Interrogating the potential of helical aromatic foldamers for protein recognition.

A biotinylated helical aromatic oligoamide foldamer equivalent in size to a 24mer peptide was designed without any prejudice other than to display various polar and hydrophobic side chains at its surface. It was synthesized on solid phase, its - and -helical conformers were separated by HPLC on a chiral stationary phase, and the solid state structure of a non-biotinylated analogue was elucidated by X-ray crystallography. Pull-down experiments from a yeast cell lysate using the foldamer as a bait followed by proteomic analysis revealed potential protein binding partners.

Dopant Control of Solution-Processed CuI:S for Highly Conductive p-Type Transparent Electrode.

Copper iodide (CuI) has garnered considerable attention as a promising alternative to p-type transparent conducting oxides owing to its low cation vacancy formation energy, shallow acceptor level, and readily modifiable conductivity via doping. Although sulfur (S) doping through liquid iodination has exhibited high efficacy in enhancing the conductivity with record high figure of merit (FOM) of 630 00 MΩ, solution-processed S-doped CuI (CuI:S) for low-cost large area fabrication has yet to be explored. Here, a highly conducting CuI:S thin-film for p-type transparent conducting electrode (TCE) is reported using low temperature solution-processing with thiourea derivatives.

Crystalline Metal-Peptide Networks: Structures, Applications, and Future Outlook.

Metal-peptide networks (MPNs), which are assembled from short peptides and metal ions, are considered one of the most fascinating metal-organic coordinated architectures because of their unique and complicated structures. Although MPNs have considerable potential for development into versatile materials, they have not been developed for practical applications because of several underlying limitations, such as designability, stability, and modifiability. In this review, we summarise several important milestones in the development of crystalline MPNs and thoroughly analyse their structural features, such as peptide sequence designs, coordination geometries, cross-linking types, and network topologies.

Designed Amyloid Fibers with Emergent Melanosomal Functions.

Short peptides designed to self-associate into amyloid fibers with metal ion-binding ability have been used to catalyze various types of chemical reactions. This manuscript demonstrates that one of these short-peptide fibers coordinated with Cu can exhibit melanosomal functions. The coordinated Cu and the amyloid structure itself are differentially functional in accelerating oxidative self-association of dopamine into melanin-like species and in regulating their material properties (e.

Determination of the Photoisomerization Quantum Yield of a Hydrazone Photoswitch.

Photoswitching organic molecules that undergo light-driven structural transformations are key components to construct adaptive molecular systems, and they are utilized in a wide variety of applications. In most studies employing photoswitches, several important photophysical properties such as maximum wavelengths of absorption and emission, molar attenuation coefficient, fluorescence lifetime, and photoisomerization quantum yield are carefully determined to investigate their electronic states and transition processes. However, measurement of the photoisomerization quantum yield, the efficiency of photoisomerization with respect to the absorbed photons, in a typical laboratory setting is often complicated and prone to error because it requires the implementation of rigorous spectroscopic measurements and calculations based on an appropriate integration method.

Synthesis of gold nano-mushrooms solvent-controlled galvanic replacement to enhance phototherapeutic efficiency.

In advanced galvanic replacement, variable factors such as the combination of two elements where actual redox reaction and post-synthetic structural transformation take place. Research on manufacturing distinctive nanostructures has mainly focused on the shape of the sacrificial nanotemplate, the presence or absence of additives, and the reaction temperature. Here, we have attempted to confirm the dependency on the solvent, which was considered to simply serve as a medium for a homogeneous chemical reaction to proceed by aiding the dispersion of the nanotemplate and reactants.

Hydrazone Photoswitches for Structural Modulation of Short Peptides.

Molecules that undergo light-driven structural transformations constitute the core components in photoswitchable molecular systems and materials. Among various families of photoswitches, photochromic hydrazones have recently emerged as a novel class of photoswitches with superb properties, such as high photochemical conversion, spectral tunability, thermal stability, and fatigue resistance. Hydrazone photoswitches have been adopted in various adaptive materials at different length scales, however, their utilization for modulating biomolecules still has not been explored.

Conformational Adaptation of β-Peptide Foldamers for the Formation of Metal-Peptide Frameworks.

Metal-coordinated frameworks derived from small peptidic ligands have received much attention thanks to peptides' vast structural and functional diversity. Various peptides with partial conformational preferences have been used to build metal-peptide frameworks, however, the use of conformationally constrained β-peptide foldamers has not been explored yet. Herein we report the first metal-coordination-mediated assembly of β-peptide foldamers with 12-helical folding propensity.

Synthetic Foldamers: Rational Design of Advanced Structures with Diverse Applications.

Fruitful Foldamers: Guest Editors Ivan Huc, Sunbum Kwon, and Hee-Seung Lee discuss the development of the field and introduce this Special Collection on the Synthesis, Properties, and Applications of Foldamers. This collection features top-quality multidisciplinary research and review articles that cover design, self-assembly, guest recognition, catalytic activity, and optical and biological properties of foldamers.

Graphene Oxide Derivatives and Their Nanohybrid Structures for Laser Desorption/Ionization Time-of-Flight Mass Spectrometry Analysis of Small Molecules.

Matrix-assisted laser desorption/ionization (MALDI) has been considered as one of the most powerful analytical tools for mass spectrometry (MS) analysis of large molecular weight compounds such as proteins, nucleic acids, and synthetic polymers thanks to its high sensitivity, high resolution, and compatibility with high-throughput analysis. Despite these advantages, MALDI cannot be applied to MS analysis of small molecular weight compounds (<500 Da) because of the matrix interference in low mass region. Therefore, numerous efforts have been devoted to solving this issue by using metal, semiconductor, and carbon nanomaterials for MALDI time-of-flight MS (MALDI-TOF-MS) analysis instead of organic matrices.

Self-Assembly of a β-Peptide Foldamer: The Role of the Surfactant in Three-Dimensional Shape Selection.

The effect of a small ionic surfactant, cetyltrimethylammonium bromide (CTAB), on the self-assembly of a β-peptide has been systematically studied by using scanning electron microscopy, X-ray diffraction, selected area electron diffraction, and molecular dynamics (MD) simulations. The latter study suggested that the formation of asymmetric microcrystals may be due to the preferential adsorption of CTAB on {011} and (001) crystal faces. This work provides a plausible rationale for the characteristic 3D morphogenesis of foldectures and elucidates the interaction between the surfactant and organic building block molecules.

Ribosomal Incorporation of Aromatic Oligoamides as Peptide Sidechain Appendages.

Derivatives of 4-aminomethyl-l-phenylalanine with aromatic oligoamide foldamers as sidechain appendages were successfully charged on tRNA by means of flexizymes. Their subsequent incorporation both at the C-terminus of, and within, peptide sequences by the ribosome, was demonstrated. These results expand the registry of chemical structures tolerated by the ribosome to sidechains significantly larger and more structurally defined than previously demonstrated.

Multifaceted Influences of Melanin-Like Particles on Amyloid-beta Aggregation.

The properties of eumelanin-like particles (EMPs) and pheomelanin-like particles (PMPs) in regulating the process of amyloid formation of amyloid-beta 42 (Aβ42) were examined. EMPs and PMPs are effective both in interfering with amyloid aggregation of Aβ42 and in remodeling matured Αβ42 fibers. The results suggest that some (but not all) molecular species consisting of melanin-like particles (MPs) are responsible for their inhibiting property toward amyloid formation, and the influence is likely manifested by long-range interactions.

Optimizing aromatic oligoamide foldamer side-chains for ribosomal translation initiation.

The tolerance of ribosomal peptide translation for helical aromatic oligoamide foldamers appended as initiators has been investigated. Small cationic foldamer side-chains were shown to expand the range of foldamer-peptide hybrids that can be produced by the ribosome to more rigid sequences.

Spontaneous Nanobelt Formation by Self-Assembly of β-Benzyl GABA.

We present the formation of a nanobelt by self-assembly of β-benzyl GABA (γ-aminobutyric acid). This simple γ-amino acid building block self-assembled to form a well-defined nanobelt in chloroform. The nanobelt showed distinct optical properties due to π-π interactions.

Publisher Correction: Ribosomal synthesis and folding of peptide-helical aromatic foldamer hybrids.

In the version of this Article originally published, in Fig.1f there was an erroneous 'Gly-Gly' label placed above the foldamer-peptide structure. Furthermore, in Fig.

Ribosomal synthesis and folding of peptide-helical aromatic foldamer hybrids.

Translation, the mRNA-templated synthesis of peptides by the ribosome, can be manipulated to incorporate variants of the 20 cognate amino acids. Such approaches for expanding the range of chemical entities that can be produced by the ribosome may accelerate the discovery of molecules that can perform functions for which poorly folded, short peptidic sequences are ill suited. Here, we show that the ribosome tolerates some artificial helical aromatic oligomers, so-called foldamers.

Magnetotactic molecular architectures from self-assembly of β-peptide foldamers.

The design of stimuli-responsive self-assembled molecular systems capable of undergoing mechanical work is one of the most important challenges in synthetic chemistry and materials science. Here we report that foldectures, that is, self-assembled molecular architectures of β-peptide foldamers, uniformly align with respect to an applied static magnetic field, and also show instantaneous orientational motion in a dynamic magnetic field. This response is explained by the amplified anisotropy of the diamagnetic susceptibilities as a result of the well-ordered molecular packing of the foldectures.

A Hollow Foldecture with Truncated Trigonal Bipyramid Shape from the Self-Assembly of an 11-Helical Foldamer.

The creation of self-assembling microscale architectures that possess new and useful physical properties remains a significant challenge. Herein we report that an 11-helical foldamer self-assembles in a controlled manner to form a series of 3D foldectures with unusual three-fold symmetrical shapes that are distinct from those generated from 12-helical foldamers. The foldamer packing motif was revealed by powder X-ray diffraction technique, and provides an important link between the molecular-level symmetry and the microscale morphologies.

Foldecture as a core material with anisotropic surface characteristics.

The synthesis of microscale, polyhedrally shaped, soft materials with anisotropic surface functionality by a bottom-up approach remains a significant challenge. Herein we report a microscale molecular architecture (foldecture) with facet-dependent surface characteristics that can potentially serve as a well-defined catalytic template. Rhombic rod shaped foldectures with six facets were obtained by the aqueous self-assembly of helical β-peptide foldamers with a C-terminal carboxylic acid.

Microtubes with rectangular cross-section by self-assembly of a short β-peptide foldamer.

In nature, complex and well-defined structures are constructed by the self-assembly of biomolecules. It has been shown that β-peptide foldamers can mimic natural peptides and self-assemble into three-dimensional molecular architectures thanks to their rigid and predictable helical conformation in solution. Using shorter foldamers, which can be prepared more easily than longer ones, to form such architectures is highly desirable, but shorter foldamers have been overlooked due to the seemingly inferior number of intramolecular hydrogen bonds to stabilize a folded state in solution.

Self-assembled peptide architecture with a tooth shape: folding into shape.

Molecular self-assembly is the spontaneous association of molecules into structured aggregates by which nature builds complex functional systems. While numerous examples have focused on 2D self-assembly to understand the underlying mechanism and mimic this process to create artificial nano- and microstructures, limited progress has been made toward 3D self-assembly on the molecular level. Here we show that a helical β-peptide foldamer, an artificial protein fragment, with well-defined secondary structure self-assembles to form an unprecedented 3D molecular architecture with a molar tooth shape in a controlled manner in aqueous solution.