Modulating the Mechanical Performance of Macroscale Fibers through Shear‐Induced Alignment and Assembly of Protein Nanofibrils

Protein‐based fibers are used by nature as high‐performance materials in a wide range of applications, including providing structural support, creating thermal insulation, and generating underwater adhesives. Such fibers are commonly generated through a hierarchical self‐assembly process, where the molecular building blocks are geometrically confined and aligned along the fiber axis to provide a high level of structural robustness. Here, this approach is mimicked by using a microfluidic spinning method to enable precise control over multiscale order during the assembly process of nanoscale protein nanofibrils into micro‐ and macroscale fibers. By varying the flow rates on chip, the degree of nanofibril alignment can be tuned, leading to an orientation index comparable to that of native silk. It is found that the Young's modulus of the resulting fibers increases with an increasing level of nanoscale alignment of the building blocks, suggesting that the mechanical properties of macroscopic fibers can be controlled through varying the level of ordering of the nanoscale building blocks. Capitalizing on strategies evolved by nature, the fabrication method allows for the controlled formation of macroscopic fibers and offers the potential to be applied for the generation of further novel bioinspired materials.     

Microfluidic Platforms toward Rational Material Fabrication for Biomedical Applications

The emergence of micro/nanomaterials in recent decades has brought promising alternative approaches in various biomedicine‐related fields such as pharmaceutics, diagnostics, and therapeutics. These micro/nanomaterials for specific biomedical applications shall possess tailored properties and functionalities that are closely correlated to their geometries, structures, and compositions, therefore placing extremely high demands for manufacturing techniques. Owing to the superior capabilities in manipulating fluids and droplets at microscale, microfluidics has offered robust and versatile platform technologies enabling rational design and fabrication of micro/nanomaterials with precisely controlled geometries, structures and compositions in high throughput manners, making them excellent candidates for a variety of biomedical applications. This review briefly summarizes the progress of microfluidics in the fabrication of various micro/nanomaterials ranging from 0D (particles), 1D (fibers) to 2D/3D (film and bulk materials) materials with controllable geometries, structures, and compositions. The applications of these microfluidic‐based materials in the fields of diagnostics, drug delivery, organs‐on‐chips, tissue engineering, and stimuli‐responsive biodevices are introduced. Finally, an outlook is discussed on the future direction of microfluidic platforms for generating materials with superior properties and on‐demand functionalities. The integration of new materials and techniques with microfluidics will pave new avenues for preparing advanced micro/nanomaterials with enhanced performance for biomedical applications.     

Recombinant Silk Fiber Properties Correlate to Prefibrillar Self‐Assembly

Spider silks are desirable materials with mechanical properties superior to most synthetic materials coupled with biodegradability and biocompatibility. In order to replicate natural silk properties using recombinant spider silk proteins (spidroins) and wet‐spinning methods, the focus to date has typically been on modifying protein sequence, protein size, and spinning conditions. Here, an alternative approach is demonstrated. Namely, using the same ≈57 kDa recombinant aciniform silk protein with a consistent wet‐spinning protocol, fiber mechanical properties are shown to significantly differ as a function of the solvent used to dissolve the protein at high concentration (the “spinning dope” solution). A fluorinated acid/alcohol/water dope leads to drastic improvement in fibrillar extensibility and, correspondingly, toughness compared to fibers produced using a previously developed fluorinated alcohol/water dope. To understand the underlying cause for these mechanical differences, morphology and structure of the two classes of silk fiber are compared, with features tracing back to dope‐state protein structuring and preassembly. Specifically, distinct classes of spidroin nanoparticles appear to form in each dope prior to fiber spinning and these preassembled states are, in turn, linked to fiber morphology, structure, and mechanical properties. Tailoring of dope‐state spidroin nanoparticle assembly, thus, appears a promising strategy to modulate fibrillar silk properties.     

Advanced Multimaterial Electronic and Optoelectronic Fibers and Textiles

The ability to integrate complex electronic and optoelectronic functionalities within soft and thin fibers is one of today's key advanced manufacturing challenges. Multifunctional and connected fiber devices will be at the heart of the development of smart textiles and wearable devices. These devices also offer novel opportunities for surgical probes and tools, robotics and prostheses, communication systems, and portable energy harvesters. Among the various fiber‐processing methods, the preform‐to‐fiber thermal drawing technique is a very promising process that is used to fabricate multimaterial fibers with complex architectures at micro‐ and nanoscale feature sizes. Recently, a series of scientific and technological breakthroughs have significantly advanced the field of multimaterial fibers, allowing a wider range of functionalities, better performance, and novel applications. Here, these breakthroughs, in the fundamental understanding of the fluid dynamics, rheology, and tailoring of materials microstructures at play in the thermal drawing process, are presented and critically discussed. The impact of these advances on the research landscape in this field and how they offer significant new opportunities for this rapidly growing scientific and technological platform are also discussed.     

Micro‐/Nanofluidics for Liquid‐Mediated Patterning of Hybrid‐Scale Material Structures

Various materials are fabricated to form specific structures/patterns at the micro‐/nanoscale, which exhibit additional functions and performance. Recent liquid‐mediated fabrication methods utilizing bottom‐up approaches benefit from micro‐/nanofluidic technologies that provide a high controllability for manipulating fluids containing various solutes, suspensions, and building blocks at the microscale and/or nanoscale. Here, the state‐of‐the‐art micro‐/nanofluidic approaches are discussed, which facilitate the liquid‐mediated patterning of various hybrid‐scale material structures, thereby showing many additional advantages in cost, labor, resolution, and throughput. Such systems are categorized here according to three representative forms defined by the degree of the free‐fluid–fluid interface: free, semiconfined, and fully confined forms. The micro‐/nanofluidic methods for each form are discussed, followed by recent examples of their applications. To close, the remaining issues and potential applications are summarized.     

2D Crystal–Based Fibers: Status and Challenges

2D crystals are emerging new materials in multidisciplinary fields including condensed state physics, electronics, energy, environmental engineering, and biomedicine. To employ 2D crystals for practical applications, these nanoscale crystals need to be processed into macroscale materials, such as suspensions, fibers, films, and 3D macrostructures. Among these macromaterials, fibers are flexible, knittable, and easy to use, which can fully reflect the advantages of the structure and properties of 2D crystals. Therefore, the fabrication and application of 2D crystal–based fibers is of great importance for expanding the impact of 2D crystals. In this Review, 2D crystals that are successfully prepared are overviewed based on their composition of elements. Subsequently, methods for preparing 2D crystals, 2D crystals dispersions, and 2D crystal–based fibers are systematically introduced. Then, the applications of 2D crystal–based fibers, such as flexible electronic devices, high‐efficiency catalysis, and adsorption, are also discussed. Finally, the status‐of‐quo, perspectives, and future challenges of 2D crystal–based fibers are summarized. This Review provides directions and guidelines for developing new 2D crystal–based fibers and exploring their potentials in the fields of smart wearable devices.     

聚乳酸纤维制备的研究进展

聚乳酸纤维是可生物降解的新型绿色纤维,它可由常见的纤维成型加工工艺--溶液纺丝和熔融纺丝制得.从原料预处理、工艺过程和影响熔纺纤维结构和性能的因素三方面详细地综述了适合工业化生产的熔融纺丝工艺,并简单介绍了在医药领域应用前景广阔的静电纺丝制备聚乳酸超细纤维的研究现状.     

Electrospun nanofibrous materials for tissue engineering and drug delivery

Abstract

The electrospinning technique, which was invented about 100 years ago, has attracted more attention in recent years due to its possible biomedical applications. Electrospun fibers with high surface area to volume ratio and structures mimicking extracellular matrix (ECM) have shown great potential in tissue engineering and drug delivery. In order to develop electrospun fibers for these applications, different biocompatible materials have been used to fabricate fibers with different structures and morphologies, such as single fibers with different composition and structures (blending and core-shell composite fibers) and fiber assemblies (fiber bundles, membranes and scaffolds). This review summarizes the electrospinning techniques which control the composition and structures of the nanofibrous materials. It also outlines possible applications of these fibrous materials in skin, blood vessels, nervous system and bone tissue engineering, as well as in drug delivery.     

Highly Adsorptive,MOF‐Functionalized Nonwoven Fiber Mats for Hazardous Gas Capture Enabled by Atomic Layer Deposition

While metal‐organic frameworks (MOFs) show great potential for gas adsorption and storage, their powder form limits deployment opportunities. Integration of MOFs on polymeric fibrous scaffolds will enable new applications in gas adsorption, membrane separation, catalysis, and toxic gas sensing. Here, we demonstrate a new synthesis route for growing MOFs on fibrous materials that achieves high MOF loadings, large surface areas and high adsorptive capacities. We find that a nanoscale coating of Al₂O₃ formed by atomic layer deposition (ALD) on the surface of nonwoven fiber mats facilitates nucleation of MOFs on the fibers throughout the mat. Functionality of MOFs is fully maintained after integration, and MOF crystals are well attached to the fibers. Breakthrough tests for HKUST‐1 MOFs [Cu₃(BTC)₂] on ALD‐coated polypropylene fibers reveal NH₃ dynamic loadings up to 5.93 ± 0.20 mol/kg_(MOF+fiber). Most importantly, this synthetic approach is generally applicable to a wide range of polymer fibers (e.g., PP, PET, cotton) and MOFs (e.g., HKUST‐1, MOF‐74, and UiO‐66).     

Understanding the Mechanical and Conductive Properties of Carbon Nanotube Fibers for Smart Electronics

The development of fiber-based smart electronics has provoked increasing demand for high-performance and multifunctional fiber materials. Carbon nanotube (CNT) fibers, the 1D macroassembly of CNTs, have extensively been utilized to construct wearable electronics due to their unique integration of high porosity/surface area, desirable mechanical/physical properties, and extraordinary structural flexibility, as well as their novel corrosion/oxidation resistivity. To take full advantage of CNT fibers, it is essential to understand their mechanical and conductive properties. Herein, the recent progress regarding the intrinsic structure–property relationship of CNT fibers, as well as the strategies of enhancing their mechanical and conductive properties are briefly summarized, providing helpful guidance for scouting ideally structured CNT fibers for specific flexible electronic applications.     

基于溶液喷射法制备顺丁橡胶纤维的结构与性能

采用溶液喷射法探索制备顺丁橡胶纤维的可行性,并对初生顺丁橡胶纤维进行紫外交联,探究了纺丝液浓度和交联剂浓度对纤维形貌和直径的影响。结果表明未交联的顺丁橡胶纤维无法保持圆形纤维形态,纤维较粗且串珠很多,其最佳纺丝液浓度为6%(质量分数);紫外交联能够显著改善顺丁橡胶纤维形貌,交联后的顺丁橡胶纤维细度较细,呈现出光滑的圆柱形,纤维间粘连情况减少,且当交联剂浓度为12%(质量分数)时,顺丁橡胶纤维最细,其平均直径为2.41μm;交联后的纤维在四氢呋喃溶液中浸泡24 h,形态保持良好;顺丁橡胶纤维的交联密度随交联剂含量的增加而增大。     

Electrospun fibers for tissue engineering, drug delivery, and wound dressing

Electrospinning, a technique well known for fabricating nanoscale fibers, has recently been studied extensively due to its various advantages such as high surface-to-volume ratio, tunable porosity, and ease of surface functionalization. The resulting fibers are extremely useful for applications in the fields of tissue engineering, drug delivery, and wound dressing. Since electrospun fiber mimic extracellular matrix of tissue in terms of scale and morphology, its potential to be used as scaffold is continuously explored by researchers, especially in the field of vascular, nerve, bone, and tendon/ligament tissue engineering. Besides morphology, physical, and chemical properties, electrospun scaffolds are often evaluated through various cell studies. Researchers have adopted approaches such as surface modification and drug loading to enhance the property and function of scaffold. This review gives an overview of some current aspects of various applications of electrospun fibers, particularly in biomedical fields, how researchers have enhanced electrospun fibers with different methods and attempted to overcome the inherent limitation of electrospinning by using novel techniques.     

湿法纺丝Amid-CNT/PAN复合纤维的结构与性能

通过溶液聚合得到胺化碳纳米管（Ami-CNT）/聚丙烯腈（PAN）复合溶液, 采用湿法纺丝技术制备了Amid-CNT/PAN复合纤维。利用红外光谱、 拉曼光谱、 差示扫描量热仪、 热失重仪和扫描电镜等方法分析Amid-CNT对PAN纤维结构的影响。结果表明: Amid-CNT与PAN大分子之间有很强的化学作用力; Amid-CNT在复合纤维中具有很高程度的取向, 使PAN纤维中氰基的取向从1.61提高到了2.30; 复合纤维在空气中的起始放热温度相对PAN纤维从212.30℃提前到206.01℃, 反应放热量从3054J/g降低到2346J/g; 复合纤维比PAN纤维的起始失重温度提前了3.7℃, 在700℃时的剩余质量提高了13.5%; 复合纤维的断面比PAN纤维具有更多的絮状结构。      

Mussel‐Inspired Defect Engineering of Graphene Liquid Crystalline Fibers for Synergistic Enhancement of Mechanical Strength and Electrical Conductivity

Inspired by mussel adhesive polydopamine (PDA), effective reinforcement of graphene‐based liquid crystalline fibers to attain high mechanical and electrical properties simultaneously is presented. The two‐step defect engineering, relying on bioinspired surface polymerization and subsequent solution infiltration of PDA, addresses the intrinsic limitation of graphene fibers arising from the folding and wrinkling of graphene layers during the fiber‐spinning process. For a clear understanding of the mechanism of PDA‐induced defect engineering, interfacial adhesion between graphene oxide sheets is straightforwardly analyzed by the atomic force microscopy pull‐off test. Subsequently, PDA could be converted into an N‐doped graphitic layer within the fiber structure by a mild thermal treatment such that mechanically strong fibers could be obtained without sacrificing electrical conductivity. Bioinspired graphene‐based fiber holds great promise for a wide range of applications, including flexible electronics, multifunctional textiles, and wearable sensors.     

Preparation and characterization of novel gelatin/cerium (III) fiber with antibacterial activity

Gelatin/Cerium (III) fibers with high tensile strength and good antibacterial activity were prepared by wet spinning method. The fiber structure and properties were investigated. The optical microscope (OPM) results showed that the fiber had a smooth surface and the fiber diameter was in the range of 60-90 µm. The mechanical properties tests showed that the tensile strength of gelatin/cerium (III) fibers increased greatly compared with the pure gelatin fibers. Furthermore, it was found that the gelatin/Ce (III) fibers have the antibacterial activity for Escherichia coli and Staphylococcus aureus.     

Advanced Carbon for Flexible and Wearable Electronics

Flexible and wearable electronics are attracting wide attention due to their potential applications in wearable human health monitoring and care systems. Carbon materials have combined superiorities such as good electrical conductivity, intrinsic and structural flexibility, light weight, high chemical and thermal stability, ease of chemical functionalization, as well as potential mass production, enabling them to be promising candidate materials for flexible and wearable electronics. Consequently, great efforts are devoted to the controlled fabrication of carbon materials with rationally designed structures for applications in next‐generation electronics. Herein, the latest advances in the rational design and controlled fabrication of carbon materials toward applications in flexible and wearable electronics are reviewed. Various carbon materials (carbon nanotubes, graphene, natural‐biomaterial‐derived carbon, etc.) with controlled micro/nanostructures and designed macroscopic morphologies for high‐performance flexible electronics are introduced. The fabrication strategies, working mechanism, performance, and applications of carbon‐based flexible devices are reviewed and discussed, including strain/pressure sensors, temperature/humidity sensors, electrochemical sensors, flexible conductive electrodes/wires, and flexible power devices. Furthermore, the integration of multiple devices toward multifunctional wearable systems is briefly reviewed. Finally, the existing challenges and future opportunities in this field are summarized.     

Graphene-Based Fibers: Recent Advances in Preparation and Application

Graphene-based fibers (GBFs) are macroscopic 1D assemblies formed by using microscopic 2D graphene sheets as building blocks. Their unique structure exhibits the same merits as graphene such as low weight, high specific surface area, excellent mechanical/electrical properties, and ease of functionalization. Furthermore, the fibrous nature of GBFs is intrinsically compatible with existing textile technologies, making them suitable for applications in flexible and wearable electronics. Recently, novel synthetic methods have endowed GBFs with new structures and functions, further improving their mechanical and electrical properties. These improvements have rapidly bridged the gaps between laboratory demonstrations and real-life applications in fiber-shaped batteries, supercapacitors, and electrochemical sensors. Recent advances in the fabrication, optimization, and application of GBFs are systematically reviewed and a perspective on their future development is given.     

Micro‐and Nanoscale Metallic Glassy Fibers

When bulk materials are made into micro‐and nanoscale fibers, there will be attractive improvement of structural and functional properties, even unusual experimental phenomena [Ref. 3 ]. The main drawback of various applications of metallic fibers is poor ability of present fabrication methods for controlling their dimensions and surface properties [Ref. 4 ]. Metallic glassy fibers (MGFs) are desired because of unique mechanical and physical properties and glass‐like thermoplastic processability of metallic glasses (MGs). Here, we report a synthetic route for production of micro‐to nanoscale MGFs (the diameter ranges from 100 µm to 70 nm) by driving bulk metallic glass rods in their supercooled liquid region via superplastic deformation. Compared with existing metallic fibers, the MGFs have precisely designed and controlled properties and size, high structural uniformity and surface smoothness, and extremely flexibility. Remarkably, the method is simple, efficient, and low cost, and the MGFs can be continuous prepared by the method. Furthermore, the MGFs circumvent brittleness of MGs by size reduction. We proposed a parameter based on the thermal and rheological properties of MG‐forming alloys to control the preparation and size of the fibers. The MGFs with superior properties might attract intensive scientific interest and open wide engineering and functional applications of glassy alloys.     

One‐Step Assembly of a Biomimetic Biopolymer Coating for Particle Surface Engineering

Advances in material design and applications are highly dependent on the development of particle surface engineering strategies. However, few universal methods can functionalize particles of different compositions, sizes, shapes, and structures. The amyloid‐like lysozyme assembly‐mediated surface functionalization of inorganic, polymeric or metal micro/nanoparticles in a unique amyloid‐like phase‐transition buffer containing lysozyme are described. The rapid formation of a robust nanoscale phase‐transitioned lysozyme (PTL) coating on the particle surfaces presents strong interfacial binding to resist mechanical and chemical peeling under harsh conditions and versatile surface functional groups to support various sequential surface chemical derivatizations, such as radical living graft polymerization, the electroless deposition of metals, biomineralization, and the facile synthesis of Janus particles and metal/protein capsules. Being distinct from other methods, the preparation of this pure protein coating under biocompatible conditions (e.g., neutral pH and nontoxic reagents) provides a reliable opportunity to directly modify living cell surfaces without affecting their biological activity. The PTL coating arms yeasts with a functional shell to protect their adhered body against foreign enzymatic digestion. The PTL coating further supports the surface immobilization of living yeasts for heterogeneous microbial reactions and the sequential surface chemical derivatization of the cell surfaces, e.g., radical living graft polymerization.     

Advances in Insight of Radial Heterogeneous Microstructure and Its Relevance to Mechanical Properties of Polyacrylonitrile-Based Carbon Fibers

Polyacrylonitrile-based carbon fibers (CFs) have demonstrated unparalleled physical and mechanical properties and are considered a promising material for aerospace, transportation, medical devices, and other applications. However, the current understanding of the heterogeneous structure of carbon fiber is still vague, and the relationship between the heterogeneous structure and the mechanical properties of carbon fiber is also unclear. In this review, the literature on the radial heterogeneous structure of CFs is summarized from four points of view: morphological structure, physical properties and chemical structures, mechanical properties, and structural models by combining different characterization tools such as nanoindentation, nanoscale infrared spectroscopy, and synchrotron wide-angle X-ray diffraction. First, the size and orientation of graphite microcrystalline, the degree of graphitization, density distribution, modulus distribution, chemical functional group distribution, and other physical and chemical properties of carbon fiber cross-sectional structures are discussed. Afterward, the relationship between the mechanical properties of carbon fiber and the heterogeneous structure is analyzed. Finally, the currently accepted models of the heterogeneous structure of carbon fibers are summarized and made some suggestions for research on the heterogeneous structure of carbon fibers.