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.
The deployment of peptide‐based self‐assembly has rapidly diversified toward the fabrication of novel functional materials with elaborate nanostructures for application in optics, energy, healthcare, and closely interrelating fields. With a focus on β‐sheet formation, peptide‐based self‐assembled nanomaterials and their recent applications in photonic devices, energy storage and conversion, biosensors, as well as to regenerative medicine are reviewed.
The field of supramolecular chemistry and molecular self-assembly has entered a new phase in which the use of chemical reactions to create out-of-equilibrium molecular assemblies is becoming more ...common. These dynamic assemblies have vastly different properties than their in-equilibrium counterparts, which include the ability to be controlled over space and time or the ability to self-replicate. Such behaviors would set significant steps toward the synthesis of artificial life. However, a limiting factor toward the revolution of the field is the lack of clear definitions and design rules for such systems. In this review, we explain the core principles that help to design energy-dissipating chemical reaction cycles that can drive molecular assemblies. We discuss strategies for coupling these reaction cycles to building blocks for the materials. We conclude with an outlook for the field of dissipative self-assembly and its potential role as a material or model for life.
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If we want to create materials as sophisticated as biological ones, we should use strategies similar to those used in biology. Living biological materials, like skin or bone, are made through the self-assembly of molecules and exist far out of chemical equilibrium, which means that these molecular assemblies require the constant input and dissipation of energy in order to be sustained. Because of their dissipative nature, living materials possess properties that we typically associate with life and do not find in classical materials: properties such as spontaneous emergence, the ability to self-heal, or the ability to adapt to a change in environment. Inspired by biology, researchers have been coupling energy-dissipative chemical reaction cycles to the creation of supramolecular materials. Indeed, the emerging materials are endowed with some of the unique properties we typically associate with life. The design strategies are the focus of this review.
Molecules can be designed to interact with one another and form assemblies. Biology also uses molecular self-assembly to create its structural components. However, this biological process is tightly regulated by chemical reaction cycles that operate out of equilibrium. If we want to create life-like materials or even synthetic life, we should use an approach similar to molecular self-assembly. The focus of this review is to lay out design strategies toward the synthesis of molecular assemblies regulated by chemical reaction cycles.
Monodisperse MgH2 nanoparticles with homogeneous distribution and a high loading percent are developed through hydrogenation‐induced self‐assembly under the structure‐directing role of graphene. ...Graphene acts not only as a structural support, but also as a space barrier to prevent the growth of MgH2 nanoparticles and as a thermally conductive pathway, leading to outstanding performance.
An injectable and self‐healing collagen–gold hybrid hydrogel is spontaneously formed by electrostatic self‐assembly and subsequent biomineralization. It is demonstrated that such collagen‐based ...hydrogels may be used as an injectable material for local delivery of therapeutic agents, showing enhanced antitumor efficacy.
This article reviews the current state of the art with respect to RAFT alcoholic dispersion polymerization processes that proceed with polymerization-induced self-assembly (PISA) and covers the bulk ...of the literature up to mid-2016. The article is arranged according to suitable comonomers that may employed in such copolymerizations. Where appropriate we have highlighted unusual nanoparticle morphologies that are accessible, and formulation specific, as well as interesting properties associated with certain final nano-objects.
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•RAFT dispersion polymerization with polymerization-induced self-assembly (PISA) proceeds in a range of alcoholic solvents.•Nanoparticles of ‘common’ and complex morphology are readily accessible.•Nano-objects responsive to changes in temperature and/or pH can be prepared.•Reversible order-order and order-disorder transitions have been observed.
To study the supramolecular polymerisation mechanisms of a self‐assembling system, concentration‐ and temperature‐dependent measurements can both be used to probe the transition from the molecular ...dissolved state to the aggregated state. In this report, both methods are evaluated to determine their effectiveness in identifying and quantifying the self‐assembly mechanism for isodesmic and cooperative self‐assembling systems. It was found that for a rapid and unambiguous determination of the self‐assembly mechanism and its thermodynamic parameters, temperature‐dependent measurements are more appropriate. These studies allow the acquisition of a large data set leading to an accurate determination of the self‐assembly mechanism and quantification of the different thermodynamic parameters that describe the supramolecular polymerisation. For a comprehensive characterisation, additional concentration‐dependent measurements can be performed.
Self‐assembly mechanisms of a self‐assembled system were studied by concentration‐ and temperature‐dependent measurements. Both methods were evaluated to determine their effectiveness in identifying and quantifying the self‐assembly mechanism for isodesmic and cooperative systems (see figure). For a fast and unambiguous determination of the assembly mechanism and its thermodynamic parameters, temperature‐dependent measurements are more appropriate.
Stripes on a plane: A set of highly ordered microscopic stripes (purple; see scheme) were produced over a large area by using controlled evaporative self‐assembly in a cylinder‐on‐Si geometry of ...conjugated homopolymers or all‐conjugated diblock copolymer (P3BHT). The crystallinity of the as‐prepared assemblies of P3BHT was greatly improved following chloroform vapor annealing, resulting in a fourfold increase in electrical conductivity.
Photoluminescent gold nanodots (Au NDs) are prepared via etching and codeposition of hybridized ligands, an antimicrobial peptide (surfactin; SFT), and 1‐dodecanethiol (DT), on gold nanoparticles ...(≈3.2 nm). As‐prepared ultrasmall SFT/DT–Au NDs (size ≈2.5 nm) are a highly efficient antimicrobial agent. The photoluminescence properties and stability as well as the antimicrobial activity of SFT/DT–Au NDs are highly dependent on the density of SFT on Au NDs. Relative to SFT, SFT/DT–Au NDs exhibit greater antimicrobial activity, not only to nonmultidrug‐resistant bacteria but also to the multidrug‐resistant bacteria. The minimal inhibitory concentration values of SFT/DT–Au NDs are much lower (>80‐fold) than that of SFT. The antimicrobial activity of SFT/DT–Au NDs is mainly due to the synergistic effect of SFT and DT–Au NDs on the disruption of the bacterial membrane. In vitro cytotoxicity and hemolysis analyses have revealed superior biocompatibility of SFT/DT–Au NDs than that of SFT. Moreover, in vivo methicillin‐resistant S. aureus–infected wound healing studies in rats show faster healing, better epithelialization, and are more efficient in the production of collagen fibers when SFT/DT–Au NDs are used as a dressing material. This study suggests that the SFT/DT–Au NDs are a promising antimicrobial candidate for preclinical applications in treating wounds and skin infections.
Surfactin, an antimicrobial lipopeptide, when self‐assembled on photoluminescent gold nanodots (Au NDs) exhibits an >80‐fold improvement in its antimicrobial activity against multidrug‐resistant bacteria. Antibacterial wound‐healing assays further reveal that the surfactin–Au ND hybrid material is superior to that of surfactin alone on a bacteria‐infected flesh wound in rats.
Since the discovery of the liquid‐crystalline state of matter 125 years ago, this field has developed into a scientific area with many facets. This Review presents recent developments in the ...molecular design and self‐assembly of liquid crystals. The focus is on new exciting soft‐matter structures distinct from the usually observed nematic, smectic, and columnar phases. These new structures have enhanced complexity, including multicompartment and cellular structures, periodic and quasiperiodic arrays of spheres, and new emergent properties, such as ferroelctricity and spontaneous achiral symmetry‐breaking. Comparisons are made with developments in related fields, such as self‐assembled monolayers, multiblock copolymers, and nanoparticle arrays. Measures of structural complexity used herein are the size of the lattice, the number of distinct compartments, the dimensionality, and the logic depth of the resulting supramolecular structures.
Liquid crystals on the way to complexity: Recent developments in liquid‐crystalline materials have lead to new structures with enhanced complexity, including honeycombs and multicompartment structures, vesicular phases, and periodic and quasiperiodic arrays. New properties emerge, such as ferroelctricity and spontaneous achiral symmetry‐breaking.
The developments in membranes based on tailored block copolymers are reported with an emphasis on isoporous membranes. These membranes can be prepared in different geometries, namely flat sheets and ...hollow fibers. They display narrow pore size distributions due to their formation by self‐assembly. The preparation of these membranes and possibilities to further functionalize such membranes will be discussed. Different ways to control the pore size will be addressed, and the potential of block copolymer blends to fabricate membranes with tailored pore sizes will be shown.
A review on integral asymmetric block copolymer membranes with isoporous separating layers is given. The article discusses the membrane formation process and possibilities to prepare membranes with tailored functionalities.
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