Tuning Molecular Self‐Assembly on Bulk Insulator Surfaces by Anchoring of the Organic Building Blocks

Molecular self‐assembly constitutes a versatile strategy for creating functional structures on surfaces. Tuning the subtle balance between intermolecular and molecule‐surface interactions allows structure formation to be tailored at the single‐molecule level. While metal surfaces usually exhibit interaction strengths in an energy range that favors molecular self‐assembly, dielectric surfaces having low surface energies often lack sufficient interactions with adsorbed molecules. As a consequence, application‐relevant, bulk insulating materials pose significant challenges when considering them as supporting substrates for molecular self‐assembly. Here, the current status of molecular self‐assembly on surfaces of wide‐bandgap dielectric crystals, investigated under ultrahigh vacuum conditions at room temperature, is reviewed. To address the major issues currently limiting the applicability of molecular self‐assembly principles in the case of dielectric surfaces, a systematic discussion of general strategies is provided for anchoring organic molecules to bulk insulating materials.     

Beta‐Sheet‐Forming,Self‐Assembled Peptide Nanomaterials towards Optical,Energy, and Healthcare Applications

Peptide self‐assembly is an attractive route for the synthesis of intricate organic nanostructures that possess remarkable structural variety and biocompatibility. Recent studies on peptide‐based, self‐assembled materials have expanded beyond the construction of high‐order architectures; they are now reporting new functional materials that have application in the emerging fields such as artificial photosynthesis and rechargeable batteries. Nevertheless, there have been few reviews particularly concentrating on such versatile, emerging applications. Herein, recent advances in the synthesis of self‐assembled peptide nanomaterials (e.g., cross β‐sheet‐based amyloid nanostructures, peptide amphiphiles) are selectively reviewed and their new applications in diverse, interdisciplinary fields are described, ranging from optics and energy storage/conversion to healthcare. The applications of peptide‐based self‐assembled materials in unconventional fields are also highlighted, such as photoluminescent peptide nanostructures, artificial photosynthetic peptide nanomaterials, and lithium‐ion battery components. The relation of such functional materials to the rapidly progressing biomedical applications of peptide self‐assembly, which include biosensors/chips and regenerative medicine, are discussed. The combination of strategies shown in these applications would further promote the discovery of novel, functional, small materials.     

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.     

Template‐Free,Surfactant‐Mediated Orientation of Self‐Assembled Supercrystals of Metal–Organic Framework Particles

Mesoscale self‐assembly of particles into supercrystals is important for the design of functional materials such as photonic and plasmonic crystals. However, while much progress has been made in self‐assembling supercrystals adopting diverse lattices and using different types of particles, controlling their growth orientation on surfaces has received limited success. Most of the latter orientation control has been achieved via templating methods in which lithographic processes are used to form a patterned surface that acts as a template for particle assembly. Herein, a template‐free method to self‐assemble (111)‐, (100)‐, and (110)‐oriented face‐centered cubic supercrystals of the metal–organic framework ZIF‐8 particles by adjusting the amount of surfactant (cetyltrimethylammonium bromide) used is described. It is shown that these supercrystals behave as photonic crystals whose properties depend on their growth orientation. This control on the orientation of the supercrystals dictates the orientation of the composing porous particles that might ultimately facilitate pore orientation on surfaces for designing membranes and sensors.     

A “Phase Separation” Molecular Design Strategy Towards Large‐Area 2D Molecular Crystals

2D molecular crystals (2DMCs) have attracted considerable attention because of their unique optoelectronic properties and potential applications. Taking advantage of the solution processability of organic semiconductors, solution self‐assembly is considered an effective way to grow large‐area 2DMCs. However, this route is largely blocked because a precise molecular design towards 2DMCs is missing and little is known about the relationship between 2D solution self‐assembly and molecular structure. A “phase separation” molecular design strategy towards 2DMCs is proposed and layer‐by‐layer growth of millimeter‐sized monolayer or few‐layer 2DMCs is realized. High‐performance organic phototransistors are constructed based on the 2DMCs with unprecedented photosensitivity (2.58 × 10⁷), high responsivity (1.91 × 10⁴ A W^?1), and high detectivity (4.93 × 10¹⁵ Jones). This “phase separation” molecular design strategy provides a guide for the design and synthesis of novel organic semiconductors that self‐assemble into large‐area 2DMCs for advanced organic (opto)electronics.     

Multi‐Component Organic Layers on Metal Substrates

Increasingly high hopes are being placed on organic semiconductors for a variety of applications. Progress along these lines, however, requires the design and growth of increasingly complex systems with well‐defined structural and electronic properties. These issues have been studied and reviewed extensively in single‐component layers, but the focus is gradually shifting towards more complex and functional multi‐component assemblies such as donor–acceptor networks. These blends show different properties from those of the corresponding single‐component layers, and the understanding on how these properties depend on the different supramolecular environment of multi‐component assemblies is crucial for the advancement of organic devices. Here, our understanding of two‐dimensional multi‐component layers on solid substrates is reviewed. Regarding the structure, the driving forces behind the self‐assembly of these systems are described. Regarding the electronic properties, recent insights into how these are affected as the molecule's supramolecular environment changes are explained. Key information for the design and controlled growth of complex, functional multicomponent structures by self‐assembly is summarized.     

Self‐Assembly of Graphene Oxide at Interfaces

Due to its amphiphilic property, graphene oxide (GO) can achieve a variety of nanostructures with different morphologies (for example membranes, hydrogel, crumpled particles, hollow spheres, sack‐cargo particles, Pickering emulsions, and so on) by self‐assembly. The self‐assembly is mostly derived from the self‐concentration of GO sheets at various interfaces, including liquid‐air, liquid‐liquid and liquid‐solid interfaces. This paper gives a comprehensive review of these assembly phenomena of GO at the three types of interfaces, the derived interfacial self‐assembly techniques, and the as‐obtained assembled materials and their properties. The interfacial self‐assembly of GO, enabled by its fantastic features including the amphiphilicity, the negatively charged nature, abundant oxygen‐containing groups and two‐dimensional flexibility, is highlighted as an easy and well‐controlled strategy for the design and preparation of functionalized carbon materials, and the use of self‐assembly for uniform hybridization is addressed for preparing hybrid carbon materials with various functions. A number of new exciting and potential applications are also presented for the assembled GO‐based materials. This contribution concludes with some personal perspectives on future challenges before interfacial self‐assembly may become a major strategy for the application‐targeted design and preparation of functionalized carbon materials.     

Native MicroRNA Targets Trigger Self‐Assembly of Nanozyme‐Patterned Hollowed Nanocuboids with Optimal Interparticle Gaps for Plasmonic‐Activated Cancer Detection

The modernized use of nucleic acid (NA) sequences to drive nanostructure self‐assembly has given rise to a new class of designed nanomaterials with controllable plasmonic functionalities for broad surface‐enhanced Raman scattering (SERS)‐based bioanalysis applications. Herein, dual usage of microRNAs (miRNAs) as both valuable cancer biomarkers and direct self‐assembly triggers is identified and capitalized upon for custom‐designed plasmonic nanostructures. Through strict NA hybridization of miRNA targets, Au nanospheres selectively self‐assemble onto hollowed Au/Ag alloy nanocuboids with ideal interparticle distances (≈2.3 nm) for optimal SERS signaling. The intrinsic material properties of the self‐assembled nanostructures further elevate miRNA detection performance via nanozyme catalytic SERS signaling cascades. This enables fM‐level miR‐107 detection limit within a clinically‐relevant range without any molecular target amplification. The miRNA‐triggered nanostructure self‐assembly approach is further applied in clinical patient samples, and showcases the potential of miR‐107 as a non‐invasive prostate cancer diagnostic biomarker. The use of miRNA targets to drive nanostructure self‐assembly holds great promise as a practical tool for miRNA detection in disease applications.     

Layer‐by‐Layer Hydrogen‐Bonded Polymer Films: From Fundamentals to Applications

Recent years have seen increasing interest in the construction of nanoscopically layered materials involving aqueous‐based sequential assembly of polymers on solid substrates. In the booming research area of layer‐by‐layer (LbL) assembly of oppositely charged polymers, self‐assembly driven by hydrogen bond formation emerges as a powerful technique. Hydrogen‐bonded (HB) LbL materials open new opportunities for LbL films, which are more difficult to produce than their electrostatically assembled counterparts. Specifically, the new properties associated with HB assembly include: 1) the ease of producing films responsive to environmental pH at mild pH values, 2) numerous possibilities for converting HB films into single‐ or two‐component ultrathin hydrogel materials, and 3) the inclusion of polymers with low glass transition temperatures (e.g., poly(ethylene oxide)) within ultrathin films. These properties can lead to new applications for HB LbL films, such as pH‐ and/or temperature‐responsive drug delivery systems, materials with tunable mechanical properties, release films dissolvable under physiological conditions, and proton‐exchange membranes for fuel cells. In this report, we discuss the recent developments in the synthesis of LbL materials based on HB assembly, the study of their structure–property relationships, and the prospective applications of HB LbL constructs in biotechnology and biomedicine.     

Fluorescent Nanoparticles Based on Self‐Assembled π‐Conjugated Systems

π‐Conjugated molecules are interesting components to prepare fluorescent nanoparticles. From the use of polymer chains that form small aggregates in water to the self‐assembly of small chromophoric segments into highly ordered structures, the preparation of these materials allows to develop systems with applications as sensors or biolabels. The potential functionalization of the nanoparticles can lead to specific probing. This progress report describes the recent advances in the preparation of such emittive organic nanoparticles.     

Self‐Assembled Monolayers as Patterning Tool for Organic Electronic Devices

The patterning of functional materials represents a crucial step for the implementation of organic semiconducting materials into functional devices. Classical patterning techniques such as photolithography or shadow masking exhibit certain limitations in terms of choice of materials, processing techniques and feasibility for large area fabrication. The use of self‐assembled monolayers (SAMs) as a patterning tool offers a wide variety of opportunities, from the region‐selective deposition of active components to guiding the crystallization direction. Here, we discuss general techniques and mechanisms for SAM‐based patterning and show that all necessary components for organic electronic devices, i.e., conducting materials, dielectrics, organic semiconductors, and further functional layers can be patterned with the use of self‐assembled monolayers. The advantages and limitations, and potential further applications of patterning approaches based on self‐assembled monolayers are critically discussed.     

Biocatalytically Triggered Co‐Assembly of Two‐Component Core/Shell Nanofibers

For the development of applications and novel uses for peptide nanostructures, robust routes for their surface functionalization, that ideally do not interfere with their self‐assembly properties, are required. Many existing methods rely on covalent functionalization, where building blocks are appended with functional groups, either pre‐ or post‐assembly. A facile supramolecular approach is demonstrated for the formation of functionalized nanofibers by combining the advantages of biocatalytic self‐assembly and surfactant/gelator co‐assembly. This is achieved by enzymatically triggered reconfiguration of free flowing micellar aggregates of pre‐gelators and functional surfactants to form nanofibers that incorporate and display the surfactants’ functionality at the surface. Furthermore, by varying enzyme concentration, the gel stiffness and supramolecular organization of building blocks can be varied.     

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.     

Self‐Assembled Peptide‐Based Nanomaterials for Biomedical Imaging and Therapy

Peptide‐based materials are one of the most important biomaterials, with diverse structures and functionalities. Over the past few decades, a self‐assembly strategy is introduced to construct peptide‐based nanomaterials, which can form well‐controlled superstructures with high stability and multivalent effect. More recently, peptide‐based functional biomaterials are widely utilized in clinical applications. However, there is no comprehensive review article that summarizes this growing area, from fundamental research to clinic translation. In this review, the recent progress of peptide‐based materials, from molecular building block peptides and self‐assembly driving forces, to biomedical and clinical applications is systematically summarized. Ex situ and in situ constructed nanomaterials based on functional peptides are presented. The advantages of intelligent in situ construction of peptide‐based nanomaterials in vivo are emphasized, including construction strategy, nanostructure modulation, and biomedical effects. This review highlights the importance of self‐assembled peptide nanostructures for nanomedicine and can facilitate further knowledge and understanding of these nanosystems toward clinical translation.     

One‐Step Construction of N,P‐Codoped Porous Carbon Sheets/CoP Hybrids with Enhanced Lithium and Potassium Storage

Despite the desirable advancement in synthesizing transition‐metal phosphides (TMPs)‐based hybrid structures, most methods depend on foreign‐template‐based multistep procedures for tailoring the specific structure. Herein, a self‐template and recrystallization–self‐assembly strategy for the one‐step synthesis of core–shell‐like cobalt phosphide (CoP) nanoparticles embedded into nitrogen and phosphorus codoped porous carbon sheets (CoP?NPPCS), is first proposed. Relying on the unusual coordination ability of melamine with metal ions and the cooperative hydrogen bonding of melamine and phytic acid to form a 2D network, a self‐synthesized single precursor can be attained. Importantly, this approach can be easily expanded to synthesize other TMPs?NPPCS. Due to the unique compositional and structural characteristics, these CoP?NPPCSs manifest outstanding electrochemical performances as anode materials for both lithium‐ and potassium‐ion batteries. The unusual hybrid architecture, the high specific surface area, and porous features make the CoP?NPPCS attractive for other potential applications, such as supercapacitors and electrocatalysis.     

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.     

Self‐Assembled Photonic Structures

Photonic crystals have proven their potential and are nowadays a familiar concept. They have been approached from many scientific and technological flanks. Among the many techniques devised to implement this technology self‐assembly has always been one of great popularity surely due to its ease of access and the richness of results offered. Self‐assembly is also probably the approach entailing more materials aspects owing to the fact that they lend themselves to be fabricated by a great many, very different methods on a vast variety of materials and to multiple purposes. To these well‐known material systems a new sibling has been born (photonic glass) expanding the paradigm of optical materials inspired by solid state physics crystal concept. It is expected that they may become an important player in the near future not only because they complement the properties of photonic crystals but because they entice the researchers’ curiosity. In this review a panorama is presented of the state of the art in this field with the view to serve a broad community concerned with materials aspects of photonic structures and more so those interested in self‐assembly.     

Temperature‐Enhanced Solvent Vapor Annealing of a C3 Symmetric Hexa‐peri‐Hexabenzocoronene: Controlling the Self‐Assembly from Nano‐ to Macroscale

Temperature‐enhanced solvent vapor annealing (TESVA) is used to self‐assemble functionalized polycyclic aromatic hydrocarbon molecules into ordered macroscopic layers and crystals on solid surfaces. A novel C₃ symmetric hexa‐peri‐hexabenzocoronene functionalized with alternating hydrophilic and hydrophobic side chains is used as a model system since its multivalent character can be expected to offer unique self‐assembly properties and behavior in different solvents. TESVA promotes the molecule's long‐range mobility, as proven by their diffusion on a Si/SiO_x surface on a scale of hundreds of micrometers. This leads to self‐assembly into large, ordered crystals featuring an edge‐on columnar type of arrangement, which differs from the morphologies obtained using conventional solution‐processing methods such as spin‐coating or drop‐casting. The temperature modulation in the TESVA makes it possible to achieve an additional control over the role of hydrodynamic forces in the self‐assembly at surfaces, leading to a macroscopic self‐healing within the adsorbed film notably improved as compared to conventional solvent vapor annealing. This surface re‐organization can be monitored in real time by optical and atomic force microscopy.     

Interfacial Capillary‐Force‐Driven Self‐Assembly of Monolayer Colloidal Crystals for Supersensitive Plasmonic Sensors

Colloidal lithography technology based on monolayer colloidal crystals (MCCs) is considered as an outstanding candidate for fabricating large‐area patterned functional nanostructures and devices. Although many efforts have been devoted to achieve various novel applicatons, the quality of MCCs, a key factor for the controllability and reproducibility of the patterned nanostructures, is often overlooked. In this work, an interfacial capillary‐force‐driven self‐assembly strategy (ICFDS) is designed to realize a high‐quality and highly‐ordered hexagonal monolayer MCCs array by resorting the capillary effect of the interfacial water film at substrate surface as well as controlling the zeta potential of the polystyrene particles. Compared with the conventional self‐assembly method, this approach can realize the reself‐assembly process on the substrate surface with few colloidal aggregates, vacancy, and crystal boundary defects. Furthermore, various typical large‐scale nanostructure arrays are achieved by combining reactive ion etching, metal‐assisted chemical etching, and so forth. Specifically, benefiting from the as‐fabricated high‐quality 2D hexagonal colloidal crystals, the surface plasmon resonance (SPR) sensors achieve an excellent refractive index sensitivity value of 3497 nm RIU^?1, which is competent for detecting bovine serum albumin with an ultralow concentration of 10^?8 m . This work opens a window to prepare high‐quality MCCs for more potential applications.     

Self‐Assembly of Hyperbranched Polymers and Its Biomedical Applications

Hyperbranched polymers (HBPs) are highly branched macromolecules with a three‐dimensional dendritic architecture. Due to their unique topological structure and interesting physical/chemical properties, HBPs have attracted wide attention from both academia and industry. In this paper, the recent developments in HBP self‐assembly and their biomedical applications have been comprehensively reviewed. Many delicate supramolecular structures from zero‐dimension (0D) to three‐dimension (3D), such as micelles, fibers, tubes, vesicles, membranes, large compound vesicles and physical gels, have been prepared through the solution or interfacial self‐assembly of amphiphilic HBPs. In addition, these supramolecular structures have shown promising applications in the biomedical areas including drug delivery, protein purification/detection/delivery, gene transfection, antibacterial/antifouling materials and cytomimetic chemistry. Such developments promote the interdiscipline researches among surpramolecular chemistry, biomedical chemistry, nano­technology and functional materials.