Abstract:The rigid geometry and tunable chemistry of D,L-cyclic peptides makes them an intriguing building-block for the rational design of nano-and microscale hierarchically structured materials. Herein, we utilize a combination of electron microscopy, nanomechanical characterization including depth sensing-based bending experiments, and molecular modeling methods to
“…Computer simulation studies also aim to predict the molecular organization of peptide molecules and can be used for the optimization of peptide design in conjunction with experimental findings [299][300][301][302][303]. Incorporation of the experimental results and the simulation outputs developed using different molecular dynamics (MD) simulation programs improves the information on the structural properties of the peptide assemblies [93,228,[304][305][306][307]. Previously, successful candidates were determined among 8000 different peptide molecules using computational approaches.…”
Section: Spectroscopic Analysismentioning
confidence: 99%
“…Nanomechanical properties of the D, L cyclic peptide assemblies were determined via depth sensing-based bending system (top) and the fractures formed on the nanostructures during the measurement were imaging using electron microscopy (bottom). Adapted with permission from [93]. Copyright 2015 American Chemical Society.…”
Nature is an important inspirational source for scientists, and presents complex and elegant examples of adaptive and intelligent systems created by self-assembly. Significant effort has been devoted to understanding these sophisticated systems. The self-assembly process enables us to create supramolecular nanostructures with high order and complexity, and peptide-based self-assembling building blocks can serve as suitable platforms to construct nanostructures showing diverse features and applications. In this review, peptide-based supramolecular assemblies will be discussed in terms of their synthesis, design, characterization and application. Peptide nanostructures are categorized based on their chemical and physical properties and will be examined by rationalizing the influence of peptide design on the resulting morphology and the methods employed to characterize these high order complex systems. Moreover, the application of self-assembled peptide nanomaterials as functional materials in information technologies and environmental sciences will be reviewed by providing examples from recently published high-impact studies.
“…Computer simulation studies also aim to predict the molecular organization of peptide molecules and can be used for the optimization of peptide design in conjunction with experimental findings [299][300][301][302][303]. Incorporation of the experimental results and the simulation outputs developed using different molecular dynamics (MD) simulation programs improves the information on the structural properties of the peptide assemblies [93,228,[304][305][306][307]. Previously, successful candidates were determined among 8000 different peptide molecules using computational approaches.…”
Section: Spectroscopic Analysismentioning
confidence: 99%
“…Nanomechanical properties of the D, L cyclic peptide assemblies were determined via depth sensing-based bending system (top) and the fractures formed on the nanostructures during the measurement were imaging using electron microscopy (bottom). Adapted with permission from [93]. Copyright 2015 American Chemical Society.…”
Nature is an important inspirational source for scientists, and presents complex and elegant examples of adaptive and intelligent systems created by self-assembly. Significant effort has been devoted to understanding these sophisticated systems. The self-assembly process enables us to create supramolecular nanostructures with high order and complexity, and peptide-based self-assembling building blocks can serve as suitable platforms to construct nanostructures showing diverse features and applications. In this review, peptide-based supramolecular assemblies will be discussed in terms of their synthesis, design, characterization and application. Peptide nanostructures are categorized based on their chemical and physical properties and will be examined by rationalizing the influence of peptide design on the resulting morphology and the methods employed to characterize these high order complex systems. Moreover, the application of self-assembled peptide nanomaterials as functional materials in information technologies and environmental sciences will be reviewed by providing examples from recently published high-impact studies.
“…However, MC stacking is generally too weak to produce nanotubes with the high aspect ratios (>10 3 ) of CNTs and biological filaments. Stacked MCs instead almost always exhibit aspect ratios around 10 as short, individual assemblies or longer structures stabilized by bundling (12)(13)(14), limiting their utility as isolated nanostructures (15). Alternatively, when functionalized with many long alkyl or alkyloxy side chains, they form bulk liquid crystalline phases (16)(17)(18)(19), with assembly sometimes driven by the presence of metal ions or organic guests (20).…”
One-dimensional nanostructures such as carbon nanotubes and actin filaments rely on strong and directional interactions to stabilize their high aspect ratio shapes. This requirement has precluded making isolated, long, thin organic nanotubes by stacking molecular macrocycles, as their noncovalent stacking interactions are generally too weak. Here we report high aspect ratio (>10), lyotropic nanotubes of stacked, macrocyclic, iminium salts, which are formed by protonation of the corresponding imine-linked macrocycles. Iminium ion formation establishes cohesive interactions that, in organic solvent (tetrahydrofuran), are two orders of magnitude stronger than the neutral macrocycles, as explained by physical arguments and demonstrated by molecular dynamics simulations. Nanotube formation stabilizes the iminium ions, which otherwise rapidly hydrolyze, and is reversed and restored upon addition of bases and acids. Acids generated by irradiating a photoacid generator or sonicating chlorinated solvents also induced nanotube assembly, allowing these nanostructures to be coupled to diverse stimuli, and, once assembled, they can be fixed permanently by cross-linking their pendant alkenes. As large macrocyclic chromonic liquid crystals, these iminium salts are easily accessible through a modular design and provide a means to rationally synthesize structures that mimic the morphology and rheology of carbon nanotubes and biological tubules.
“…69 Recent advances in electron microscopy techniques, combined with novel nanomechanical analysis allowed the insightful characterization of the mechanical properties and the aggregation propensity of the Leu substituted peptide. 70 This study revealed that the assembly of this CP, followed by a hierarchical bundling pattern, resulted in the formation of nanotube fibers. This bundling process gave rise to longer (several tens of μm) and thick (up to 1 μm) nanotubular bundles.…”
The fabrication of functional molecular devices constitutes one of the most important current challenges for chemical sciences. The complex processes accomplished by living systems continuously demand the assistance of non-covalent interactions between molecular building blocks. Additionally, these building blocks (proteins, membranes, nucleotides) are also constituted by self-assembled structures. Therefore, supramolecular chemistry is the discipline required to understand the properties of the minimal self-assembled building blocks of living systems and to develop new functional smart materials. In the first part of this feature article, we highlight selected examples of the preparation of supramolecular membrane transporters with special emphasis on the application of dynamic covalent bonds. In the second section of the paper we review recent breakthroughs in the preparation of peptide nanotube hybrids with functional applications. The development of these devices constitutes an exciting process from where we can learn how to understand and manipulate supramolecular functional assemblies.
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