The Design and Synthesis of Hollow Micro‐/Nanostructures: Present and Future Trends

Hollow micro‐/nanostructures have attracted tremendous interest owing to their intriguing structure‐induced physicochemical properties and great potential for widespread applications. With the development of modern synthetic methodology and analytical instruments, a rapid structural/compositional evolution of hollow structures from simple to complex has occurred in recent decades. Here, an updated overview of research progress made in the synthesis of hollow structures is provided. After an introduction of definition and classification, achievements in synthetic approaches for these delicate hollow architectures are presented in detail. According to formation mechanisms, these strategies can be categorized into four different types, including hard‐templating, soft‐templating, self‐templated, and template‐free methods. In particular, the rationales and emerging innovations in conventional templating syntheses are in focus. The development of burgeoning self‐templating strategies based on controlled etching, outward diffusion, and heterogeneous contraction is also summarized. In addition, a brief overview of template‐free methods and recent advances on combined mechanisms is provided. Notably, the strengths and weaknesses of each category are discussed in detail. In conclusion, a perspective on future trends in the research of hollow micro‐/nanostructures is given.     

Programmable Liquid Adhesion on Bio‐Inspired Re‐Entrant Structures

Surfaces combining antispreading and high adhesion can find wide applications in the manipulation of liquid droplets, generation of micropatterns and liquid enrichment. To fabricate such surfaces, almost all the traditional methods demand multi‐step processes and chemical modification. And even so, most of them cannot be applied for some liquids with extremely low surface energy. In the past decade, multiply re‐entrant structures have aroused much attention because of their universal and modification‐independent antiadhesion or antipenetration ability. Unfortunately, theories and applications about their liquid adhesion behavior are still rare. In this work, inspired by the springtail skin and gecko feet in the adhered state, it is demonstrated that programmable liquid adhesion is realized on the 3D‐printed micro doubly re‐entrant arrays. By arranging the arrays reasonably, three different Cassie adhesion behaviors can be obtained: I) no residue adhesion, II) tunable adhesion, and III) absolute adhesion. Furthermore, various arrays are designed to tune macro/micro liquid droplet manipulation, which can find applications in the transportation of liquid droplets, liquid enrichment, generation of tiny droplets, and micropatterns.     

Hollow Micro‐/Nanostructures: Synthesis and Applications

Hollow micro‐/nanostructures are of great interest in many current and emerging areas of technology. Perhaps the best‐known example of the former is the use of fly‐ash hollow particles generated from coal power plants as partial replacement for Portland cement, to produce concrete with enhanced strength and durability. This review is devoted to the progress made in the last decade in synthesis and applications of hollow micro‐/nanostructures. We present a comprehensive overview of synthetic strategies for hollow structures. These strategies are broadly categorized into four themes, which include well‐established approaches, such as conventional hard‐templating and soft‐templating methods, as well as newly emerging methods based on sacrificial templating and template‐free synthesis. Success in each has inspired multiple variations that continue to drive the rapid evolution of the field. The Review therefore focuses on the fundamentals of each process, pointing out advantages and disadvantages where appropriate. Strategies for generating more complex hollow structures, such as rattle‐type and nonspherical hollow structures, are also discussed. Applications of hollow structures in lithium batteries, catalysis and sensing, and biomedical applications are reviewed.     

Micro‐/Nanostructured Interface for Liquid Manipulation and Its Applications

Understanding the relationship between liquid manipulation and micro‐/nanostructured interfaces has gained much attention due to the wide potential applications in many fields, such as chemical and biomedical assays, environmental protection, industry, and even daily life. Much work has been done to construct various materials with interfacial liquid manipulation abilities, leading to a range of interesting applications. Herein, different fabrication methods from the top‐down approach to the bottom‐up approach and subsequent surface modifications of micro‐/nanostructured interfaces are first introduced. Then, interactions between the surface and liquid, including liquid wetting, liquid transportation, and a number of corresponding models, together with the definition of hydrophilic/hydrophobic, oleophilic/olephobic, the definition and mechanism of superwetting, including superhydrophobicity, superhydrophilicity, and superoleophobicity, are presented. The micro‐/nanostructured interface, with major applications in self‐cleaning, antifogging, anti‐icing, anticorrosion, drag‐reduction, oil–water separation, water collection, droplet (micro)array, and surface‐directed liquid transport, is summarized, and the mechanisms underlying each application are discussed. Finally, the remaining challenges and future perspectives in this area are included.     

Simultaneous Fabrication of Very High Aspect Ratio Positive Nano‐ to Milliscale Structures

A simple and inexpensive technique for the simultaneous fabrication of positive (i.e., protruding), very high aspect (>10) ratio nanostructures together with micro‐ or millistructures is developed. The method involves using residual patterns of thin‐film over‐etching (RPTO) to produce sub‐micro‐/nanoscale features. The residual thin‐film nanopattern is used as an etching mask for Si deep reactive ion etching. The etched Si structures are further reduced in size by Si thermal oxidation to produce amorphous SiO₂, which is subsequently etched away by HF. Two arrays of positive Si nanowalls are demonstrated with this combined RPTO‐SiO₂‐HF technique. One array has a feature size of 150 nm and an aspect ratio of 26.7 and another has a feature size of 50 nm and an aspect ratio of 15. No other parallel reduction technique can achieve such a very high aspect ratio for 50‐nm‐wide nanowalls. As a demonstration of the technique to simultaneously achieve nano‐ and milliscale features, a simple Si nanofluidic master mold with positive features with dimensions varying continuously from 1 mm to 200 nm and a highest aspect ratio of 6.75 is fabricated; the narrow 200‐nm section is 4.5 mm long. This Si master mold is then used as a mold for UV embossing. The embossed open channels are then closed by a cover with glue bonding. A high aspect ratio is necessary to produce unblocked closed channels after the cover bonding process of the nanofluidic chip. The combined method of RPTO, Si thermal oxidation, and HF etching can be used to make complex nanofluidic systems and nano‐/micro‐/millistructures for diverse applications.     

Fabrication of nanofluidic biochips with nanochannels for applications in DNA analysis

With the development of nanotechnology, great progress has been made in the fabrication of nanochannels. Nanofluidic biochips based on nanochannel structures allow biomolecule transport, bioseparation, and biodetection. The domain applications of nanofluidic biochips with nanochannels are DNA stretching and separation. In this Review, the general fabrication methods for nanochannel structures and their applications in DNA analysis are discussed. These representative fabrication approaches include conventional photolithography, interference lithography, electron-beam lithography, nanoimprint lithography and polymer nanochannels. Other nanofabrication methods used to fabricate unique nanochannels, including sub-10-nm nanochannels, single nanochannels, and vertical nanochannels, are also mentioned. These nanofabrication methods provide an effective way to form nanoscale channel structures for nanofluidics and biosensor devices for DNA separation, detection, and sensing. The broad applications of nanochannels and future perspectives are also discussed.     

Fuel‐Free Synthetic Micro‐/Nanomachines

Inspired by the swimming of natural microorganisms, synthetic micro‐/nanomachines, which convert energy into movement, are able to mimic the function of these amazing natural systems and help humanity by completing environmental and biological tasks. While offering autonomous propulsion, conventional micro‐/nanomachines usually rely on the decomposition of external chemical fuels (e.g., H₂O₂), which greatly hinders their applications in biologically relevant media. Recent developments have resulted in various micro‐/nanomotors that can be powered by biocompatible fuels. Fuel‐free synthetic micro‐/nanomotors, which can move without external chemical fuels, represent another attractive solution for practical applications owing to their biocompatibility and sustainability. Here, recent developments on fuel‐free micro‐/nanomotors (powered by various external stimuli such as light, magnetic, electric, or ultrasonic fields) are summarized, ranging from fabrication to propulsion mechanisms. The applications of these fuel‐free micro‐/nanomotors are also discussed, including nanopatterning, targeted drug/gene delivery, cell manipulation, and precision nanosurgery. With continuous innovation, future autonomous, intelligent and multifunctional fuel‐free micro‐/nanomachines are expected to have a profound impact upon diverse biomedical applications, providing unlimited opportunities beyond one's imagination.     

Light‐Powered Directional Nanofluidic Ion Transport in Kirigami‐Made Asymmetric Photonic‐Ionic Devices

Nacre‐mimetic 2D nanofluidic materials with densely packed sub‐nanometer‐height lamellar channels find widespread applications in water‐, energy‐, and environment‐related aspects by virtue of their scalable fabrication methods and exceptional transport properties. Recently, light‐powered nanofluidic ion transport in synthetic materials gained considerable attention for its remote, noninvasive, and active control of the membrane transport property using the energy of light. Toward practical application, a critical challenge is to overcome the dependence on inhomogeneous or site‐specific light illumination. Here, asymmetric photonic‐ionic devices based on kirigami‐tailored graphene oxide paper are fabricated, and directional nanofluidic ion transport properties therein powered by full‐area light illumination are demonstrated. The in‐plane asymmetry of the graphene oxide paper is essential to the generation of photoelectric driving force under homogeneous illumination. This light‐powered ion transport phenomenon is explained based on a modified carrier diffusion model. In asymmetric nanofluidic structures, enhanced recombination of photoexcited charge carriers at the membrane boundary breaks the electric potential balance in the horizontal direction, and thus drives the ion transport in that direction under symmetric illumination. The kirigami‐based strategy provides a facile and scalable way to fabricate paper‐like photonic‐ionic devices with arbitrary shapes, working as fundamental elements for large‐scale light‐harvesting nanofluidic circuits.     

Freestanding Nanostructures via Layer‐by‐Layer Assembly

Freestanding flexible nanocomposite structures fabricated by layer‐by‐layer (LbL) assembly are promising candidates for many potential applications, such as in the fields of thermomechanical sensing, controlled release, optical detection, and drug delivery. In this article, we review recent advances in the fabrication and characterization of different types of freestanding LbL structures in air and at air/liquid and liquid/liquid interfaces, including micro‐ and nanocapsules, microcantilevers, freely suspended membranes, encapsulated nanoparticle arrays, and sealed‐cavity arrays. Several recently developed fabrication techniques, such as spin‐assisted coating, dipping, and micropatterning, make the assembly process more efficient and impart novel physical properties to the freestanding films.     

Motion Manipulation of Micro‐ and Nanomotors

Inspired by the self‐migration of microorganisms in nature, artificial micro‐ and nanomotors can mimic this fantastic behavior by converting chemical fuel or external energy into mechanical motion. These self‐propelled micro‐ and nanomotors, designed either by top‐down or bottom‐up approaches, are able to achieve different applications, such as environmental remediation, sensing, cargo/sperm transportation, drug delivery, and even precision micro‐/nanosurgery. For these various applications, especially biomedical applications, regulating on‐demand the motion of micro‐ and nanomotors is quite essential. However, it remains a continuing challenge to increase the controllability over motors themselves. Here, we will discuss the recent advancements regarding the motion manipulation of micro‐ and nanomotors by different approaches.     

Fluid flow in carbon nanotubes and nanopipes

Nanoscale carbon tubes and pipes can be readily fabricated using self-assembly techniques and they have useful electrical, optical and mechanical properties. The transport of liquids along their central pores is now of considerable interest both for testing classical theories of fluid flow at the nanoscale and for potential nanofluidic device applications. In this review we consider evidence for novel fluid flow in carbon nanotubes and pipes that approaches frictionless transport. Methods for controlling such flow and for creating functional device architectures are described and possible applications are discussed.     

Tunable Confinement for Bridging Single‐Cell Manipulation and Single‐Molecule DNA Linearization

DNA linearization by nanoconfinement has offered a new avenue toward large‐scale genome mapping. The ability to smoothly interface the widely different length scales from cell manipulation to DNA linearization is critical to the development of single‐cell genomic mapping or sequencing technologies. Conventional nanochannel technologies for DNA analysis suffer from complex fabrication procedures, DNA stacking at the nanochannel entrance, and inefficient solution exchange. In this work, a dynamic and tunable confinement strategy is developed to manipulate and linearize genomic‐length DNA molecules from a single cell. By leveraging pneumatic microvalve control and elastomeric collapse, an array of nanochannels with confining dimension down to 20 nm and length up to sub‐millimeter is created and can be dynamically tuned in size. The curved edges of the microvalve form gradual transitions from microscale to nanoscale confinement, smoothly facilitating DNA entry into the nanochannels. A unified micro/nanofluidic device that integrates single‐cell trapping and lysis, DNA extraction, purification, labeling, and linearization is developed based on dynamically controllable nanochannels. Mbp‐long DNA molecules are extracted directly from a single cell and in situ linearized in the nanochannels. The device provides a facile and promising platform to achieve the ultimate goal of single‐cell, single‐genome analysis.     

Microfluidic‐Based Approaches in Targeted Cell/Particle Separation Based on Physical Properties: Fundamentals and Applications

Cell separation is a key step in many biomedical research areas including biotechnology, cancer research, regenerative medicine, and drug discovery. While conventional cell sorting approaches have led to high‐efficiency sorting by exploiting the cell's specific properties, microfluidics has shown great promise in cell separation by exploiting different physical principles and using different properties of the cells. In particular, label‐free cell separation techniques are highly recommended to minimize cell damage and avoid costly and labor‐intensive steps of labeling molecular signatures of cells. In general, microfluidic‐based cell sorting approaches can separate cells using “intrinsic” (e.g., fluid dynamic forces) versus “extrinsic” external forces (e.g., magnetic, electric field, etc.) and by using different properties of cells including size, density, deformability, shape, as well as electrical, magnetic, and compressibility/acoustic properties to select target cells from a heterogeneous cell population. In this work, principles and applications of the most commonly used label‐free microfluidic‐based cell separation methods are described. In particular, applications of microfluidic methods for the separation of circulating tumor cells, blood cells, immune cells, stem cells, and other biological cells are summarized. Computational approaches complementing such microfluidic methods are also explained. Finally, challenges and perspectives to further develop microfluidic‐based cell separation methods are discussed.     

Robust Free‐Standing Nano‐Thin SiC Membranes Enable Direct Photolithography for MEMS Sensing Applications

This work presents fabrication of micro structures on sub–100 nm SiC membranes with a large aspect ratio up to 1:3200. Unlike conventional processes, this approach starts with Si wet etching to form suspended SiC membranes, followed by micro‐machined processes to pattern free‐standing microstructures such as cantilevers and micro bridges. This technique eliminates the sticking or the under‐etching effects on free‐standing structures, enhancing mechanical performance which is favorable for MEMS applications. In addition, post‐Si‐etching photography also enables the formation of metal electrodes on free standing SiC membranes to develop electrically‐measurable devices. To proof this concept, the authors demonstrate a SiC pressure sensor by applying lithography and plasma etching on released ultrathin SiC films. The sensors exhibit excellent linear response to the applied pressure, as well as good repeatability. The proposed method opens a pathway for the development of self‐sensing free‐standing SiC sensors.     

Assembly and Self‐Assembly of Nanomembrane Materials—From 2D to 3D

Nanoscience and nanotechnology offer great opportunities and challenges in both fundamental research and practical applications, which require precise control of building blocks with micro/nanoscale resolution in both individual and mass‐production ways. The recent and intensive nanotechnology development gives birth to a new focus on nanomembrane materials, which are defined as structures with thickness limited to about one to several hundred nanometers and with much larger (typically at least two orders of magnitude larger, or even macroscopic scale) lateral dimensions. Nanomembranes can be readily processed in an accurate manner and integrated into functional devices and systems. In this Review, a nanotechnology perspective of nanomembranes is provided, with examples of science and applications in semiconductor, metal, insulator, polymer, and composite materials. Assisted assembly of nanomembranes leads to wrinkled/buckled geometries for flexible electronics and stacked structures for applications in photonics and thermoelectrics. Inspired by kirigami/origami, self‐assembled 3D structures are constructed via strain engineering. Many advanced materials have begun to be explored in the format of nanomembranes and extend to biomimetic and 2D materials for various applications. Nanomembranes, as a new type of nanomaterials, allow nanotechnology in a controllable and precise way for practical applications and promise great potential for future nanorelated products.     

Emerging Strategies of Nanomaterial‐Mediated Tumor Radiosensitization

Nano‐radiosensitization has been a hot concept for the past ten years, and the nanomaterial‐mediated tumor radiosensitization method is mainly focused on increasing intracellular radiation deposition by high atomic number (high Z) nanomaterials, particularly gold (Au)‐mediated radiation enhancement. Recently, various new nanomaterial‐mediated radiosensitive approaches have been successively reported, such as catalyzing reactive oxygen species (ROS) generation, consuming intracellular reduced glutathione (GSH), overcoming tumor hypoxia, and various synergistic radiotherapy ways. These strategies may open a new avenue for enhancing the radiotherapeutic effect and avoiding its side effects. Nevertheless, reviews systematically summarizing these newly emerging methods and their radiosensitive mechanisms are still rare. Therefore, the general strategies of nanomaterial‐mediated tumor radiosensitization are comprehensively summarized, particularly aiming at introducing the emerging radiosensitive methods. The strategies are divided into three general parts. First, methods on account of the intrinsic radiosensitive properties of nanoradiosensitizers for radiosensitization are highlighted. Then, newly developed synergistic strategies based on multifunctional nanomaterials for enhancing radiotherapy efficacy are emphasized. Third, nanomaterial‐mediated radioprotection approaches for increasing the radiotherapeutic ratio are discussed. Importantly, the clinical translation of nanomaterial‐mediated tumor radiosensitization is also covered. Finally, further challenges and outlooks in this field are discussed.     

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.     

Nanopore Sensing in Aqueous Two‐Phase System: Simultaneous Enhancement of Signal and Translocation Time via Conformal Coating

Nanofluidic resistive pulse sensing (RPS) has been extensively used to measure the size, concentration, and surface charge of nanoparticles in electrically conducting solutions. Although various methods have been explored for improving detection performances, intrinsic problems including the extremely low particle‐to‐pore volume ratio (<0.01%) and fast nanoparticle translocation (10–1000 µs) still induce difficulties in detection, such as low signal magnitudes and short translocation times. Herein, we present an aqueous two‐phase system (ATPS) in a nanofluidic RPS for amplifying translocation signals and decreasing translocation speeds simultaneously. Two immiscible aqueous liquids build a liquid‐liquid interface inside nanopores. As particles translocate from a high‐affinity liquid phase into a lower‐affinity one, the high‐affinity liquid forms a conformal coating on the particles, which increases the effective particle size and amplifies the current‐blockage signal. The translocation time is also increased, as the ATPS interface impedes the particle translocation. For 20 nm particles, 7.92‐fold and 5.82‐fold enhancements of signal magnitude and translocation time can be achieved. To our knowledge, this is the first attempt to improve nanofluidic RPS by treating an interface of solution reservoirs for manipulating target particles rather than nanopores. This direct particle manipulation allows us to solve the two intrinsic problems all at once.     

Heavy‐Metal‐Free Colloidal Semiconductor Nanorods: Recent Advances and Future Perspectives

Quasi‐1D colloidal semiconductor nanorods (NRs) are at the forefront of nanoparticle (NP) research owing to their intriguing size‐dependent and shape‐dependent optical and electronic properties. The past decade has witnessed significant advances in both fundamental understanding of the growth mechanisms and applications of these stimulating materials. Herein, the state‐of‐the‐art of colloidal semiconductor NRs is reviewed, with special emphasis on heavy‐metal‐free materials. The main growth mechanisms of heavy‐metal‐free colloidal semiconductor NRs are first elaborated, including anisotropic‐controlled growth, oriented attachment, solution–liquid–solid method, and cation exchange. Then, structural engineering and properties of semiconductor NRs are discussed, with a comprehensive overview of core/shell structures, alloying, and doping, as well as semiconductor–metal hybrid nanostructures, followed by highlighted practical applications in terms of photocatalysis, photodetectors, solar cells, and biomedicine. Finally, challenges and future opportunities in this fascinating research area are proposed.     

Multifunctional Micro/Nanoscale Fibers Based on Microfluidic Spinning Technology

Superfine multifunctional micro/nanoscale fibrous materials with high surface area and ordered structure have attracted intensive attention for widespread applications in recent years. Microfluidic spinning technology (MST) has emerged as a powerful and versatile platform because of its various advantages such as high surface‐area‐to‐volume ratio, effective heat transfer, and enhanced reaction rate. The resultant well‐defined micro/nanoscale fibers exhibit controllable compositions, advanced structures, and new physical/chemical properties. The latest developments and achievements in microfluidic spun fiber materials are summarized in terms of the underlying preparation principles, geometric configurations, and functionalization. Variously architected structures and shapes by MST, including cylindrical, grooved, flat, anisotropic, hollow, core–shell, Janus, heterogeneous, helical, and knotted fibers, are emphasized. In particular, fiber‐spinning chemistry in MST for achieving functionalization of fiber materials by in situ chemical reactions inside fibers is introduced. Additionally, the applications of the fabricated functional fibers are highlighted in sensors, microactuators, photoelectric devices, flexible electronics, tissue engineering, drug delivery, and water collection. Finally, recent progress, challenges, and future perspectives are discussed.