and encryption patterns are crafted by weaving or seaming to exemplify the promising applications of these PVA-based fibers with outstanding adaptivity in cutting-edge anti-counterfeiting technology.
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Uncontrollable side reactions at the metal interface have been identified as the root cause of the formation of a fragile solid electrolyte interphase, leading to irreversible sodium loss in sodium metal batteries. Here, we proposed an interface engineering strategy that employed a carboxyl functionalized cellulose separator to provide strong dipole moments and induce the cleavage of P-F bond to construct a SEI rich in NaF. In addition, we employed nuclear magnetic resonance technology confirmed that the separator with strong dipole moments prevented the reduction of organic solvents by attracting electrons, thereby inhibiting the formation of organic oligomers. SEI with high NaF content and few oligomers is smooth and robust, obviously decreasing the interface impedance of the Na anode. The symmetric Na||Na cells, equipped with the functionalized separator, efficiently operated for 1400 hours with a stable 72 mV overpotential at 0.25 mA cm-2, exhibiting low energy barrier and fast ion transport kinetics. The Na||Na3V2(PO4)3 cell also showed stable cycling performance, with the capacity remaining at 94.83% of the initial capacity after 1000 cycles at 1C. The proposed separator could control the formation and composition of SEI, paving the way for the development of long-life sodium metal batteries.
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Sliding-freestanding triboelectric nanogenerators (SF-TENGs) are desirable for application in wearable power sources; however, improving their durability is the primary challenge. Meanwhile, few studies focus on enhancing the service life of tribo-materials, especially from an anti-friction perspective during dry operation. Herein, for the first time, a surface-textured film with self-lubricating property is introduced into the SF-TENG as a tribo-material, which is obtained by the self-assembly of hollow SiO2 microspheres (HSMs) close to a polydimethylsiloxane (PDMS) surface under vacuum conditions. The PDMS/HSMs film with micro-bump topography simultaneously reduces the dynamic coefficient of friction from 1.403 to 0.195 and increases the electrical output of SF-TENG by an order of magnitude. Subsequently, a textured film and self-adapting contact synergized bidirectional rotary TENG (TAB-TENG) is developed, and the superiorities of the soft flat rotator with bidirectional reciprocating rotation are systematically investigated. The obtained TAB-TENG exhibits a remarkable output stability and an outstanding mechanical durability over 350 000 cycles. Furthermore, a smart foot system for stepping energy harvesting and wireless walking states monitoring is realized. This study proposes a pioneering strategy for extending the lifetime of SF-TENGs and advances it toward practical wearable applications.
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The aggregation-caused quenching, premature drug release, and hypoxia-caused resistance of photodynamic therapy (PDT) are challenges in the design and preparation of novel porphyrin-containing photosensitizers. In this work, a series of block copolymers consisting of a hydrophilic glycopolymer block and a porphyrin-containing hydrophobic block were prepared via reversible addition-fragmentation chain transfer polymerization. The polymeric photosensitizers generate singlet oxygen and excellent PDT against HepG2, which can be strengthened by the addition of cholic acid. To combine with chemotherapy, doxorubicin (Dox) was successfully loaded into copolymers, which were observed to be more phototoxic, indicating that the therapeutic benefit of the synergistic effect of PDT and chemotherapy is better than their simple combination. The sugar-cell-specific interaction of galactose-containing photosensitizers results in a stronger mean fluorescent index (MFI) intracellular uptake in HepG2 cells in vitro compared to L929 and MCF-7 cells. These polymeric nanoplatforms present a versatile and effective avenue for developing synergistic therapy for cancer treatment.
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Nanopartículas , Fotoquimioterapia , Porfirinas , Humanos , Fármacos Fotosensibilizantes/química , Fotoquimioterapia/métodos , Ácido Cólico/farmacología , Nanopartículas/química , Doxorrubicina/farmacología , Doxorrubicina/química , Polímeros/farmacología , Polímeros/química , Porfirinas/química , Línea Celular TumoralRESUMEN
Two triplet excitons are generated through an ultrafast photophysical process, namely singlet fission (SF), providing a solution for efficient solar energy usage. In this work, we provide an effective guideline for designing SF materials by adjusting the planarity in cyclopentadithiophene (CPDT) derivatives. A practical strategy is proposed for tuning the quinoidal-biradical resonance structures by varying the electron push-pull groups of CPDTs for SF. The localized, delocalized, and intermediate charge-transfer excited configurations are predicted in the singlet excited state via computational simulations, which is further confirmed by ultrafast spectroscopy. Deduced from the potential energy surfaces in the low-lying excited states and transient absorption, the delocalized excited state is formed in 2.1 ps via postulated intramolecular SF in a polar solvent, followed by the ultrafast formation of the free triplet state with a lifetime of 6.8 ps. In comparison with different cross-conjugated chromophores, it is found that the increase in the charge separation could enhance the triplet-pair generation for iSF. We expect that by introducing symmetry-breaking modifications in the electronic configurations and adjusting the separation between the push-pull groups of CPDTs, it should be possible to prolong the duration of the free triplet state by preventing recombination within the triplet-pair excited configuration.
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The combination of ring-closing metathesis with betulin enables the design and synthesis of novel biomolecules representing a library of triterpenoid derivatives for potential pharmacological research. In this work, cyclic olefin betulin derivatives were attempted to be prepared by the combination of ring-closing metathesis with betulin. Dicyclohexyl carbodiimide coupling reaction allowed the transformation of betulin into two types of linear olefin derivatives that have different methylene spacer lengths between the olefin and ester groups. Subsequently, betulin-based cycloolefins were synthesized by ring-closing metathesis using Grubbs first-generation catalyst. The influence of different parameters including solvents, temperature, catalysts, and catalyst loading on ring-closing metathesis was investigated. Cytotoxicity results indicated that these betulin-based olefin derivatives, derived from renewable bioresources, have potential applications in the biomedical field.
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Rutenio , Ciclización , Alquenos , CatálisisRESUMEN
OBJECTIVE: To investigate the accuracy of ultrasonic diagnosis using the tele-ultrasound robot in Leishen Shan Hospital. METHOD: Twenty-two patients with novel coronavirus pneumonia from Leishen Shan Hospital voluntarily participated in this study. Their thyroids, neck vessels, hepatobiliaries and kidneys were scanned by both a tele-ultrasound robot manufactured by Imabot Co., Ltd, Wuhan and conventional method. The ultrasound diagnosis of each patient was compared, and the ultrasound images obtained by the two methods were mixed together and double-blindly diagnosed by an experienced ultrasound radiologist. RESULTS: There were 44 positive lesions in 110 sites of 22 patients. Of which the two methods, 40 positive lesions were detected by the robotic method with 4 lesions missed (2 small polyps of gallbladder, 1 small hemangioma of liver and 1 small cyst of kidney) and 1 lesion misdiagnosed (normal carotid artery was misdiagnosed as carotid atherosclerotic plaque); 44 positive lesions were detected by conventional method with 1 small cyst of the liver was missed. There was no statistically significant difference in the accuracy rate between the robotic method and the conventional method using the chi-square test of the four-grid data (P>.05). CONCLUSION: The application of tele-ultrasound robot meets the standard of patient care during the pandemic. The method is feasible to provide adequate ultrasound information to diagnose common abdominal, vascular, superficial organ pathologies in patients with COVID-19 with acceptable accuracy compared with a conventional ultrasound scan.
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COVID-19 , Quistes , Robótica , Humanos , Pandemias , Robótica/métodos , Estudios de Factibilidad , Ultrasonografía/métodosRESUMEN
The rational creation of two-component conjugated polymer systems with high levels of phase purity in each component is challenging but crucial for realizing printed soft-matter electronics. Here, we report a mixed-flow microfluidic printing (MFMP) approach for two-component π-polymer systems that significantly elevates phase purity in bulk-heterojunction solar cells and thin-film transistors. MFMP integrates laminar and extensional flows using a specially microstructured shear blade, designed with fluid flow simulation tools to tune the flow patterns and induce shear, stretch, and pushout effects. This optimizes polymer conformation and semiconducting blend order as assessed by atomic force microscopy (AFM), transmission electron microscopy (TEM), grazing incidence wide-angle X-ray scattering (GIWAXS), resonant soft X-ray scattering (R-SoXS), photovoltaic response, and field effect mobility. For printed all-polymer (poly[(5,6-difluoro-2-octyl-2H-benzotriazole-4,7-diyl)-2,5-thiophenediyl[4,8-bis[5-(2-hexyldecyl)-2-thienyl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl]-2,5-thiophenediyl]) [J51]:(poly{[N,N'-bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)}) [N2200]) solar cells, this approach enhances short-circuit currents and fill factors, with power conversion efficiency increasing from 5.20% for conventional blade coating to 7.80% for MFMP. Moreover, the performance of mixed polymer ambipolar [poly(3-hexylthiophene-2,5-diyl) (P3HT):N2200] and semiconducting:insulating polymer unipolar (N2200:polystyrene) transistors is similarly enhanced, underscoring versatility for two-component π-polymer systems. Mixed-flow designs offer modalities for achieving high-performance organic optoelectronics via innovative printing methodologies.
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A nitrogen-doped carbon bubble-carbon nanotube@red phosphorus (N-CBCNT@rP) network composite is fabricated, featuring an rP film embedded in a highly N-doped CBCNT network with hierarchical pores of different sizes and interior void spaces. Highly N-doped CBCNT with an optimized structure is utilized to achieve an ultrahigh rP content of 53 wt% in the N-CBCNT@rP composite by the NP bond, which shows a record rP content for rP-carbon composites by the vaporization-condensation process. When tested as an anode for lithium-ion batteries, the N-CBCNT@rP composite exhibits an ultrahigh initial Coulombic efficiency of 87.5%, high specific capacity, outstanding rate performance, and superior cycling stability at a high current density (capacity decay of 0.011% per cycle over 1500 cycles at 5 A g-1 ), which is the lowest capacity fading rate of those previously reported for rP-based electrodes. The superior lithium-ion storage performance of the N-CBCNT@rP composite electrode is primarily attributed to its structure. The 3D hierarchical conducting network of the N-CBCNT@rP composite with abundant N-P bonds endows the entire electrode with maximized conductivity for superior ion and electron transfer kinetics. Moreover, N-CBCNT networks with hierarchical pores of different sizes can fix the location of rP, prevent agglomeration, and avoid volume expansion of rP.
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Mesoscopic aggregate is important to transfer or even amplify the molecular information in macroscopic materials. As an important branch of aggregate science, aggregation-induced emissive luminogens (AIEgens) often show slight or even no emission in solutions but exhibit bright emission when they aggregate, which open a new avenue for the practical applications. Due to the flexible and rotor structure of AIEgens, the aggregate structure of AIEgens is highly sensitive to the surrounding microenvironment, resulting in adjustable optical properties. Fibers integrated of a multiplicity of functional components are ideal carriers to control the aggregation processes, further assembly of fibers produces large-scale fabrics with amplified functions and practical values. In this Concept article, we focus on the latest advances on the synergy between "AIE+Fiber" for the boosted performance that beyond AIE, and their applications are presented and abstracted out to stimulate new ideas for developing "AIE+Fiber" systems.