Programmable Construction of Peptide‐Based Materials in Living Subjects: From Modular Design and Morphological Control to Theranostics

Self‐assembled nanomaterials show potential high efficiency as theranostics for high‐performance bioimaging and disease treatment. However, the superstructures of pre‐assembled nanomaterials may change in the complicated physiological conditions, resulting in compromised properties and/or biofunctions. Taking advantage of chemical self‐assembly and biomedicine, a new strategy of “in vivo self‐assembly” is proposed to in situ construct functional nanomaterials in living subjects to explore new biological effects. Herein, recent advances on peptide‐based nanomaterials constructed by the in vivo self‐assembly strategy are summarized. Modular peptide building blocks with various functions, such as targeting, self‐assembly, tailoring, and biofunctional motifs, are employed for the construction of nanomaterials. Then, self‐assembly of these building blocks in living systems to construct various morphologies of nanostructures and corresponding unique biological effects, such as assembly/aggregation‐induced retention (AIR), are introduced, followed by their applications in high‐performance drug delivery and bioimaging. Finally, an outlook and perspective toward future developments of in vivo self‐assembled peptide‐based nanomaterials for translational medicine are concluded.     

Directed Self‐Assembly of Liquid‐Crystalline Molecular Building Blocks for Sub‐5 nm Nanopatterning

The thin‐film directed self‐assembly of molecular building blocks into oriented nanostructure arrays enables next‐generation lithography at the sub‐5 nm scale. Currently, the fabrication of inorganic arrays from molecular building blocks is restricted by the limited long‐range order and orientation of the materials, as well as suitable methodologies for creating lithographic templates at sub‐5 nm dimensions. In recent years, higher‐order liquid crystals have emerged as functional thin films for organic electronics, nanoporous membranes, and templated synthesis, which provide opportunities for their use as lithographic templates. By choosing examples from these fields, recent progress toward the design of molecular building blocks is highlighted, with an emphasis on liquid crystals, to access sub‐5 nm features, their directed self‐assembly into oriented thin films, and, importantly, the fabrication of inorganic arrays. Finally, future challenges regarding sub‐5 nm patterning with liquid crystals are discussed.     

“Dual‐Template” Synthesis of One‐Dimensional Conductive Nanoparticle Superstructures from Coordination Metal–Peptide Polymer Crystals

Bottom‐up fabrication of self‐assembled structures made of nanoparticles may lead to new materials, arrays and devices with great promise for myriad applications. Here a new class of metal–peptide scaffolds is reported: coordination polymer Ag(I)‐DLL belt‐like crystals, which enable the dual‐template synthesis of more sophisticated nanoparticle superstructures. In these biorelated scaffolds, the self‐assembly and recognition capacities of peptides and the selective reduction of Ag(I) ions to Ag are simultaneously exploited to control the growth and assembly of inorganic nanoparticles: first on their surfaces, and then inside the structures themselves. The templated internal Ag nanoparticles are well confined and closely packed, conditions that favour electrical conductivity in the superstructures. It is anticipated that these Ag(I)‐DLL belts could be applied to create long (>100 μm) conductive Ag@Ag nanoparticle superstructures and polymetallic, multifunctional Fe₃O₄@Ag nanoparticle composites that marry the magnetic and conductive properties of the two nanoparticle types.     

Self‐Assembled Peptide‐ and Protein‐Based Nanomaterials for Antitumor Photodynamic and Photothermal Therapy

Tremendous interest in self‐assembly of peptides and proteins towards functional nanomaterials has been inspired by naturally evolving self‐assembly in biological construction of multiple and sophisticated protein architectures in organisms. Self‐assembled peptide and protein nanoarchitectures are excellent promising candidates for facilitating biomedical applications due to their advantages of structural, mechanical, and functional diversity and high biocompability and biodegradability. Here, this review focuses on the self‐assembly of peptides and proteins for fabrication of phototherapeutic nanomaterials for antitumor photodynamic and photothermal therapy, with emphasis on building blocks, non‐covalent interactions, strategies, and the nanoarchitectures of self‐assembly. The exciting antitumor activities achieved by these phototherapeutic nanomaterials are also discussed in‐depth, along with the relationships between their specific nanoarchitectures and their unique properties, providing an increased understanding of the role of peptide and protein self‐assembly in improving the efficiency of photodynamic and photothermal therapy.     

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.     

Self‐Templating Approaches to Hollow Nanostructures

This current research progress on the fabrication of hollow nanostructures by using self‐templating methods is reviewed. After a brief introduction to the unique properties and applications of hollow nanostructures and the three general fabrication routes, the discussions are focused on the five main self‐templating strategies, including galvanic replacement, the Kirkendall effect, Ostwald ripening, dissolution–regrowth, and the surface‐protected hollowing process. Some newly developed synthetic routes are selected and discussed in detail. In conclusion, a summary and the perspectives on the directions that might lead the future development of this exciting field are presented.     

Supramolecular Materials via Block Copolymer Self‐Assembly

This review discusses the potential of block copolymer type macromolecular building blocks for the preparation of self‐assembled materials. Three different classes of block copolymer type architectures will be distinguished: (i) coil–coil diblock copolymers, (ii) rod–coil diblock copolymers, and (iii) rod–coil diblock oligomers. The basic principles that underlie the self‐assembly of each of these different building blocks will be discussed. These theoretical considerations are complemented with examples from recent literature that illustrate the potential of the different types of block copolymers to prepare (functional) supramolecular materials. Finally, several strategies will be presented that could allow the preparation of stimuli‐sensitive self‐assembled materials, i.e., materials whose properties can be reversibly manipulated under the action of appropriate external stimuli.     

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.     

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.     

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.     

Interparticle Forces Underlying Nanoparticle Self‐Assemblies

Studies on the self‐assembly of nanoparticles have been a hot topic in nanotechnology for decades and still remain relevant for the present and future due to their tunable collective properties as well as their remarkable applications to a wide range of fields. The novel properties of nanoparticle assemblies arise from their internal interactions and assemblies with the desired architecture key to constructing novel nanodevices. Therefore, a comprehensive understanding of the interparticle forces of nanoparticle self‐assemblies is a pre‐requisite to the design and control of the assembly processes, so as to fabricate the ideal nanomaterial and nanoproducts. Here, different categories of interparticle forces are classified and discussed according to their origins, behaviors and functions during the assembly processes, and the induced collective properties of the corresponding nanoparticle assemblies. Common interparticle forces, such as van der Waals forces, electrostatic interactions, electromagnetic dipole‐dipole interactions, hydrogen bonds, solvophonic interactions, and depletion interactions are discussed in detail. In addition, new categories of assembly principles are summarized and introduced. These are termed template‐mediated interactions and shape‐complementary interactions. A deep understanding of the interactions inside self‐assembled nanoparticles, and a broader perspective for the future synthesis and fabrication of these promising nanomaterials is provided.     

3D Nanofabrication via Chemo‐Mechanical Transformation of Nanocrystal/Bulk Heterostructures

Planar nanocrystal/bulk heterostructures are transformed into 3D architectures by taking advantage of the different chemical and mechanical properties of nanocrystal and bulk thin films. Nanocrystal/bulk heterostructures are fabricated via bottom‐up assembly and top‐down fabrication. The nanocrystals are capped by long ligands introduced in their synthesis, and therefore their surfaces are chemically addressable, and their assemblies are mechanically “soft,” in contrast to the bulk films. Chemical modification of the nanocrystal surface, exchanging the long ligands for more compact chemistries, triggers large volume shrinkage of the nanocrystal layer and drives bending of the nanocrystal/bulk heterostructures. Exploiting the differential chemo‐mechanical properties of nanocrystal and bulk materials, the scalable fabrication of designed 3D, cell‐sized nanocrystal/bulk superstructures is demonstrated, which possess unique functions derived from nanocrystal building blocks.     

Block Copolymers as a Tool for Nanomaterial Fabrication

In this review the latest developments regarding the use of self‐assembled copolymers for the fabrication of nanomaterials will be presented and their real potential evaluated. Most of the strategies reported so far are herewith classified under two main approaches: a) use of block copolymers as nanostructured materials, either “as they are” or through a selective isolation of one or more component blocks, and b) as templates for the synthesis of metallic or semiconducting nanomaterials. The problems of the orientation and large‐scale order of self‐organizing block copolymer mesophases will be also introduced, due to their importance as a route towards further improvements of the nanofabrication means.     

A Nonconventional Approach to Patterned Nanoarrays of DNA Strands for Template‐Assisted Assembly of Polyfluorene Nanowires

DNA molecules have been widely recognized as promising building blocks for constructing functional nanostructures with two main features, that is, self‐assembly and rich chemical functionality. The intrinsic feature size of DNA makes it attractive for creating versatile nanostructures. Moreover, the ease of access to tune the surface of DNA by chemical functionalization offers numerous opportunities for many applications. Herein, a simple yet robust strategy is developed to yield the self‐assembly of DNA by exploiting controlled evaporative assembly of DNA solution in a unique confined geometry. Intriguingly, depending on the concentration of DNA solution, highly aligned nanostructured fibrillar‐like arrays and well‐positioned concentric ring‐like superstructures composed of DNAs are formed. Subsequently, the ring‐like negatively charged DNA superstructures are employed as template to produce conductive organic nanowires on a silicon substrate by complexing with a positively charged conjugated polyelectrolyte poly[9,9‐bis(6′‐N,N,N‐trimethylammoniumhexyl)fluorene dibromide] (PF2) through the strong electrostatic interaction. Finally, a monolithic integration of aligned arrays of DNA‐templated PF2 nanowires to yield two DNA/PF2‐based devices is demonstrated. It is envisioned that this strategy can be readily extended to pattern other biomolecules and may render a broad range of potential applications from the nucleotide sequence and hybridization as recognition events to transducing elements in chemical sensors.     

Nanogap Electrodes

Nanogap electrodes (namely, a pair of electrodes with a nanometer gap) are fundamental building blocks for the fabrication of nanometer‐sized devices and circuits. They are also important tools for the examination of material properties at the nanometer scale, even at the molecular scale. In this review, the techniques for the fabrication of nanogap electrodes, the preparation of assembled devices based on the nanogap electrodes, and the potential application of these nanodevices for analysis of material properties are introduced. The history, the research status, and the prospects of nanogap electrodes are also discussed.     

Peptide‐Based Nanotubes and Their Applications in Bionanotechnology

In nature, biological nanomaterials are synthesized under ambient conditions in a natural microscopic‐sized laboratory, such as a cell. Biological molecules, such as peptides and proteins, undergo self‐assembly processes in vivo and in vitro, and these monomers are assembled into various nanometer‐scale structures at room temperature and atmospheric pressure. The self‐assembled peptide nanostructures can be further organized to form nanowires, nanotubes, and nanoparticles via their molecular‐recognition functions. The application of molecular self‐assemblies of synthetic peptides as nanometer‐scale building blocks in devices is robust, practical, and affordable due to their advantages of reproducibility, large‐scale production ability, monodispersity, and simpler experimental methods. It is also beneficial that smart functionalities can be added at desired positions in peptide nanotubes through well‐established chemical and peptide syntheses. These features of peptide‐based nanotubes are the driving force for investigating and developing peptide nanotube assemblies for biological and non‐biological applications.     

Bioinspired Photonic Pigments from Colloidal Self‐Assembly

The natural world is a colorful environment. Stunning displays of coloration have evolved throughout nature to optimize camouflage, warning, and communication. The resulting flamboyant visual effects and remarkable dynamic properties, often caused by an intricate structural design at the nano‐ and microscale, continue to inspire scientists to unravel the underlying physics and to recreate the observed effects. Here, the methodologies to create bioinspired photonic pigments using colloidal self‐assembly approaches are considered. The physics governing the interaction of light with structural features and natural examples of structural coloration are briefly introduced. It is then outlined how the self‐assembly of colloidal particles, acting as wavelength‐scale building blocks, can be particularly useful to replicate coloration from nature. Different coloration effects that result from the defined structure of the self‐assembled colloids are introduced and it is highlighted how these optical properties can be translated into photonic pigments by modifications of the assembly processes. The importance of absorbing elements, as well as the role of surface chemistry and wettability to control structural coloration is discussed. Finally, approaches to integrate dynamic control of coloration into such self‐assembled photonic pigments are outlined.     

A Hydrangea‐Like Superstructure of Open Carbon Cages with Hierarchical Porosity and Highly Active Metal Sites

Carbon micro‐/nanocages have attracted great attention owing to their wide potential applications. Herein, a self‐templated strategy is presented for the synthesis of a hydrangea‐like superstructure of open carbon cages through morphology‐controlled thermal transformation of core@shell metal–organic frameworks (MOFs). Direct pyrolysis of core@shell zinc (Zn)@cobalt (Co)‐MOFs produces well‐defined open‐wall nitrogen‐doped carbon cages. By introducing guest iron (Fe) ions into the core@shell MOF precursor, the open carbon cages are self‐assembled into a hydrangea‐like 3D superstructure interconnected by carbon nanotubes, which are grown in situ on the Fe–Co alloy nanoparticles formed during the pyrolysis of Fe‐introduced Zn@Co‐MOFs. Taking advantage of such hierarchically porous superstructures with excellent accessibility, synergetic effects between the Fe and the Co, and the presence of catalytically active sites of both metal nanoparticles and metal–N_x species, this superstructure of open carbon cages exhibits efficient bifunctional catalysis for both oxygen evolution reaction and oxygen reduction reaction, achieving a great performance in Zn–air batteries.     

Hollow Micro/Nanostructured Ceria‐Based Materials: Synthetic Strategies and Versatile Applications

Hollow micro/nanostructured CeO₂‐based materials (HMNCMs) have triggered intensive attention as a result of their unique structural traits, which arise from their hollowness and the fascinating physicochemical properties of CeO₂. This attention has led to widespread applications with improved performance. Herein, a comprehensive overview of methodologies applied for the synthesis of various hollow structures, such as hollow spheres, nanotubes, nanoboxes, and multishelled hollow spheres, is provided. The synthetic strategies toward CeO₂ hollow structures are classified into three major categories: 1) well‐established template‐assisted (hard‐, soft‐, and in situ template) methods; 2) newly emerging self‐template approaches, including selective etching, Ostwald ripening, the Kirkendall effect, galvanic replacement, etc.; 3) bottom‐up self‐organized formation synthesis (namely, oriented attachment and self‐deformation). Their underlying mechanisms are concisely described and discussed in detail, the differences and similarities of which are compared transversely and longitudinally. Niche applications of HMNCMs in a wide range of fields including catalysis, energy conversion and storage, sensors, absorbents, photoluminescence, and biomedicines are reviewed. Finally, an outlook of future opportunities and challenges in the synthesis and application of CeO₂‐based hollow structures is also presented.     

Hollow Functional Materials Derived from Metal–Organic Frameworks: Synthetic Strategies,Conversion Mechanisms,and Electrochemical Applications

Hollow materials derived from metal–organic frameworks (MOFs), by virtue of their controllable configuration, composition, porosity, and specific surface area, have shown fascinating physicochemical properties and widespread applications, especially in electrochemical energy storage and conversion. Here, the recent advances in the controllable synthesis are discussed, mainly focusing on the conversion mechanisms from MOFs to hollow‐structured materials. The synthetic strategies of MOF‐derived hollow‐structured materials are broadly sorted into two categories: the controllable synthesis of hollow MOFs and subsequent pyrolysis into functional materials, and the controllable conversion of solid MOFs with predesigned composition and morphology into hollow structures. Based on the formation processes of hollow MOFs and the conversion processes of solid MOFs, the synthetic strategies are further conceptually grouped into six categories: template‐mediated assembly, stepped dissolution–regrowth, selective chemical etching, interfacial ion exchange, heterogeneous contraction, and self‐catalytic pyrolysis. By analyzing and discussing 14 types of reaction processes in detail, a systematic mechanism of conversion from MOFs to hollow‐structured materials is exhibited. Afterward, the applications of these hollow structures as electrode materials for lithium‐ion batteries, hybrid supercapacitors, and electrocatalysis are presented. Finally, an outlook on the emergent challenges and future developments in terms of their controllable fabrications and electrochemical applications is further discussed.