Helical Building Blocks Research Articles

VoroNoodles: Topological Interlocking with Helical Layered 2‐Honeycombs

An approach for modeling topologically interlocked building blocks that can be assembled in a water‐tight manner (space filling) to design a variety of spatial structures is introduced. This approach takes inspiration from recent methods utilizing Voronoi tessellation of spatial domains using symmetrically arranged Voronoi sites. Attention is focused on building blocks that result from helical stacking of planar 2‐honeycombs (i.e., tessellations of the plane with a single prototile) generated through a combination of wallpaper symmetries and Voronoi tessellation. This unique combination gives rise to structures that are both space‐filling (due to Voronoi tessellation) and interlocking (due to helical trajectories). Algorithms are developed to generate two different varieties of helical building blocks, namely, corrugated and smooth. These varieties result naturally from the method of discretization and shape generation and lead to distinct interlocking behavior. In order to study these varieties, finite‐element analyses (FEA) are conducted on different tiles parametrized by 1) the polygonal unit cell determined by the wallpaper symmetry and 2) the parameters of the helical line generating the Voronoi tessellation. Analyses reveal that the new design of the geometry of the building blocks enables strong variation of the engagement force between the blocks.

Collectively Enhanced Giant Circular Dichroism of Germanium Nanohelix Square Lattice Arrays

Circular dichroism is a unique chiroptical signature of the chirality of a system and is a prevalent way to characterize and distinguish systems on a fundamental level and for their technological applicability. Thus, engineering and maximizing the chiroptical response of a single chiral object or a metasurface composed of chiral entities is a formidable task. Current efforts strongly focus on individual metallic nanostructures and their periodic ensembles to harvest on (resonant) plasmonic properties and interactions. This route, however, waives the advantages of high‐refractive‐index nanoscale materials embracing low dissipative losses at optical wavelengths and electromagnetic fields penetrating and propagating in such materials. Herein, a strong circular dichroism is demonstrated in square lattices of nanohelices made of the high‐refractive‐index semiconductor germanium, with dissymmetry factors outperforming metal‐based ensembles. The observation of a much higher dissymmetry emerges for illumination with spatially coherent light, in comparison to spatially incoherent light. High dissymmetry is attributed to cooperative coupling between single helices, resulting from the combination of dielectric resonances of both the individual helical building blocks and the highly ordered lattice.

Formation of Multiple Supramolecular Helices for Spontaneous Resolution

AbstractRelating supramolecular helices to the spontaneous resolution that generates conglomerate crystals is meaningful to the production of enantiopure compounds and to the understanding of natural homochirality as well. While homochiral elongation is favored along the axis of 1D supramolecular helical chains, conglomerate crystallization requires a 3D homochiral framework. This inspires us to explore new avenues to the spontaneous resolution through the formation of multiple supramolecular helices during crystallization. This Concept outlines and reviews multiple supramolecular helices found in the conglomerate crystals, i. e. three supramolecular helices along one crystallographic axis and two or three supramolecular helices along different crystallographic axes, followed by our observations of homochiral elongation of the helicity of the helical building blocks, the azapeptides, during the formation of supramolecular helices, as well as the spontaneous resolution of amino acid alanine that is made into a helical azapeptide derivative via the formation of supramolecular helices along two different crystallographic axes.

Spontaneous Resolution of Helical Building Blocks through the Formation of Homochiral Helices in Two Dimensions

AbstractSpontaneous resolution leading to conglomerate crystals remains a significant challenge. Here we propose the formation of orthogonal homochiral supramolecular helices in at least two dimensions to allow spontaneous resolution. We suggest the design rationale that the chiral species is made into helical building blocks to allow the helix formation. As a proof‐of‐concept, acetylalanine was made into a helical short azapeptide, its N‐amidothiourea derivative containing a β‐turn structure, to which a halogen atom was further introduced at the phenylthiourea aromatic ring. The resultant folded species undergoes both intermolecular hydrogen and halogen bonding across the turn structure to form orthogonal intermolecular hydrogen‐bonded and halogen‐bonded supramolecular helices in two dimensions, and undergoes chiral resolution upon crystallization. Meanwhile, counterparts containing either an F‐substituent with weak halogen bonding or no halogen atom crystallize as racemic compounds.

Spontaneous Resolution of Helical Building Blocks through the Formation of Homochiral Helices in Two Dimensions.

Spontaneous resolution leading to conglomerate crystals remains a significant challenge. Here we propose the formation of orthogonal homochiral supramolecular helices in at least two dimensions to allow spontaneous resolution. We suggest the design rationale that the chiral species is made into helical building blocks to allow the helix formation. As a proof-of-concept, acetylalanine was made into a helical short azapeptide, its N-amidothiourea derivative containing a β-turn structure, to which a halogen atom was further introduced at the phenylthiourea aromatic ring. The resultant folded species undergoes both intermolecular hydrogen and halogen bonding across the turn structure to form orthogonal intermolecular hydrogen-bonded and halogen-bonded supramolecular helices in two dimensions, and undergoes chiral resolution upon crystallization. Meanwhile, counterparts containing either an F-substituent with weak halogen bonding or no halogen atom crystallize as racemic compounds.

Supramolecular helices from helical building blocks via head-to-tail intermolecular interactions.

Supramolecular helices from helical building blocks represent an emerging analogue of the α-helix. In cases where the helicity of the helical building block is well propagated, the head-to-tail intermolecular interactions that lead to the helix could be enhanced to promote the formation and the stability of the supramolecular helix, wherein homochiral elongation dominates and functional helical channel structures could also be generated. This feature article outlines the supramolecular helices built from helical building blocks, i.e., helical aromatic foldamers and helical short peptides that are held together by intermolecular π-π stacking, hydrogen/halogen/chalcogen bonding, metal coordination, dynamic covalent bonding and solvophobic interactions, with emphasis on the influence of efficient propagation of helicity during assembly, favouring homochirality and channel functions.

Chalcogen bonding mediates the formation of supramolecular helices of azapeptides in crystals.

To explore whether chalcogen bonding was able to drive the formation of supramolecular helices, alanine-based azapeptides containing a β-turn structure, with a thiophene group, respectively, incorporated in the N- or C-terminus, were employed as helical building blocks. While the former derivative formed a supramolecular M-helix via intermolecular SS chalcogen bonding in crystals, the latter formed P-helix via intermolecular SO chalcogen bonding.

Functionalized Helical Building Blocks for Nanoelectronics

Molecular building blocks are designed and created for the cis- and trans-dibrominated perylenediimides. The syntheses are simple and provide these useful materials on the gram scale. To demonstrate their synthetic versatility, these building blocks were used to create new dimeric perylenediimide helixes. Two of these helical dimers are twistacenes, and one is a helicene. Crucially, each possesses regiochemically defined functionality that allows the dimer helix to be elaborated into higher oligomers. It would be very difficult to prepare these helical PDI building blocks regioselectively without the methods described.

Plasmonic Toroidal Metamolecules Assembled by DNA Origami

We show hierarchical assembly of plasmonic toroidal metamolecules that exhibit tailored optical activity in the visible spectral range. Each metamolecule consists of four identical origami-templated helical building blocks. Such toroidal metamolecules show a stronger chiroptical response than monomers and dimers of the helical building blocks. Enantiomers of the plasmonic structures yield opposite circular dichroism spectra. Experimental results agree well with the theoretical simulations. We also show that given the circular symmetry of the structures s distinct chiroptical response along their axial orientation can be uncovered via simple spin-coating of the metamolecules on substrates. Our work provides a new strategy to create plasmonic chiral platforms with sophisticated nanoscale architectures for potential applications such as chiral sensing using chemically based assembly systems.

Constructing various metal–organic frameworks by mixed pyridine–acylamide and carboxylate ligands: ring-like or helical building blocks

To some extent, this work has demonstrated the coordination affinity of the L ligand and gives us some understanding of how to direct the next syntheses of L-based compounds.

Chiroptical Inversion in Helical Si–Si Bond Polymer Aggregates

To elucidate the factors involved in the chiroptical properties of polymer aggregates composed of helical building blocks, a series of rigid rod helical poly[alkyl-(S)-2-methylbutylsilane]s (achiral alkyl side chains = ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl) have been investigated. It was found that the chiroptical sign in the circular dichroism (CD) spectra of the polysilane aggregates depends on the achiral side chain length and cosolvent fraction. Concerning the achiral side chains, the n-propyl group was of a critical length for solvent-dependent chiroptical inversion on aggregation. This unique side chain length-dependent chiroptical inversion was theoretically predictable by using the novel approach of combining the cholesteric hard-core model and exciton chirality method. The latter was also investigated theoretically by Gaussian 03 (TD-DFT, B3LYP, 6-31G(d) basis set) calculations applied to two spatially arranged helical Si-Si bonded decamer models.

Fibrils or Globules? Tuning the Morphology of Peptide Aggregates from Helical Building Blocks

The aggregation propensity of helical oligopeptides formed exclusively by the conformationally constrained α-aminoisobutyric acid (Aib or U in a three- or single-letter code, respectively) was studied in methanol and methanol/water solutions by spectroscopic methods (UV-vis absorption, steady-state and time-resolved fluorescence, and FT-IR absorption) and atomic force microscopy (AFM) imaging. The peptides investigated have the general formula UnN, where n = 6, 12, and 15 and N stands for a naphthyl chromophore introduced with the dual aim to serve as a spectroscopic probe and to analyze the effect of an extended aromatic group on the aggregation process. Experiments showed that the aggregation propensity in (70/30)v/v and (50/50)v/v methanol/water solutions increases with increasing the length of the peptide chain, i.e., U6N < U12N < U15N. When the peptides are immobilized on mica as a dried film, the interplay of aromatic-aromatic and interhelix interactions, the latter becoming more and more important with the elongation of the peptide chain, governs the morphology of the resulting mesoscopic aggregates. AFM imaging revealed the formation of globular or fibrillar structures, the predominance of which is controlled by the helix length of the peptide building block.

Deliberate Design of a 3D Homochiral CuII/l-met/AgI Coordination Network Based on the Distinct Soft−Hard Recognition Principle

A homochiral amino acid coordination network [{Ag3Cu3(l-methioninato)6(NO3)3(H2O)3}.7H2O]n, self-assembled from CuII, AgI, and l-methionine via a distinct soft-hard recognition process, shows interesting characteristics, in that it is constructed from 1D helical building blocks and contains homochiral channels in which 1D water chains are hosted. This result provides an effective and controllable strategy for the preparation of enantiopure heterometallic supramolecular structures that are relevant to biopolymers.

Ortho-Tetraaryls as helical building blocks: a study of structure, theory, electrochemistry, and optical properties

( ortho)-3,3′-Diphenyl-2,2′-bithiophene is shown to exhibit a solid-state helical conformation that is consistent with MMFF predictions of structure. The optical, electronic, and conformational properties of this compound are examined, and the results are commensurate with a helical building block capable of exhibiting redox-induced conformational changes along the long molecular axis. Such a property demonstrates promise for this tetramer to function as building block for a spring-like electromechanical actuator.