Noncovalent systems are adaptive and allow facile processing and recycling. Can they be at the same time robust? How can one rationally design such systems? Can they compete with high-performance ...covalent materials? The recent literature reveals that noncovalent systems can be robust yet adaptive, self-healing, and recyclable, featuring complex nanoscale structures and unique functions. We review such systems, focusing on the rational design of strong noncovalent interactions, kinetically controlled pathway-dependent processes, complexity, and function. The overview of the recent examples points at the emergent field of noncovalent nanomaterials that can represent a versatile, multifunctional, and environmentally friendly alternative to conventional covalent systems.
Self‐assembly processes are very important in material sciences but are particularly difficult to predict quantitatively. This is the case for particulate magnetic materials in which field‐induced ...self‐assembly processes are essential. This article describes the recent advances in the development of predictive theoretical tools for the study of directed self‐assembly of superparamagnetic colloids under magnetic fields. A practical view is presented of how to employ the new concepts (derived from thermodynamic theory) to predict the possible assembled structures from the properties of the colloids and thermodynamic conditions. Quantitative prediction of kinetics is also discussed for the cases in which equilibrium theory is not relevant. Finally, an outline of fundamental aspects of the theory is presented.
Recent theoretical advances allow quantitative predictions of self‐assembly of superparamagnetic colloids under magnetic fields. This article describes how to employ self‐assembly thermodynamics to predict the possible assembled structures from the properties of the colloidal suspension (particle, size, magnetization, concentration, temperature). Quantitative prediction of kinetics is also discussed for the cases in which equilibrium theory is not relevant.
This article presents the recent developments of radical dispersion polymerizaton controlled by reversible addition fragmentation chain transfer (RAFT) for the production of block copolymer ...particles of various morphologies, such as core‐shell spheres, worms, or vesicles. It is not meant to be an exhaustive review but it rather provides guidelines for non‐specialists. The article is subdivided into eight sections. After a general introduction, the mechanism of polymerization‐induced self‐assembly (PISA) through RAFT‐mediated dispersion polymerization is presented and the different parameters that control the morphology produced are discussed. The next two sections are devoted to the choice of the monomer/solvent pair and the macroRAFT agent. Afterwards, post‐polymerization morphological order‐to‐order transitions (i.e. morphological transitions triggered by extrinsic stimuli) or order‐to‐disorder transitions (i.e. disassembly of chains) are discussed. Assemblies based on more complex polymer architectures, such as triblock copolymers, are presented next, and finally the possibility to stabilize these structures by crosslinking is reported. The manuscript ends with a short conclusion and an outlook.
RAFT dispersion polymerization is a versatile and efficient tool to prepare core‐shell particles of various morphologies by polymerization‐induced self‐assembly. This article reviews recent developments in this field, critically comments on them, and gives an outlook on further expected developments. It provides guidelines for non‐experts by highlighting important aspects that must carefully be considered when planning the preparation of core‐shell nanoobjects using this approach.
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‐ and protein‐based nanomaterials are important and promising for the novel and emerging antitumor techniques of photodynamic therapy and photothermal therapy. Recent advances in fabrication and application of phototherapeutic nanomaterials based on peptide and protein self‐assembly are highlighted, providing an increased understanding of the role of peptide and protein self‐assembly in improving the efficiency of antitumor phototherapies.
Luminescent hydrogels are of great potential for many fields, particularly serving as biomaterials ranging from fluorescent sensors to bioimaging agents. Here, robust luminescent hydrogels are ...reported using lanthanide complexes as emitting sources via a hierarchical organic–inorganic self‐assembling strategy. A new organic ligand is synthesized, consisting of a terpyridine unit and two flexibly linked methylimidazole moieties to coordinate with europium(III) (Eu3+) tri‐thenoyltrifluoroacetone (Eu(TTA)3), leading to a stable amphiphilic Eu3+‐containing monomer. Synergistic coordination of TTA and terpyridine units allows the monomer to self‐assemble into spherical micelles in water, thus maintaining the luminescence of Ln complexes in water. The micelles further coassemble with exfoliated Laponite nanosheets coated with sodium polyacrylate into networks based on the electrostatic interactions, resulting in the supramolecular hydrogel possessing strong luminescence, extraordinary mechanical property, as well as self‐healing ability. The results demonstrate that hierarchical organic–inorganic self‐assembly is a versatile and effective strategy to create luminescent hydrogels containing lanthanide complexes, giving rise to great potential applications as a soft material.
A luminescent supramolecular hydrogel using lanthanide complexes as emitting sources is constructed via a hierarchical organic–inorganic self‐assembling strategy, showing ultrastrong mechanical performance and extraordinary photophysical property.
Abstract Adaptation transcends scale in both natural and artificial systems, but delineating the causative factors of this phenomenon requires urgent clarification. Herein, we unravel the molecular ...requirements for adaptation and establish a link to rationalize adaptive behavior on a self-assembled level. These concepts are established by analyzing a model compound exhibiting both light- and pH-responsive units, which enable the combined or independent application of different stimuli. On a molecular level, adaptation arises from coupled stimuli, as the final outcome of the system depends on their sequence of application. However, in a self-assembled state, a single stimulus suffices to induce adaptation as a result of collective molecular behavior and the reversibility of non-covalent interactions. Our findings go beyond state-of-the-art (multi)stimuli-responsive systems and allow us to draw up design guidelines for adaptive behavior both at the molecular and supramolecular levels, which are fundamental criteria for the realization of intelligent matter.
Proteinaceous materials based on the amyloid core structure have recently been discovered at the origin of biological functionality in a remarkably diverse set of roles, and attention is increasingly ...turning towards such structures as the basis of artificial self‐assembling materials. These roles contrast markedly with the original picture of amyloid fibrils as inherently pathological structures. Here we outline the salient features of this class of functional materials, both in the context of the functional roles that have been revealed for amyloid fibrils in nature, as well as in relation to their potential as artificial materials. We discuss how amyloid materials exemplify the emergence of function from protein self‐assembly at multiple length scales. We focus on the connections between mesoscale structure and material function, and demonstrate how the natural examples of functional amyloids illuminate the potential applications for future artificial protein based materials.
Amyloid materials have recently been discovered at the origin of biological functionality and attention is increasingly turning toward their use in artificial materials. These roles contrast markedly with their original picture as pathological materials. A unified view of this class of functional materials, both in their natural roles and as synthetic materials, is given, and how function emerges directly from the hierarchical protein self‐assembly process is illustrated.
Ionic crystals (ICs) of the azobenzene derivatives show photoinduced IC–ionic liquid (IL) phase transition (photoliquefaction) upon UV‐irradiation, and the resulting cis‐azobenzene ILs are reversibly ...photocrystallized by illumination with visible light. The photoliquefaction of ICs is accompanied by a significant increase in ionic conductivity at ambient temperature. The photoliquefaction also brings the azobenzene ICs further significance as photon energy storage materials. The cis‐IL shows thermally induced crystallization to the trans‐IC phase. This transition is accompanied by exothermic peaks with a total ΔH of 97.1 kJ mol−1, which is almost double the conformational energy stored in cis‐azobenzene chromophores. Thus, the integration of photoresponsive ILs and self‐assembly pushes the limit of solar thermal batteries.
Going through a phase: ICs of azobenzene derivatives show a photoinduced IC–IL phase transition (photoliquefaction) upon UV irradiation, and the resulting cis‐azobenzene ILs are reversibly photocrystallized by illumination with visible light. The photoliquefaction of ICs is accompanied by a significant increase in ionic conductivity at ambient temperature and holds potential as energy storage materials.
Recent advances in polymer synthesis have significantly enhanced the ability to rationally design block copolymers with tailored functionality. The self‐assembly of these macromolecules in the solid ...state or in solution allows the formation of nanostructured materials with a variety of properties and potential functions. This Review illustrates recent progress in the field of block copolymer materials by highlighting selected emerging applications.
Form and function: Functional block copolymers of well‐defined composition and length are readily available today thanks to recent advances in synthetic polymer chemistry. Their ability to self‐assemble into a great diversity of structures on the nanoscale, along with their customizable chemical functionalities, makes block copolymers highly desirable materials for a wide range of applications.
