Self‐Correction Strategy for Precise,Massive, and Parallel Macroscopic Supramolecular Assembly

Macroscopic supramolecular assembly (MSA) represents a new advancement in supramolecular chemistry involving building blocks with sizes beyond tens of micrometers associating through noncovalent interactions. MSA is established as a unique method to fabricate supramolecularly assembled materials by shortening the length scale between bulk materials and building blocks. However, improving the precise alignment during assembly to form orderly assembled structures remains a challenge. Although the pretreatment of building blocks can ameliorate order to a certain degree, defects or mismatching still exists, which limits the practical applications of MSA. Therefore, an iterative poststrategy is proposed, where self‐correction based on dynamic assembly/disassembly is applied to achieve precise, massive, and parallel assembly. The self‐correction process consists of two key steps: the identification of poorly ordered structures and the selective correction of these structures. This study develops a diffusion‐kinetics‐dependent disassembly to well identify the poorly aligned structures and correct these structures through iterations of disassembly/reassembly in a programmed fashion. Finally, a massive and parallel assembly of 100 precise dimers over eight iteration cycles is achieved, thus providing a powerful solution to the problem of processing insensitivity to errors in self‐assembly‐related methods.     

Combining Bottom‐Up Self‐Assembly with Top‐Down Microfabrication to Create Hierarchical Inverse Opals with High Structural Order

Colloidal particles can assemble into ordered crystals, creating periodically structured materials at the nanoscale without relying on expensive equipment. The combination of small size and high order leads to strong interaction with visible light, which induces macroscopic, iridescent structural coloration. To increase the complexity and functionality, it is important to control the organization of such materials in hierarchical structures with high degrees of order spanning multiple length scales. Here, a bottom‐up assembly of polystyrene particles in the presence of a silica sol–gel precursor material (tetraethylorthosilicate, TEOS), which creates crack‐free inverse opal films with high positional order and uniform crystal alignment along the (110) crystal plane, is combined with top‐down microfabrication techniques. Micrometer scale hierarchical superstructures having a highly regular internal nanostructure with precisely controlled crystal orientation and wall profiles are produced. The ability to combine structural order at the nano‐ and microscale enables the fabrication of materials with complex optical properties resulting from light–matter interactions at different length scales. As an example, a hierarchical diffraction grating, which combines Bragg reflection arising from the nanoscale periodicity of the inverse opal crystal with grating diffraction resulting from a micrometer scale periodicity, is demonstrated.     

Morphosynthesis of Molecular Magnetic Materials

Although molecule‐based materials can combine physical and chemical properties associated with molecular‐scale building blocks, their successful integration into real applications depends also on higher‐order properties, such as crystal size, shape, and organization. New approaches involving templating and self‐ or facilitated assembly of nanoscale building blocks to prepare novel multifunctional molecular magnetic materials with complex form and organization are described.     

Fabrication of Flexible Metal‐Nanoparticle Films Using Graphene Oxide Sheets as Substrates

Graphene‐based sheets that possess a unique nanostructure and a variety of fascinating properties are appealing as promising nanoscale building blocks of new composites. Herein, graphene oxide sheets are used as the nanoscale substrates for the formation of silver‐nanoparticle films. These silver‐nanoparticle films assembled on graphene oxide sheets are flexible and can form stable suspensions in aqueous solutions. They can also be easily processed, forming macroscopic films with high reflectivity. Raman signals of graphene oxide in such hybrid films are increased by the attached silver nanoparticles, displaying surface‐enhanced Raman scattering activity. The degree of enhancement can be adjusted by varying the quantity of silver nanoparticles on the graphene oxide sheets.     

Multifunctional Nanoparticles Self‐Assembled from Small Organic Building Blocks for Biomedicine

Supramolecular self‐assembly shows significant potential to construct responsive materials. By tailoring the structural parameters of organic building blocks, nanosystems can be fabricated, whose performance in catalysis, energy storage and conversion, and biomedicine has been explored. Since small organic building blocks are structurally simple, easily modified, and reproducible, they are frequently employed in supramolecular self‐assembly and materials science. The dynamic and adaptive nature of self‐assembled nanoarchitectures affords an enhanced sensitivity to the changes in environmental conditions, favoring their applications in controllable drug release and bioimaging. Here, recent significant research advancements of small‐organic‐molecule self‐assembled nanoarchitectures toward biomedical applications are highlighted. Functionalized assemblies, mainly including vesicles, nanoparticles, and micelles are categorized according to their topological morphologies and functions. These nanoarchitectures with different topologies possess distinguishing advantages in biological applications, well incarnating the structure–property relationship. By presenting some important discoveries, three domains of these nanoarchitectures in biomedical research are covered, including biosensors, bioimaging, and controlled release/therapy. The strategies regarding how to design and characterize organic assemblies to exhibit biomedical applications are also discussed. Up‐to‐date research developments in the field are provided and research challenges to be overcome in future studies are revealed.     

Macroscopic carbon nanotube assemblies: preparation, properties, and potential applications

As classical 1D nanoscale structures, carbon nanotubes (CNTs) possess remarkable mechanical, electrical, thermal, and optical properties. In the past several years, considerable attention has been paid to the use of CNTs as building blocks for novel high-performance materials. In this way, the production of macroscopic architectures based on assembled CNTs with controlled orientation and configurations is an important step towards their application. So far, various forms of macroscale CNT assemblies have been produced, such as 1D CNT fibers, 2D CNT films/sheets, and 3D aligned CNT arrays or foams. These macroarchitectures, depending on the manner in which they are assembled, display a variety of fascinating features that cannot be achieved using conventional materials. This review provides an overview of various macroscopic CNT assemblies, with a focus on their preparation and mechanical properties as well as their potential applications in practical fields.     

Self‐Assembly of Functional Molecules into 1D Crystalline Nanostructures

Self‐assembled functional nanoarchitectures are employed as important nanoscale building blocks for advanced materials and smart miniature devices to fulfill the increasing needs of high materials usage efficiency, low energy consumption, and high‐performance devices. One‐dimensional (1D) crystalline nanostructures, especially molecule‐composed crystalline nanostructures, attract significant attention due to their fascinating infusion structure and functionality which enables the easy tailoring of organic molecules with excellent carrier mobility and crystal stability. In this review, we discuss the recent progress of 1D crystalline self‐assembled nanostructures of functional molecules, which include both a small molecule‐derived and a polymer‐based crystalline nanostructure. The basic principles of the molecular structure design and the process engineering of 1D crystalline nanostructures are also discussed. The molecular building blocks, self‐assembly structures, and their applications in optical, electrical, and photoelectrical devices are overviewed and we give a brief outlook on crucial issues that need to be addressed in future research endeavors.     

Effective Light Directed Assembly of Building Blocks with Microscale Control

Light‐directed forces have been widely used to pattern micro/nanoscale objects with precise control, forming functional assemblies. However, a substantial laser intensity is required to generate sufficient optical gradient forces to move a small object in a certain direction, causing limited throughput for applications. A high‐throughput light‐directed assembly is demonstrated as a printing technology by introducing gold nanorods to induce thermal convection flows that move microparticles (diameter = 40 µm to several hundreds of micrometers) to specific light‐guided locations, forming desired patterns. With the advantage of effective light‐directed assembly, the microfluidic‐fabricated monodispersed biocompatible microparticles are used as building blocks to construct a structured assembly (≈10 cm scale) in ≈2 min. The control with microscale precision is approached by changing the size of the laser light spot. After crosslinking assembly of building blocks, a novel soft material with wanted pattern is approached. To demonstrate its application, the mesenchymal stem‐cell‐seeded hydrogel microparticles are prepared as functional building blocks to construct scaffold‐free tissues with desired structures. This light‐directed fabrication method can be applied to integrate different building units, enabling the bottom‐up formation of materials with precise control over their internal structure for bioprinting, tissue engineering, and advanced manufacturing.     

Large‐Area 3D Hierarchical Superstructures Assembled from Colloidal Nanoparticles

Assembling nanosized building blocks into macroscopic 3D complex structures is challenging. Here, nanosized metal and semiconductor building blocks with a variety of sizes and shapes (spheres, stars, and rods) are successfully assembled into a broad range of hierarchical (nanometer to micrometer) assemblies of functional materials in centimeter size using butterfly wings as templates. This is achieved by the introduction of steric hindrance to the assembly process, which compensates for attraction from the environmentally sensitive hydrogen bonds and prevents the aggregation of nanosized building blocks. Of these materials, Au nanostar assemblies show a superior enhancement in surface‐enhanced Raman scattering (SERS) performance (rhodamine 6G, 1506 cm^?1) under 532, 633, and 780 nm excitation—this is 3.1–4.4, 3.6–3.9, and 2.9–47.3 folds surpassing Au nanosphere assemblies and commercial SERS substrates (Q‐SERS), respectively. This method provides a versatile route for the assembly of various nanosized building blocks into different 3D superstructures and for the construction of hybrid nanomaterials and nanocomposites.     

Programmable Atom Equivalents: Atomic Crystallization as a Framework for Synthesizing Nanoparticle Superlattices

Decades of research efforts into atomic crystallization phenomenon have led to a comprehensive understanding of the pathways through which atoms form different crystal structures. With the onset of nanotechnology, methods that use colloidal nanoparticles (NPs) as nanoscale “artificial atoms” to generate hierarchically ordered materials are being developed as an alternative strategy for materials synthesis. However, the assembly mechanisms of NP‐based crystals are not always as well‐understood as their atomic counterparts. The creation of a tunable nanoscale synthon whose assembly can be explained using the context of extensively examined atomic crystallization will therefore provide significant advancement in nanomaterials synthesis. DNA‐grafted NPs have emerged as a strong candidate for such a “programmable atom equivalent” (PAE), because the predictable nature of DNA base‐pairing allows for complex yet easily controlled assembly. This Review highlights the characteristics of these PAEs that enable controlled assembly behaviors analogous to atomic phenomena, which allows for rational material design well beyond what can be achieved with other crystallization techniques.     

Nanoconfinement of spider silk fibrils begets superior strength, extensibility, and toughness

Silk is an exceptionally strong, extensible, and tough material made from simple protein building blocks. The molecular structure of dragline spider silk repeat units consists of semiamorphous and nanocrystalline β-sheet protein domains. Here we show by a series of computational experiments how the nanoscale properties of silk repeat units are scaled up to create macroscopic silk fibers with outstanding mechanical properties despite the presence of cavities, tears, and cracks. We demonstrate that the geometric confinement of silk fibrils to diameters of 50 ± 30 nm is critical to facilitate a powerful mechanism by which hundreds of thousands of protein domains synergistically resist deformation and failure to provide enhanced strength, extensibility, and toughness at the macroscale, closely matching experimentally measured mechanical properties. Through this mechanism silk fibers exploit the full potential of the nanoscale building blocks, regardless of the details of microscopic loading conditions and despite the presence of large defects. Experimental results confirm that silk fibers are composed of silk fibril bundles with diameters in the range of 20-150 nm, in agreement with our predicted length scale. Our study reveals a general mechanism to map nanoscale properties to the macroscale and provides a potent design strategy toward novel fiber and bulk nanomaterials through hierarchical structures.     

Tuning the Amphiphilicity of Building Blocks: Controlled Self‐Assembly and Disassembly for Functional Supramolecular Materials

Amphiphilicity is one of the molecular bases for self‐assembly. By tuning the amphiphilicity of building blocks, controllable self‐assembly can be realized. This article reviews different routes for tuning amphiphilicity and discusses different possibilities for self‐assembly and disassembly in a controlled manner. In general, this includes irreversible and reversible routes. The irreversible routes concern irreversible reactions taking place on the building blocks and changing their molecular amphiphilicity. The building blocks are then able to self‐assemble to form different supramolecular structures, but cannot remain stable upon loss of amphiphilicity. Compared to the irreversible routes, the reversible routes are more attractive due to the good control over the assembly and disassembly of the supramolecular structure formed via tuning of the amphiphilicity. These routes involve reversible chemical reactions and supramolecular approaches, and different external stimuli can be used to trigger reversible changes of amphiphilicity, including light, redox, pH, and enzymes. It is anticipated that this line of research can lead to the fabrication of new functional supramolecular assemblies and materials.     

Tubulin Double Helix: Lateral and Longitudinal Curvature Changes of Tubulin Protofilament

By virtue of their native structures, tubulin dimers are protein building blocks that are naturally preprogrammed to assemble into microtubules (MTs), which are cytoskeletal polymers. Here, polycation‐directed (i.e., electrostatically tunable) assembly of tubulins is demonstrated by conformational changes to the tubulin protofilament in longitudinal and lateral directions, creating tubulin double helices and various tubular architectures. Synchrotron small‐angle X‐ray scattering and transmission electron microscopy reveal a remarkable range of nanoscale assembly structures: single‐ and double‐layered double‐helix tubulin tubules. The phase transitions from MTs to the new assemblies are dependent on the size and concentration of polycations. Two characteristic scales that determine the number of observed phases are the size of polycation compared to the size of tubulin (≈4 nm) and to MT diameter (≈25 nm). This work suggests the feasibility of using polycations that have scissor‐ and glue‐like properties to achieve “programmable breakdown” of protein nanotubes, tearing MTs into double‐stranded tubulins and building up previously undiscovered nanostructures. Importantly, a new role of tubulins is defined as 2D shape‐controllable building blocks for supramolecular architectures. These findings provide insight into the design of protein‐based functional materials, for example, as metallization templates for nanoscale electronic devices, molecular screws, and drug delivery vehicles.     

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.     

Directing Gold Nanoparticles into Free‐Standing Honeycomb‐Like Ordered Mesoporous Superstructures

2D mesoporous materials fabricated via the assembly of nanoparticles (NPs) not only possess the unique properties of nanoscale building blocks but also manifest additional collective properties due to the interactions between NPs. In this work, reported is a facile and designable way to prepare free‐standing 2D mesoporous gold (Au) superstructures with a honeycomb‐like configuration. During the fabrication process, Au NPs with an average diameter of 5.0 nm are assembled into a superlattice film on a diethylene glycol substrate. Then, a subsequent thermal treatment at 180 °C induces NP attachment, forming the honeycomb‐like ordered mesoporous Au superstructures. Each individual NP connects with three neighboring NPs in the adjacent layer to form a tetrahedron‐based framework. Mesopores confined in the superstructure have a uniform size of 3.5 nm and are arranged in an ordered hexagonal array. The metallic bonding between Au NPs increases the structural stability of architected superstructures, allowing them to be easily transferred to various substrates. In addition, electron energy‐loss spectroscopy experiments and 3D finite‐difference time‐domain simulations reveal that electric field enhancement occurs at the confined mesopores when the superstructures are excited by light, showing their potential in nano‐plasmonic applications.     

Electrophoretic Build‐Up of Alternately Multilayered Films and Micropatterns Based on Graphene Sheets and Nanoparticles and their Applications in Flexible Supercapacitors

Graphene nanosheets and metal nanoparticles (NPs) have been used as nano‐building‐blocks for assembly into macroscale hybrid structures with promising performance in electrical devices. However, in most graphene and metal NP hybrid structures, the graphene sheets and metal NPs (e.g., AuNPs) do not enable control of the reaction process, orientation of building blocks, and organization at the nanoscale. Here, an electrophoretic layer‐by‐layer assembly for constructing multilayered reduced graphene oxide (RGO)/AuNP films and lateral micropatterns is presented. This assembly method allows easy control of the nano‐architecture of building blocks along the normal direction of the film, including the number and thickness of RGO and AuNP layers, in addition to control of the lateral orientation of the resultant multilayered structures. Conductivity of multilayered RGO/AuNP hybrid nano‐architecture shows great improvement caused by a bridging effect of the AuNPs along the out‐of‐plane direction between the upper and lower RGO layers. The results clearly show the potential of electrophoretic build‐up in the fabrication of graphene‐based alternately multilayered films and patterns. Finally, flexible supercapacitors based on multilayered RGO/AuNP hybrid films are fabricated, and excellent performance, such as high energy and power densities, are achieved.     

Electron Mobility of 24 cm2 V−1 s−1 in PbSe Colloidal‐Quantum‐Dot Superlattices

Colloidal quantum dots (CQDs) are nanoscale building blocks for bottom‐up fabrication of semiconducting solids with tailorable properties beyond the possibilities of bulk materials. Achieving ordered, macroscopic crystal‐like assemblies has been in the focus of researchers for years, since it would allow exploitation of the quantum‐confinement‐based electronic properties with tunable dimensionality. Lead‐chalcogenide CQDs show especially strong tendencies to self‐organize into 2D superlattices with micrometer‐scale order, making the array fabrication fairly simple. However, most studies concentrate on the fundamentals of the assembly process, and none have investigated the electronic properties and their dependence on the nanoscale structure induced by different ligands. Here, it is discussed how different chemical treatments on the initial superlattices affect the nanostructure, the optical, and the electronic‐transport properties. Transistors with average two‐terminal electron mobilities of 13 cm² V^?1 s^?1 and contactless mobility of 24 cm² V^?1 s^?1 are obtained for small‐area superlattice field‐effect transistors. Such mobility values are the highest reported for CQD devices wherein the quantum confinement is substantially present and are comparable to those reported for heavy sintering. The considerable mobility with the simultaneous preservation of the optical bandgap displays the vast potential of colloidal QD superlattices for optoelectronic applications.     

Mesoscale Block Copolymers

Materials composed of well‐defined mesoscale building blocks are ubiquitous in nature, with noted ability to assemble into hierarchical structures possessing exceptional physical and mechanical properties. Fabrication of similar synthetic mesoscale structures will offer opportunities for precise conformational tuning toward advantageous bulk properties, such as increased toughness or elastic modulus. This requires new materials designs to be discovered to impart such structural control. Here, the preparation of mesoscale polymers is achieved by solution fabrication of functional polymers containing photoinduced chemical triggers. Subsequent photopatterning affords mesoscale block copolymers composed of distinct segments of alternating chemical composition. When dispersed in appropriate solvents, selected segments form helices to generate architectures resembling block copolymers, but on an optically observable size scale. This approach provides a platform for producing mesoscale geometries with structural control and potential for driving materials assembly comparable to examples found in nature.     

Modulation of Multiscale 3D Lattices through Conformational Control: Painting Silk Inverse Opals with Water and Light

Structural proteins from naturally occurring materials are an inspiring template for material design and synthesis at multiple scales. The ability to control the assembly and conformation of such materials offers the opportunity to define fabrication approaches that recapitulate the dimensional hierarchy and structure–function relationships found in nature. A simple and versatile directed assembly method of silk fibroin, which allows the design of structures across multiple dimensional scales by generating and tuning structural color in large‐scale, macro defect‐free colloidally assembled 3D nanostructures in the form of silk inverse opals (SIOs) is reported. This approach effectively combines bottom‐up and top‐down techniques to obtain control on the nanoscale (through silk conformational changes), microscale (through patterning), and macroscale (through colloidal assembly), ultimately resulting in a controllable photonic lattice with predefined spectral behavior, with a resulting palette spanning almost the entire visible range. As a demonstration of the approach, examples of “multispectral” SIOs, paired with theoretical calculations and analysis of their response as a function of changes of lattice constants and refractive index contrast are illustrated.