Chiral Pattern Research Articles

Dynamic Dance of Chirality and Morphology: Interplay of Solvent-Sensitive Self-Assembly in Topological Evolution and Chirality Amplification.

The building block Pyra-Chol has been designed and synthesized, which exhibits different achiral morphologies in good solvents, forming nanospheres in THF and nanoflowers in 1,4-dioxane. In the presence of water as a poor cosolvent, Pyra-Chol demonstrates an agnostic behavior, generating left-handed superhelices in the water:THF (80:20) solvent system. However, when the good solvent is switched to 1,4-dioxane, a change in chirality is observed in the water:1,4-dioxane (30:70) solvent system, resulting in the formation of fused nanospheres. Interestingly, when the poor cosolvent is changed from water to MCH in THF, the chiral pattern remains unchanged, but the morphology changes completely. Supported by the collective spectroscopic and microscopic analysis, the present study efficaciously demonstrates the remarkable control of hydrophobic building block over the chiral sense and also highlights the fascinating influence of good as well as poor cosolvent in supporting the distinct molecular packing.

Long range juxtacrine signalling through cadherin for collective cell orientation

Many life phenomena, such as development, morphogenesis, tissue remodelling, and wound healing, are often driven by orderly and directional migration of collective cells. However, when cells are randomly oriented or localized disorder exists in orderly oriented collective cells, cell migration cannot occur in an orderly manner although various motion modes such as global rotation and local swirling and/or various motion patterns such as radial pattern and chiral pattern often occur. Therefore, it is important to control cell orientation to ensure the orderly migration of collective cells. Here, we show that it is not force transmission, but juxtacrine signalling through cadherin that plays a critical role in the orientation of collective cells. Surprisingly, juxtacrine signalling for cell orientation reached cells on a plastic dish that were not directly subjected to mechanical stimulation, up to 7 mm away from the actuator. The present study suggests that even weak mechanical stimulation is transmitted in a long range without force transmission through juxtacrine signalling. The long range juxtacrine signalling might play an important role in various life phenomena. Statement of SignificanceJuxtacrine signalling is direct cell-cell contact-dependent signalling, which plays a crucial role in cell behaviors such as mechanosensing, mechanotransduction and collective cell behaviors, however, there is not enough understanding about juxtacrine signalling. The present study has demonstrated that juxtacrine signalling for collective cell orientation is transmitted over a long range through cadherin. To the best of our knowledge, this is the first report of long range juxtacrine signalling. This finding may lead to the elucidation of various life phenomena such as development, morphogenesis, tissue remodelling, and wound healing.

Polar and quasicrystal vortex observed in twisted-bilayer molybdenum disulfide.

We report the observation of an electric field in twisted-bilayer molybdenum disulfide (MoS2) and elucidate its correlation with local polar domains using four-dimensional scanning transmission electron microscopy (4D-STEM) and first-principles calculations. We reveal the emergence of in-plane topological vortices within the periodic moiré patterns for both commensurate structures at small twist angles and the incommensurate quasicrystal structure that occurs at a 30° twist. The large-angle twist leads to mosaic chiral vortex patterns with tunable characteristics. A twisted quasicrystal bilayer, characterized by its 12-fold rotational symmetry, hosts complex vortex patterns and can be manipulated by picometer-scale interlayer displacement. Our findings highlight that twisting 2D bilayers is a versatile strategy for tailoring local electric polar vortices.

Unveiling the Loss Mode Enabled Tunable Plasmonic Chirality at Flat Metal Surface.

Plasmonic chirality has garnered significant interest in the past decade due to its enhanced chiral light-matter interactions. Current methods for achieving plasmonic chirality often rely on complex nanostructures or metamaterials, which are hampered by intricate fabrication processes. In this work, we present an approach to generate plasmonic chiral structured surface plasmon polariton (s-SPP) fields on a single, flat metal surface, bypassing elaborate fabrication techniques. The plasmonic chiral s-SPP fields are excited by the superposition of multiple differently oriented transverse magnetic polarized plane waves. We demonstrate, both theoretically and experimentally, the flexible tuning of chiral plasmonic patterns by adjusting the symmetry and phase differences of the incident waves. This method provides a facile mean to optically tailor plasmonic chiral properties on a subwavelength scale, offering potential applications in sensing, enantioselective reactions, imaging, and reconfigurable chiral switches.

Stereoselective Interactions of Chiral Polyurea Nanocapsules with Albumins.

Exploiting the chirality of nanometric structures to modulate biological systems is an emerging and compelling area of research. In this study, we reveal that chiral polyurea nanocapsules exhibit significant stereoselective interactions with albumins from various sources despite their nearly neutral surface potential. Moreover, these interactions can be modulated by altering the nanocapsule surface composition, offering new opportunities to impact their distribution and, if used as a drug delivery system, the pharmacokinetics of the drug. Notably, these interactions promote preferential cellular internalization of only one chiral configuration. We synthesized chiral polyurea nanocapsules with reproducible sizes via interfacial polymerization between toluene 2,4-diisocyanate and d- or l-lysine enantiomers on a volatile oil-in-water emulsion interface, followed by solvent evaporation. Further synthesis optimization reduced the capsule size to a range compatible with in vivo administration, and capsules with alternating chiral patterns were also produced. The stereoselective interactions with albumins were assessed through capsule size changes, fluorescence quenching, and surface charge measurements. Biocompatibility, stability, and cellular internalization were evaluated. Additionally, scanning transmission electron and atomic force microscopy were carried out to assess the capsule shape, surface composition, and morphology. We discovered that d-nanocapsules exhibited 2.1-2.6 times greater albumin adsorption compared with their l-counterparts. This difference is attributed to the distinct morphology of d-nanocapsules, characterized by a more concave shape, central depression, and rougher surface. The extent of adsorption could be finely tuned by adjusting the d- and l-lysine monomer ratios during synthesis. Both chiral configurations demonstrated biocompatibility and stability with d-nanocapsules showing a 2.5-fold increase in cellular internalization.

The perpendicular gyroscope: modal analysis of plate, beam and gyroscope multistructures.

This paper presents a study of the perpendicular gyroscope, which is formed of two orthogonal beams, a flexural plate and a gyroscope. Two sets of chiral-torsional boundary conditions are derived to analytically model the dynamic effects of the gyroscope while taking into account the broken symmetries of the system. The perpendicular junction causes the coupling of the compressional, flexural and torsional displacements in the system. This complex behaviour is accounted for with a comprehensive set of kinematic and dynamic junction conditions. Modal analysis demonstrates the fully coupled system and reveals how the spinning gyroscope induces dynamic chiral Chladni patterns in the plate.This article is part of the theme issue 'Current developments in elastic and acoustic metamaterials science (Part 2)'.

Dynamics of multicellular swirling on micropatterned substrates

Chirality plays a crucial role in biology, as it is highly conserved and fundamentally important in the developmental process. To better understand the relationship between the chirality of individual cells and that of tissues and organisms, we develop a generalized mechanics model of chiral polarized particles to investigate the swirling dynamics of cell populations on substrates. Our analysis reveals that cells with the same chirality can form distinct chiral patterns on ring-shaped or rectangular substrates. Interestingly, our studies indicate that an excessively strong or weak individual cellular chirality hinders the formation of such chiral patterns. Our studies also indicate that there exists the influence distance of substrate boundaries in chiral patterns. Smaller influence distances are observed when cell-cell interactions are weaker. Conversely, when cell-cell interactions are too strong, multiple cells tend to be stacked together, preventing the formation of chiral patterns on substrates in our analysis. Additionally, we demonstrate that the interaction between cells and substrate boundaries effectively controls the chiral distribution of cellular orientations on ring-shaped substrates. This research highlights the significance of coordinating boundary features, individual cellular chirality, and cell-cell interactions in governing the chiral movement of cell populations and provides valuable mechanics insights into comprehending the intricate connection between the chirality of single cells and that of tissues and organisms.

Spatiotemporal-Dependent Confinement Effect of Bubble Swarms Enables a Fractal Hierarchical Assembly with Promoted Chirality.

The submarine-confined bubble swarm is considered an important constraining environment for the early evolution of living matter due to the abundant gas/water interfaces it provides. Similarly, the spatiotemporal characteristics of the confinement effect in this particular scenario may also impact the origin, transfer, and amplification of chirality in organisms. Here, we explore the confinement effect on the chiral hierarchical assembly of the amphiphiles in the confined bubble array stabilized by the micropillar templates. Compared with the other confinement conditions, the assembly in the bubble scenario yields a fractal morphology and exhibits a unique level of the chiral degree, ordering, and orientation consistency, which can be attributed to the characteristic interfacial effects of the rapidly formed gas/water interfaces. Thus, molecules with a balanced amphiphilicity can be more favorable for the promotion. Not limited to the pure enantiomers, chiral amplification of the enantiomer-mixed assembly is observed only in the bubble scenario. Beyond the interfacial mechanism, the fast formation kinetics of the confined liquid bridges in the bubble scenario endows the assembly with the tunable hierarchical morphology when regulating the amphiphilicity, aggregates, and confined spaces. Furthermore, the chiral-induced spin selectivity (CISS) effect of the fractal hierarchical assembly was systematically investigated, and a strategy based on photoisomerization was developed to efficiently modulate the CISS effect. This work provides insights into the robustness of confined bubble swarms in promoting a chiral hierarchical assembly and the potential applications of the resulting chiral hierarchical patterns in solid-state spintronic and optical devices.

Chiral and directional optical emission from a dipole source coupled to a helical plasmonic antenna

Plasmonic antennas with helical geometry can convert linearly polarized dipole radiation into purely circularly polarized far-fields, and vice versa. Besides large Purcell enhancements, they possess a wide tunability due to the geometry dependence of their resonant modes. Here, the coupling of a dipole emitter embedded in a thin film to plasmonic single and double helices is numerically studied. Using a higher-order finite element method (FEM), the wavelength dependent Purcell enhancement of a dipole with different positions and orientations is calculated and the far-fields with respect to their chirality and radiation patterns are analyzed. Both single and double helices demonstrate highly directional and circularly polarized far-fields for resonant excitation but with significantly improved directional radiation for the case of double helices.

Delusive chirality and periodic strain pattern in moiré systems

Geometric phase analysis (GPA) is a widely used technique for extracting displacement and strain fields from scanning probe images. Here, we demonstrate that GPA should be implemented with caution when several fundamental lattices contribute to the image, in particular in twisted heterostructures featuring moiré patterns. We find that in this case, GPA is likely to suggest the presence of chiral displacement and periodic strain fields, even if the structure is completely relaxed and without distortions. These delusive fields are subject to change with varying twist angles, which could mislead the interpretation of twist angle-dependent properties.

Effects of non-uniformity in thickness and volume fraction of agglomerated CNTs on the dynamics of a spinning CNT-reinforced nanocomposite truncated conical shell

In the presented work, the free vibration analysis of a rotating truncated conical shell whose thickness varies in the meridional direction is examined. The material that the shell is made of is a polymeric matrix (epoxy) enriched with carbon nanotubes (CNTs) whose volume fraction varies in the meridional direction. CNTs agglomeration is considered and the density and elastic constants of such a two-phase nanocomposite are calculated sequentially based on the Eshelby–Mori–Tanaka approach alongside the rule of mixture. The conical shell is modeled using the first-order shear deformation theory (FSDT) including the relative acceleration, Coriolis acceleration, and centrifugal acceleration along with the initial hoop tension, and the governing equations are obtained utilizing Hamilton’s principle. The solution of governing equations is performed via the combination of an analytical solution in the circumferential direction and a numerical one in the meridional direction via the differential quadrature method (DQM). The impacts of several parameters on the forward and backward natural frequencies of such a rotating shell are studied such as chirality, mass fraction and dispersion pattern of the CNTs, thickness variation parameters, and boundary conditions. It is observed that higher natural frequencies and critical rotational speeds can be achieved for CNT-reinforced conical shells when the volume fraction of the CNTs and the thickness of the shell increase from its small radius to the large one.

Chirality effects in panto-cylindrical structures

In this paper, we apply a numerical integration strategy recently developed for determining the deformation shapes of structures constituted by Cosserat rods, to predict the behavior of panto-cylinders. Panto-cylinders have, as microstructure, a set of two families of helicoidal beams interconnected by perfect or elastic joints. The pivot’s free rotation axis is, in the reference configuration, orthogonal to the cylindrical surfaces spanned by the beams. We perform a series of numerical simulations looking for the mechanical parameters which exalt the chirality effects in the structure. For the performed compression, extensions, shear, and torsion tests, we find chiral deformation patterns with a dependence on the type of joint and its length.

Chiral helix amplification and enhanced bioadhesion of two-component low molecular weight hydrogels regulated by OH to eradicate MRSA biofilms.

The supramolecular chemistry of small chiral molecules has attracted widespread attention owing to their similarity to natural assembly codes. Two-component low-molecular-weight (LMW) hydrogels are crucial as they form helical structures via chirality transfer, enabling diverse functions. Herein, we report a pair of two-component chiral LMW hydrogels based on the small molecular drugs baicalin (BA), scutellarin (SCU) and berberine (BBR). The two hydrogels exhibited different helicities and abilities to adhere to methicillin-resistant staphylococcus aureus (MRSA) biofilms. The BA or SCU can each laterally interact with BBR in a tail-to-tail configuration, forming a stable hydrophobic structure, while hydrophilic glucuronide groups are exposed to a water solution to form a hydrogel. However, the tiny variant steric hindrance of the terminal OH moiety of SCU affects π-π stacking in the layered assembly, resulting in SCU-BBR having much stronger chirality deviation and supramolecular chirality amplification than BA-BBR. Thereafter, the OH group in SCU-BBR forms more intermolecular hydrogen bonds with MRSA biofilms, enhancing stronger adhesion and better scavenging effects than BA-BBR. This work provides a unique chiral supramolecular assembly pattern, expands the antibacterial application prospect of a two-component LMW hydrogel accompanying chirality amplification, and provides a new perspective and strategy for biofilm removal.

Unrestricted Chiral Patterning by Laser Writing in Liquid Crystalline and Plasmonic Nanocomposite Thin Films.

Obtaining hierarchical structures with arbitrarily controlled chirality remains a challenge. Here, thin films featuring chiroptically bipolar patterns are produced by a device utilizing microscale photothermal re-melting of materials exhibiting chirality synchronization. This device operates autonomously, guided by an algorithm that facilitates the homochiral growth of supramolecular organic helices through controlling their re-melting. The chirality synchronization phenomena of constitutionally achiral molecules grants availability of both handednesses of the helices, enabling unrestricted chiral writing in the film. The collective chiroptical response of assembled molecules is utilised to guide the patterning process, creating a foundation for optically secured information. The established methodology enables achieving dissymmetry factor values for circular dichroism (CD) a magnitude higher than previously reported, as confirmed with state-of-the-art, synchrotron-based Mueller matrix polarimetry (MMP). Moreover, the developed method is extended to nanocomposites comprising gold nanoparticles, providing the opportunity to tune the CD toward the plasmonic region. This strategic application of photothermal processing, specifically laser-directed melting, uncovers the potential to broaden the selection of nanostructured materials with precisely designed functionalities for photonic applications.

Homochiral Nanopropeller via Chiral Active Surface Growth.

Under the control of chiral ligand glutathione and in the presence of hexadecyltrimethylammonium bromide, Au deposition on Au seeds is known to give chiral nanostructures. We have previously shown that the protruding chiral patterns, as opposed to flat facets, are likely caused by active surface growth, where nonuniform ligand coverage could be responsible for the focused growth at a few active sites. By pushing the limit of such a growth mode, here, we use decahedral seeds to prepare homochiral nanopropellers with intricate patterns of deep valleys and protruding ridges. Control experiments show that the focused growth depends on the rates of Au deposition by changing either the seed concentration or the reductant concentration, consistent with the proposed mechanism. The dynamic growth competition between the ligand-deficient active sites and the ligand-rich surfaces gradually focuses the growth onto a few active sites, causing the expansion of grooves, squeezing of steep ridges, and a surprising 36° rotation of the pentagonal outline. The imbalanced deposition on the prochiral slopes is responsible for the tilted grooves, the twisted walls, and thus the well-separated and distorted blades, which become the origin of the chiroptical responses.

Nanotube Slidetronics.

One-dimensional slidetronics is predicted for double-walled boron-nitride nanotubes. Local electrostatic polarization patterns along the body of the nanotube are found to be determined by the nature of the two nanotube walls, their relative configuration, and circumferential faceting modulation during coaxial interwall sliding. By careful choice of chiral indices, chiral polarization patterns can emerge that spiral around the nanotube circumference. The potential usage of the discovered slidetronic effect for low-dimensional nanogenerators is briefly discussed.

Gravitational waves from SU(N)/SP(N) composite Higgs models

We study possible strong first-order electroweak phase transitions in Composite Higgs models and we quantify the part of parameter space that can be probed with future gravitational wave experiments. We focus on models where the Composite Higgs sector arises from underlying four-dimensional strongly interacting gauge theories with fermions, and where the Standard Model fermion masses are induced via linear mixing terms with composite fermions — the so-called fermion partial compositeness framework. We perform our analysis for the general class of Composite Higgs models arising from N Weyl fermions in a pseudo-real representation of the new strongly interacting gauge group that dynamically triggers the global chiral symmetry breaking pattern SU(N) → Sp(N). The minimal model has N = 4 and for N > 4 the models feature complex scalar dark matter candidates arising as pseudo-Nambu-Goldstone bosons. We find a large number of points in the models parameter space which yield strong first-order electroweak phase transitions and identify the most important operators characterizing the strength of the phase transition. Almost all of these points are testable with future GW detectors such as LISA, Taiji, Tianqin, BBO, DECIGO and Ultimate-DECIGO.

Metamaterial boat fenders with supreme shape recovery and energy absorption/dissipation via FFF 4D printing

In maritime transportation, a fender acts like a bumper to absorb the kinetic energy of a boat berthing against a jetty, pier wall, or other boats. They have high energy absorption and low reaction forces, preventing damage to boats and berthing structures. The aim of this paper is to introduce a novel conceptual design for a new class of lightweight boat-fendering systems with superior energy absorption/dissipation and shape recovery features. Different metamaterials with honeycomb, re-entrant, and re-entrant chiral auxetic patterns are designed in the form of boat fender panels, and their thermo-mechanical behaviors are analyzed experimentally and numerically. A finite element modeling (FEM) is developed to investigate the compressive behaviors of boat fenders. Some of designs are 4D printed by fused filament fabrication of shape memory polylactic acid polymers and then tested thermo-mechanically. A good correlation is observed between numerical and experimental results, supporting the FEM accuracy. Results reveal that proposed boat fenders have considerable energy absorption/dissipation along with the capability to fully recover plastic deformations by simply heating up. The excellent mechanical property recovery of the proposed boat-fendering system is also shown under cycling loadings. Due to the absence of similar conceptual designs, models, and results in the specialized literature, this paper is expected to be instrumental towards 4D printing novel boat fenders with supreme energy absorption/dissipation and shape recovery properties promoting sustainability.

Nucleation-mediated growth of chiral 3D organic-inorganic perovskite single crystals.

Although their zero- to two-dimensional counterparts are well known, three-dimensional chiral hybrid organic-inorganic perovskite single crystals have remained difficult because they contain no chiral components and their crystal phases belong to centrosymmetric achiral point groups. Here we report a general approach to grow single-crystalline 3D lead halide perovskites with chiroptical activity. Taking MAPbBr3 (MA, methylammonium) perovskite as a representative example, whereas achiral MAPbBr3 crystallized from precursors in solution by inverse temperature crystallization method, the addition of micro- or nanoparticles as nucleating agents promoted the formation of chiral crystals under a near equilibrium state. Experimental characterization supported by calculations showed that the chirality of the 3D APbX3 (where A is an ammonium ion and X is Cl, Br or mixed Cl-Br or Br-I) perovskites arises from chiral patterns of the A-site cations and their interaction with the [PbX6]4- octahedra in the perovskite structure. The chiral structure obeys the lowest-energy principle and thereby thermodynamically stable. The chiral 3D hybrid organic-inorganic perovskites served in a circularly polarized light photodetector prototype successfully.

Long‐Range Magnetic Exchange Coupling in Quasi‐2D CrTe Ferromagnetic Thin Films

The 2D chromium telluride family (CrxTey) is an outstanding candidate for creating high‐density and dissipationless nanodevices because of its high Curie temperature, chiral spin patterns, and large saturation magnetic moment. However, the precise magnetic exchange mechanism and crucial phase transitional property of CrxTey must be fully analyzed. Herein, a large‐area CrTe (x:y = 1:1) single‐crystalline films deposited on an Al2O3 substrate. Based on the analysis of critical isothermal magnetization around the Curie temperature TC = 201 K and the modified Arrott plot, the precise critical exponents β = 0.386(3) and γ = 1.391(2) are obtained. Both their reliability and accuracy are also verified by Kouvel–Fisher theory, Widom scaling law, and scaling equation. Moreover, using the renormalization group theory, it is confirmed that CrTe belongs to a quasi‐2D Heisenberg‐like behavior with long‐range interactions. Finally, the density functional theory calculations indicate that, near the Fermi level, the CrTe band structure is mainly composed of Cr atom. The spin‐polarized density of states shows that the total magnetic moments are determined mainly by the polarized spin‐up t2g electron of Cr atom. This work is an important asset for a series of CrxTey materials in future spintronic applications.