静电纺丝中空纳米纤维在催化领域的应用

更大的比表面积、更丰富的界面组成及更高效的传质路径是构筑多元催化体系,实现催化剂效率提升的关键.中空纳米纤维具有的多元空腔结构赋予其比表面积和界面组成上广阔的调变空间,使其成为制备高效异相催化剂的理想平台.静电纺丝技术的发展为中空纳米纤维的可控制备提供了更简易高效的方法,促进了中空纳米纤维的结构创新和应用扩展.本文从构筑策略、结构特点及结构与性能的对应关系3个角度总结了基于静电纺丝法制备的不同组成和形态的中空纳米纤维材料在催化领域(包括光催化、电催化、热催化)应用中的独特优势.首先展示了创新的静电纺丝方法结合后续工艺制备的中空纳米纤维的不同结构形态,然后梳理了基于中空纳米纤维构筑高效催化剂的研究进展,最后展望了中空纳米纤维在催化领域应用的未来发展趋势,以期为高效异相催化剂的设计提供有益的参考.     

Synthetic chemoselective rewiring of cell surfaces: generation of three-dimensional tissue structures

Proper cell-cell communication through physical contact is crucial for a range of fundamental biological processes including, cell proliferation, migration, differentiation, and apoptosis and for the correct function of organs and other multicellular tissues. The spatial and temporal arrangements of these cellular interactions in vivo are dynamic and lead to higher-order function that is extremely difficult to recapitulate in vitro. The development of three-dimensional (3D), in vitro model systems to investigate these complex, in vivo interconnectivities would generate novel methods to study the biochemical signaling of these processes, as well as provide platforms for tissue engineering technologies. Herein, we develop and employ a strategy to induce specific and stable cell-cell contacts in 3D through chemoselective cell-surface engineering based on liposome delivery and fusion to display bio-orthogonal functional groups from cell membranes. This strategy uses liposome fusion for the delivery of ketone or oxyamine groups to different populations of cells for subsequent cell assembly via oxime ligation. We demonstrate how this method can be used for several applications including, the delivery of reagents to cells for fluorescent labeling and cell-surface engineering, the formation of small, 3D spheroid cell assemblies, and the generation of large and dense, 3D multilayered tissue-like structures for tissue engineering applications.     

Compartmentalization within Nanofibers of Double-Decker Phthalocyanine Induces High-Performance Sensing in both Aqueous Solution and the Gas Phase

The functionalization of natural 1D architectures is dependent on hierarchically inner nanostructures. However, the artificial supramolecular nanofibers or nanotubes were rarely developed with complex inner structures. Inspired by a biomimetic strategy, single-molecule-diameter nanofibers of double-decker phthalocyanine (EuPc2) with compartmentalized internal space and fantastic electrochemical features were developed upon air/water interfacial assembly with poly-l -lysine. EuPc2/poly-l -lysine nanofibers can be electrochemical sensors both in water and the gas phase and have the best analytical performances for nitrite among all the porphyrins or phthalocyanines monomers and assemblies. Imbedding nitrite in compartments not only promotes the sensing but also changes the supramolecular chirality of nanofibers, and the morphological-dependent sensing properties of EuPc2 assemblies in water are different from that in the gas phase. These results suggest the unprecedented properties for diverse applications of artificial 1D architectures containing complex inner nanostructures.     

Nanocomposites and macroscopic materials: assembly of chemically modified graphene sheets

Self-assembly of chemically modified graphenes (CMGs), including graphene oxide (GO), reduced graphene oxide (RGO) and their derivatives, has emerged as one of the most appealing strategies to develop unprecedented graphene-based functional materials. With the assistance of various non-covalent forces such as hydrogen bonding, ionic, amphiphilic and π-π interactions, CMGs decorated with multiple functional groups are favorable for assembly with different organic and inorganic components which can result in hierarchical composites possessing unique structures and functions. In this review, we will summarize the state-of-the-art self-assembly strategies that have been established to construct CMG based nanomaterials, including nanoparticles, nanospheres, nanofibers, nanorods, nanosheets, and macroscopic thin films, fibers and porous networks. The driving forces involved in the self-assembly process will be elucidated in the context. Further, we will also highlight several representative examples of applications regarding the self-assembled CMG based materials.     

Morphology-Dependent Peroxidase Mimicking Enzyme Activity of Copper Metal-Organic Polyhedra Assemblies

The morphology of nanomaterials (geometric shape and dimension) play a significant role in its various physical and chemical properties. Thus, it is essential to link morphology with performance in specific applications. For this purpose, the morphology of copper metal–organic polyhedra (Cu-MOP) can be modulated through distinct assembly process, which facilitates the exploration of the relationship between morphology and catalytic performance. In this work, the assemblies of Cu-MOP with three different morphologies (nanorods, nanofibers and nanosheets) were facilely prepared by the variation of solvent mixture of N, N-dimethylformamide (DMF) and methanol, revealed the important role of the interaction between the surface group and the solvent on the morphology of these assemblies. Cu-MOP nanofibers exhibited the highest mimetic peroxidase enzyme activity over the Cu-MOP nanosheets and nanorods, which have been utilized in the detection of glucose. Cu-MOPs assemblies with tunable morphology accompanied with adjustable mimic peroxidase activity, had great potential applications in the field of bioanalytical chemistry and biomedicals.     

高性能磁性纳米粒子的有机相制备与生物应用的研究进展

磁性纳米粒子(MNPs)的合成开发在基础科学研究和技术应用方面得到了深入的发展。与大块的磁性材料不同,MNPs展现出了独特的磁性,并且可以通过系统的纳米尺寸工程调控它们的性能。本文首先简要介绍了MNPs的基本特征,总结了不同MNPs的制备方法,包括金属、合金、金属氧化物和多功能的MNPs;重点关注了可精确控制MNPs尺寸、形状、组成和结构的有机相合成方法;最后讨论了这些MNPs在生物方面的应用。     

Mammalian cell viability in electrospun composite nanofiber structures

Incorporation of mammalian cells into nanofibers (cell electrospinning) and multilayered cell-nanofiber structures (cell layering) via electrospinning are promising techniques for tissue engineering applications. We investigate the viability of 3T3-L1 mouse fibroblasts after incorporation into poly(vinyl alcohol) nanofibers and multilayering with poly(caprolactone) nanofibers and analyze the possible factors that affect cell viability. We observe that cells do not survive cell electrospinning but survive cell layering. Assessing the factors involved in cell electrospinning, we find that dehydration and fiber stretching are the main causes of cell death. In cell layering, the choice of solvent is critical, as residual solvent in the electrospun fibers could be detrimental to the cells.     

Multivalent nanofibers of a controlled length: regulation of bacterial cell agglutination

Control of the size and shape of molecular assemblies on the nanometer scale in aqueous solutions is very important for the regulation of biological functions. Among the well-defined supramolecular structures of organic amphiphiles, one-dimensional nanofibers have attracted much attention because of their potential applications in biocompatible materials. Although much progress has been made in the field of self-assembled nanofibers, the ability to control the fiber length remains limited. The approach for control of the fiber length presented herein overcomes this limitation through the coassembly of amphiphilic rod-coil molecules in which the crystallinity of the aromatic segment can be regulated by π-π stacking interactions. The introduction of carbohydrate segments into the fiber exterior endows the nanofibers with the ability to adhere to bacterial cells. Notably, the fiber length systematically regulates the agglutination and proliferation of bacterial cells exposed to these fibers.     

A review on electrospun nanofibers for multiple biomedical applications

Electrospinning is a well-known technique since 1544 to fabricate nanofibers using different materials like polymers, metals oxides, proteins, and many more. In recent years, electrospinning has become the most popular technique for manufacturing nanofibers due to its ease of use and economic viability. Nanofibers have remarkable properties like high surface-to-volume ratio, variable pore size distribution (10–100 nm), high porosity, low density, and are suitable for surface functionalization. Therefore, electrospun nanofibers have been utilized for numerous applications in the pharmaceutical and biomedical field like tissue engineering, scaffolds, grafts, drug delivery, and so on. In this review article, we will be focusing on the versatility, current scenario, and future endeavors of electrospun nanofibers for various biomedical applications. This review discusses the properties of nanofibers, the background of the electrospinning technique, and its emergence in chronological order. It also covers the various types of electrospinning methods and their mechanism, further elaborating the factors affecting the properties of nanofibers, and applications in tissue engineering, drug delivery, nanofibers as biosensor, skin cancer treatment, and magnetic nanofibers.     

Recent progress in MXenes incorporated into electrospun nanofibers for biomedical application: Study focusing from 2017 to 2022

After discovering a new class of two-dimensional (2D) material, i.e., MXene, a further new scope, came into existence for researchers. Due to their remarkable physical, chemical, and biological properties, MXenes find their role in almost every research discipline. They have been used in biosensors, bioimaging, tissue engineering, drug delivery systems, and other areas. The MXenes can be functionalized with a wide range of atoms/molecules, making them diverse materials. Therefore, the potential of using MXenes in nanofibers can be much more than expected. In this review, we will understand the structure, synthesis, and general properties of MXenes. We will explain using MXenes while encasing them into nanofibers, providing their specific properties. For instance, MXenes-incorporated nanofibers are used in biomedical applications, including soft and hard-tissue engineering and delivery of antimicrobials. Furthermore, MXenes, when incorporated into nanofibers, are used in promoting cellular differentiation, wound healing, and neural tissue restoration, which are briefly discussed in this communication.     

基于静电纺丝技术的多级结构聚合物纳米纤维复合材料的研究进展

静电纺丝技术是目前制备纳米纤维最重要的方法之一,以其制备的纤维具有直径可控、比表面积大、孔隙率高等优点,因而被广泛应用于过滤、催化、传感器及生物医学等众多领域.以静电纺丝纤维为模板可进一步构建多级结构的功能性聚合物纳米纤维复合材料,拓宽其应用范围.本文着重概述了近年来基于静电纺丝技术的简单共混型、核壳结构及多级结构的聚合物纳米纤维复合材料的制备、结构及性能,并展望了其应用研究前景.     

静电纺纳米纤维基超级电容器无粘合剂电极材料的研究进展

对高性能超级电容器不断增长的需求促进了无粘合剂电极材料的快速发展。静电纺纳米纤维由于具有良好的柔性、大比表面积、高孔隙率、容易制备等优点引起了研究者们的强烈关注。本文综述了静电纺纳米纤维基无粘合剂电极材料在超级电容器领域的研究进展,阐述了不同材料的设计制备过程和提升电化学性能的诸多方法,并指明了静电纺纳米纤维基超级电容器无粘合剂电极材料的发展机遇与挑战,为性能优异的无粘合剂超级电容器电极材料的进一步开发与应用拓宽了思路。     

Pillararene‐Based Assemblies: Design Principle,Preparation and Applications

In this review, we highlight recent advancements on pillararene‐based assemblies. The driving forces for the formation of the pillararene‐based assemblies are discussed first. The host–guest interactions are deemed as not only general strategy for constructing assemblies but also essential components for preventing the assemblies from the dissociation. Solvent effect is also important in the assembling process, since it could influence the host–guest interactions and provide solvophobic effect on pillararenes for the assembly. Then, several pillararene‐based assembly architectures are introduced, including pillararene‐based interlocked structures, such as (poly)pseudorotaxanes, (poly)rotaxanes, and daisy chains, classified by their topological structures and synthetic strategy. The morphologies of the supramolecular assemblies are divided into several types, for example, nanospheres, nanotubes and supramolecular polymers. Furthermore, the functions and potential applications are summarized accompanied with related assembly structures. The review not only provides fundamental findings, but also foresights future research directions in the research area of pillararene‐based assemblies.     

Surface modification of natural cellulose substances:toward functional materials and applications

Combining various synthetic chemical processes and biological assemblies provides a promising strategy for the design and fabrication of functional materials with tailored structures and properties.The unique multilevel structures and morphologies of natural cellulose substances such as ordinary commercial laboratory filter paper make them ideal platforms for the self-assemblies of various functional guest molecules that are to be deposited on the surfaces of their fine structures,and the resulting composite matters show significant potentials for various applications.The surface sol-gel process was employed to deposit ultrathin metal-oxide(e.g.,titania and zirconia)gel films to coat the cellulose nanofibers in bulk filter papers;thereafter,monolayers of specific guest substrates were immobilized onto the surfaces of the metal-oxide gel films.Highly selective,sensitive,and reversible chemosensors based on the surface modification of filter paper were obtained toward the fluorescence and colorimetric detection of various analytes such as heavy-metal ions,inorganic anions,amino acids,and gases.Cellulosebased composite materials with superhydrophobic,antibacterial,or luminescent properties were fabricated by self-assembly approaches toward practical applications.     

Fabrication and characterization of polycrystalline WO3 nanofibers and their application for ammonia sensing

We describe the fabrication and characterization of tungsten oxide nanofibers using the electrospinning technique and sol-gel chemistry. Tungsten isopropoxide sol-gel precursor was incorporated into poly(vinyl acetate)(PVAc)/DMF solutions and electrospun to form composite nanofibers. The as-spun composite nanofibers were subsequently calcinated to obtain pure tungsten oxide nanofibers with controllable diameters of around 100 nm. SEM and TEM were utilized to investigate the structure and morphology of tungsten oxide nanofibers before and after calcination. The relationship between solution concentration and ceramic nanofiber morphology has been studied. A synchrotron-based in situ XRD method was employed to study the dynamic structure evolution of the tungsten oxide nanofibers during the calcination process. It has been shown that the as-prepared tungsten oxide ceramic nanofibers have a quick response to ammonia with various concentrations, suggesting potential applications of the electrospun tungsten oxide nanofibers as a sensor material for gas detection.     

Characterization of 3D DNA Assemblies Using Cryogenic Electron Microscopy

DNA nanotechnology utilizes DNA double strands as building units for self-assembly of DNA nanostructures.The specific base-pairing interaction between DNA molecules is the basis of these assemblies.After decades of development,this technology has been able to construct complex and programmable structures.With the increase in delicate nature and complexity of the synthesized nanostructures,a characterization technology that can observe these structures in three dimensions has become necessary,and developing such a technology is considerably challenging.DNA assemblies have been studied using different characterization methods including atomic force microscopy(AFM),scanning electron microscopy(SEM),and transmission electron microscopy(TEM).However,the three-dimensional(3D)DNA assemblies always collapse locally due to the dehydration during the drying process.Cryogenic electron microscopy(cryo-EM)can overcome the challenge by maintaining three-dimensional morphologies of the cryogenic samples and reconstruct the 3D models from cryogenic samples accordingly by collecting thousands of two-dimensional(2D)projection images,which can restore their original morphologies in solution.Here,we have reviewed several typical cases of 3D DNA-assemblies and highlighted the applications of cryo-EM in characterization of these assemblies.By comparing with some other characterization methods,we have shown how cryo-EM promoted the development of structural characterization in the field of DNA nanotechnology.     

Highly porous core-shell polymeric fiber network

Core-shell nanofibers are of great interest in the field of tissue engineering and cell biology. We fabricated porous core-shell fiber networks using an electrospinning system with a water-immersed collector. We hypothesized that the phase separation and solvent evaporation process would enable the control of the pore formation on the core-shell fiber networks. To synthesize porous core-shell fiber networks, we used polycaprolactone (PCL) and gelatin. Quantitative analysis showed that the sizes of gelatin-PCL core-shell nanofibers increased with PCL concentrations. We also observed that the shapes of the pores created on the PCL fiber networks were elongated, whereas the gelatin-PCL core-shell fiber networks had circular pores. The surface areas of porous nanofibers were larger than those of the nonporous nanofibers due to the highly volatile solvent and phase separation process. The porous core-shell fiber network was also used as a matrix to culture various cell types, such as embryonic stem cells, breast cancer cells, and fibroblast cells. Therefore, this porous core-shell polymeric fiber network could be a potentially powerful tool for tissue engineering and biological applications.     

Emerging advances in plasmonic nanoassemblies for biosensing and cell imaging

Integrating discrete plasmonic nanoparticles into assemblies can induce plasmonic coupling that produces collective plasmonic properties, which are not available for single nanoparticles. Theoretical analysis revealed that plasmonic coupling derived from assemblies could produce stronger electromagnetic field enhancement effects. Thus, plasmonic assemblies enable better performance in plasmon-based applications,such as enhanced fluorescence and Raman effects. This makes them hold great potential...     

Flexible generation of gradient electrospinning nanofibers using a microfluidic assisted approach

The nanofiber surface modified with physical or chemical gradients is very useful in a wide range of areas including tissue engineering, regenerative medicine, drug screening, and biomaterial chemistry. In this work, we presented a novel and straightforward microfluidic assisted approach to produce electrospinning nanofibers containing gradients in different compositions, nanoparticles and biomolecule concentrations. The series of gradient nanofibers were mainly produced by using a two inlet microfluidic device in combination with an electrospinning nozzle on a 3-D controllable platform, which exhibited different functions and properties. The controlled nanofibers with incorporated biomolecule gradient were used for guiding the spatial differentiation in mesenchymal stem cells (MSCs). This established approach is very simple, and flexible to operate, which might find enormous potential for biology and tissue engineering applications.     

An optimistic approach “from hydrophobic to super hydrophilic nanofibers” for enhanced absorption properties

Water holding capacity becomes essential for hygiene applications including baby diapers. Microfibers of hydrophilic polymers have been useful source for such applications. While, super hydrophilic and stable nanofibers incorporation with functional antibacterial agent are essential to get higher absorption of water along with antimicrobial activity against harmful bacteria. In current work, hydrophobic polymeric nanofibers are transformed to super hydrophilic nanofibers by addition of copper (II) oxide (CuO hereafter) nanoparticles. CuO nanoparticles provided two distinctive properties to existing nanofibers. Firstly, nanofibers surface area was significantly increased, and secondly copper (II) oxide itself is hydrophilic material which imparted hydrophilicity to base polymer. Polyacrylonitrile, crosslinked Polyvinyl Alcohol, and PICT were selected as super hydrophobic polymeric nanofibers. Copper II oxide nanoparticles (same concentration) were added in all polymer solution and electrospun. Surface, morphological, and hydrophilic properties were characterized and it was concluded that copper II oxide is suitable for transforming hydrophobic nanofibers to super hydrophilic nanofibers. Water holding capacity (WHC) was also improved for all prepared nanofiber mats. WHC for PVA/CuO, PAN/CuO, and PICT/CuO were recorded an average of 23 g/g, 21 g/g, and 18 g/g respectively. Combining all useful results from possible characterization of nanofiber mats, it is expected that CuO nanoparticles loaded nanofibers will have potential application as antibacterial, sustainable, and stable replacement of hygiene products.