Chirality Distribution Research Articles

Polar domain walls induced by sequential symmetry breaking in frustrated mechanical metamaterials

Frustration hinders ideal local interactions in systems ranging from artificial spin ices with ice rules to mechanical metamaterials featuring regular floppy modes. While geometric frustrations have been known to promote complex ordered patterns in tessellated lattice structures, there is growing interest in global frustrations due to the topologically nontrivial geometry of metamaterials. However, multiferroic orders in globally frustrated metamaterials have remained elusive. Here, we present polar domain walls constrained in flexible mechanical metamaterials with global frustration and sequential symmetry breaking. We showcase that under simple compressive loading, competing interactions in globally frustrated metamaterials give rise to mixed deformations with high-order buckling modes described by an emergent order parameter. Utilizing an elastic mechanism model, we unveil the process of sequential symmetry breaking and capture the formation of polar domain walls exhibiting a chiral distribution within a multi-well potential landscape. We further demonstrate how to eliminate frustration through torsional loading, leading to symmetry restoration. These results provide insights into the intricate interactions between order and frustration, inspiring the modulation of domain walls in macroscopic systems.

Length-based quantitative characterization of metallic and semiconducting single-wall carbon nanotubes using electrostatic force microscopy

Precise and quantitative evaluation of the semiconducting (or metallic) purity of single-wall carbon nanotubes (SWCNTs) is extremely significant, not only for obtaining an indicator on their separation process development, but also for the property analysis in their electronic applications. In this work, electrostatic force microscopy (EFM) was applied to quantify the semiconducting (s-) type purity for as-grown and separated SWCNT samples. Count-based and length-based analyses for hundreds of SWCNTs observed in EFM images were carried out. By analyzing 1826 SWCNTs of as-grown sample based on the count, the s-type purity was estimated around 77.8 %. On the other hand, the length-based analysis showed the s-type purity of 67.3 %. The latter result, suggesting approximately equal to the semiconducting purity of SWCNTs with a random chiral distribution, is probably because the length-based analysis provides weighted statistics that is more suitable for the quantitative evaluation, and supports the validity in terms of precision. Furthermore, it was also demonstrated that the length-based EFM analysis for 850 SWCNTs of s-type enriched SWCNTs showed the s-type purity of 98.6 %.

A Mechanism of Resistance Switching in CNT Based Memory Devices

Carbon nanotubes (CNTs) show promise for high energy efficiency electronic devices due to their high electrical conductivity. One possible application is in the fabrication of resistance-change computer memory, where the application of an external electrical bias can use a CNT layer as the switching element in a RAM cell. Memory cells of this type have been extensively demonstrated, where the electrical resistance of a switching layer of CNTs can be reversibly controlled by the application of external bias [1].To better understand these devices, we have developed a nanoscale model of their electrical switching. Towards this end, first-principles calculations of the electrical conductivity of CNT-CNT junctions were performed using the Density Functional Tight Binding (DFTB) in combination with the Non-Equilibrium Greens functions (NEGF) approach, enabling an improved understanding of the tunnelling of electrons across a range of CNT junctions [2]. These results demonstrate that the conductivity of CNT contacts depends on the overlap area between nanotubes and exponentially on the distances between the carbon atoms of the interacting CNTs. Secondly, we employed coarse-grained molecular dynamics [3,4] to produce nanoscale dense CNT film models like those used in the devices. We devise a set of metrics for characterising the structural properties of CNT films, and apply them to a set of model films designed to mimic those used in microelectronics devices. In order to understand how the geometrical properties of CNTs affect the film structure, we analyse films with different CNT chirality and length distributions. Unlike previous studies that focused on relatively low-density systems below ∼0.4 g/cm3, we also consider films with density of ∼0.6 g/cm3, as employed in experimentally fabricated CNT-based NRAM devices. By adding amorphous carbon to the film models, in varying amounts, we are then able to assess its effects. Finally, these two elements were combined to produce electrical simulations of the conductivity of the CNT films connected to TiN electrodes. These electrodes are shown to be partially oxidized during the device fabrication. The electrical conductivity in a device is characterized by formation of conduction paths formed by CNTs between the electrodes and connected via the CNT junctions. The conductivity is modulated by charging of CNTs and amorphous carbon present in the film.Using these simulations, we propose a resistance switching mechanism in TiN/CNT/TiN devices based on the physical movement of CNTs. During the initial operation of the device, oxygen is released from the oxidized bottom electrode and this readily reacts with individual CNTs to form charge trapping sites. Once these sites have become charged, they enable controllable movement of CNTs at the bottom electrode under the application of electric field. By reversibly connecting and disconnecting such CNTs from the bottom electrode, the electrical conductivity through the CNT film as a whole can be controlled.

Generation of chiral optical vortex lattice for controlled aggregation of particles

The chiral light field has attracted great attention owing to its interaction with chiral matter. The generation of chiral light fields with rich structures has become crucial as it can expand application scenarios. Herein, we introduce a chiral optical vortex lattice. As a whole, the optical vortex lattice has a chiral intensity distribution, with each spiral arm having sub-vortices (chiral phase). By using an expansion factor to adjust the involute of a circular lattice, this helical optical vortex lattice can be continuously varied from a circular lattice. The chirality of intensity and phase can be controlled independently. Furthermore, the optical tweezers using the lattice demonstrate the capability of sub-vortices to manipulate particle movement, with the chiral intensity determining the trajectory of particle motion. As the lattice possesses both intensity and phase chirality, it may also find potential applications in tasks such as chiral structure microfabrication.

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.

Chemical Variability, Antioxidant and Larvicidal Efficacy of EOs from Citrus sinensis (L.) Osbeck Peel, Leaf, and Flower

Essential oils (EOs) from Citrus sinensis (Rutaceae) possess diverse biological activities. However, a comprehensive comparison of their chemical composition and bioactivity across different plant parts has not been studied yet. The current research comparatively assesses the yield, chemical composition, chiral distribution, antioxidant properties, and larvicidal activity of EOs extracted from the peels, leaves, and flowers of C. sinensis. EOs extracted via hydro-distillation (HD) and steam distillation (SD) were analyzed by gas chromatography–mass spectrometry (GC-MS) and chiral GC-MS to explore their chemical composition and enantiomeric distribution. In addition, their larvicidal and antioxidant potentials were evaluated following standard protocols. Peels of C. sinensis exhibited significantly higher oil content (1.75–2.25%) compared to its leaves (0.75–0.78%) and flowers (0.20–0.25%). The GC-MS analysis identified around 60 compounds, including terpenoids, sesquiterpenoids, and oxygenated terpenoids in the HD and SD extractions. Higher concentrations of sabinene were found in flower extract (38.05–39.89%) and leaf extract (32.30–36.91%), while peel extract contained more than 90% limonene. The larvicidal activity of peel oil was primarily attributed to limonene, with an LC50 value of 0.0031 µL/mL. The current study reports the first chiral (GC-MS) analysis in the essential oil of the leaves and flowers of C. sinensis, paving the way for authenticity and purity. Furthermore, the chemical profiling of citrus EOs, particularly from the peel, demonstrates a safe and promising candidate for diverse biological applications.

Parametric resonance in Abelian and non-Abelian gauge fields via spacetime oscillations

We study the evolution of Abelian U(1) electromagnetic as well as non-Abelian SU(2) gauge fields, in the presence of spacetime oscillations. Analysis of the time evolution of Abelian gauge fields shows the presence of parametric resonance in spatial modes. A similar analysis in the case of non-Abelian gauge fields, in the linear approximation, shows the presence of the same resonant spatial modes. The resonant modes induce large fluctuations in physical observables including those that break the CP symmetry. We also carry out time evolution of small random fluctuations of the gauge fields, using numerical simulations in 2+1 and 3+1 dimensions. These simulations help to study nonlinear effects in the case of non-Abelian gauge theories. Our results show that there is an increase in energy density with the coupling, at late times. These results suggest that gravitational waves may excite non-Abelian gauge fields more efficiently than electromagnetic fields. Also, gravitational waves in the early Universe and from the merger of neutron stars, black holes, etc., may enhance CP violation and generate an imbalance in chiral charge distributions, magnetic fields, etc. Published by the American Physical Society 2024

An efficient approach toward production of near-zigzag single-chirality carbon nanotubes.

Synthesizing single-walled carbon nanotubes (SWCNTs) with a narrow chirality distribution is essential for obtaining pure chirality materials through postgrowth sorting techniques. Using carbon monoxide chemical vapor deposition, we devise a ruthenium (Ru) catalyst supported by silica for the bulk production of SWCNTs containing only a few (n, m) species. The result is attributed to the limited carbon dissociation on the supported Ru clusters, favoring the growth of only small-diameter SWCNTs at comparable growth rates. The resulting materials expedite high-purity single chirality separation using gel chromatography, leading to unprecedented yields of 3.5% for (9, 1) and 5.2% for (9, 2) nanotubes, which surpass those separated from HiPco SWCNTs by two orders of magnitude. This work sheds light on the large-quantity synthesis of SWCNTs with enriched species beyond near-armchair ones for their high-yield separation.

Enantiomeric separation of four pairs of alkaloids by using a C18 column tandem polysaccharide-based chiral column

Abstract Alkaloid enantiomers have different physiological and pharmacological effects, and different chiral compositions have a large impact on cigarette sensory and use safety. Studying the effects of different configurations of alkaloid enantiomers on cigarette sensory is important for the development of tobacco products, but the chiral separation of alkaloid enantiomers has become the core problem. Here, the application of a C18 column coupled with a polysaccharide-based chiral column to separate and detect four pairs of alkaloid enantiomers in tobacco and cigarette smoke of different brands was investigated. Results showed that the tandem technology of the two columns enabled the baseline separation of four pairs of alkaloid enantiomers. The resolution of enantiomers of alkaloids in different tobacco samples differed in content and ratio, showing different chiral distribution characteristics. According to the different distribution characteristics of alkaloid enantiomers, tobacco samples of different brands can be distinguished and real cigarettes can be identified.

Iterative Strategy for Sorting Single-Chirality Single-Walled Carbon Nanotubes from Aqueous to Organic Systems.

Significant advancements in electronic devices and integrated circuits have been facilitated by semiconducting single-walled carbon nanotubes (SWCNTs) sorted by conjugated polymers (CPs). However, the variety of CPs with single-chirality selectivity is limited, and the sorting results are strongly dependent on the chiral distribution of the starting materials. To address this, we develop an iterative strategy to achieve single-chirality SWCNT separation from aqueous to organic systems, based on a multistep tandem extraction technique that allows a gentle and nondestructive separation of surfactants from SWCNTs, ensuring an efficient system transfer. In parallel, we refined the iterative sorting process between CPs. Employing two starting materials with narrow diameter distributions, using three CPs, we successfully sorted out five single-chirality SWCNTs of the (9,5), (8,6), (10,5), (8,7), and (11,3) species in organic systems. This strategy bridges the gap between aqueous and organic separation systems, achieving efficient complementarity between them.

Growth of Single-Walled Carbon Nanotubes from Solid Supported Heterogeneous Catalysts: Achievements and Challenges

Single-walled carbon nanotubes (SWNTs) have gained worldwide attention because of their exceptional electronic, optical, and mechanical properties, which are contingent on their structures denoted by chiral indices (n, m). To fully harness the extraordinary properties and advance SWNT-based technology, large scale synthesis of SWNTs with a narrow chirality distribution or even a specific (n, m) is highly demanded. Among various SWNT preparation techniques, chemical vapor deposition growth from solid supported heterogeneous catalysts has emerged as a promising approach in terms of large yield and (n, m) structure control. In this review, we provide an overview of the progress in developing heterogeneous catalysts for bulk synthesis of SWNTs. Firstly, the advantages and disadvantages of using solid supported catalysts for chemical vapor deposition growth of SWNTs are discussed. Secondly, the key components in supported catalysts, including the metallic component and the nature of support material, as well as their respective roles in affecting the catalyst performances and SWNT chirality distribution, are highlighted. Finally, the current challenges and future directions in the field of SWNT synthesis from solid supported catalysts are proposed.

Structural Diversity of Single-Walled Transition Metal Dichalcogenide Nanotubes Grown via Template Reaction.

Monolayers of transition metal dichalcogenides (TMDs) are an ideal 2D platform for studying a wide variety of electronic properties and potential applications due to their chemical diversity. Similarly, single-walled TMD nanotubes (SW-TMDNTs)-seamless cylinders of rolled-up TMD monolayers-are 1D materials that can exhibit tunable electronic properties depending on both their chirality and composition. However, much less has been explored about their geometrical structures and chemical variations due to their instability under ambient conditions. Here, the structural diversity of SW-TMDNTs templated by boron nitride nanotubes (BNNTs) is reported. The outer surfaces and inner cavities of the BNNTs promote and stabilize the coaxial growth of SW-TMDNTs with various diameters, including few-nanometers-wide species. The chiral indices (n,m) of individual SW-MoS2 NTs are assigned by high-resolution transmission electron microscopy, and statistical analyses reveals a broad chirality distribution ranging from zigzag to armchair configurations. Furthermore, this methodology can be applied to the synthesis of various TMDNTs,such as selenides and alloyed Mo1- x Wx S2 . Comprehensive microscopic and spectroscopic analyses also suggest the partial formation of Janus MoS2(1- x ) Se2 x nanotubes. The BNNT-templated reaction provides a universal platform to characterize the chirality-dependent properties of 1D nanotubes with various electronic structures.

Molecular Doping Modulation and Applications of Structure-Sorted Single-Walled Carbon Nanotubes: A Review.

Single-walled carbon nanotubes (SWCNTs) that have a reproducible distribution of chiralities or single chirality are among the most competitive materials for realizing post-silicon electronics. Molecular doping, with its non-destructive and fine-tunable characteristics, is emerging as the primary doping approach for the structure-controlled SWCNTs, enabling their eventual use in various functional devices. This review provides an overview of important advances in the area of molecular doping of structure-controlled SWCNTs and their applications. The first part introduces the underlying physical process of molecular doping, followed by a comprehensive survey of the commonly used dopants for SWCNTs to date. Then, it highlights how the convergence of molecular doping and structure-sorting strategies leads to significantly improved functionality of SWCNT-based field-effect transistor arrays, transparent electrodes in optoelectronics, thermoelectrics, and many emerging devices. At last, several challenges and opportunities in this field are discussed, with the hope of shedding light on promoting the practical application of SWCNTs in future electronics.

(Invited) Diameter-Dependent Stacking of Squaraine Dye Molecules inside Chirality-Sorted Single-Wall Carbon Nanotubes

Filling of single-wall carbon nanotubes (SWCNTs) with organic dye molecules is a promising strategy to add new functionalities, for instance by aligning dipolar dyes in a one-dimensional (1D) head-to-tail coupled chain to obtain a giant enhancement of their nonlinear optical response,[1] or by photo-sensitizing the tubes in new wavelength ranges by excitation energy transfer (EET) from the dye to the SWCNTs, useful for photo-conversion applications.[2] The 1D stacking of molecules inside SWCNTs modulates both the properties of the molecules and of the SWCNTs. We found that the EET of squaraine-dye-filled SWCNTs reveals a pronounced SWCNT-diameter-dependence of the dye absorption, indicating a diameter-dependent stacking. By performing IR fluorescence excitation spectroscopy on a range of chirality-enriched samples of dye-filled SWCNTs with different chirality distributions, each shifted dye absorption wavelength observed through the EET can be unambiguously assigned to a specific encapsulating SWCNT chirality.[3] This reveals a systematic trend with diameter that can be associated with the J-aggregate- and H-aggregate-like interactions expected in close-packed single- and double-file stackings, as corroborated by a simple geometric model, and enables tuning of the optical properties of the 1D molecular arrays through the selection of proper SWCNT diameters.[1] S. Cambré, J. Campo, C. Beirnaert, C. Verlackt, P. Cool, W. Wenseleers, Nature Nanotechnol. 10(3) 248-252 (2015). [2] S. van Bezouw, D.H. Arias, R. Ihly, S. Cambré, A.J. Ferguson, J. Campo, J.C. Johnson, J. Defillet, W. Wenseleers, J.L. Blackburn, ACS Nano 12(7) 6881-6894 (2018). [3] S. Forel, H. Li, S. van Bezouw, J. Campo, L. Wieland, W. Wenseleers, B.S. Flavel, S. Cambré, Nanoscale 14, 8385-8397 (2022).

All-plasmonic-metal chiral nanostructures fabricated by circularly polarized light

Chiral plasmonic nanostructures, which would be applied to enantioselective sensors and metasurfaces, can be prepared in an enantioselective manner by irradiation with circularly polarized light (CPL). However, their resonance sites have been covered with non-plasmonic, dielectric moieties. Here, we prepared all-silver chiral plasmonic nanostructures on a glass plate in one-step by irradiating 380–450 nm right- or left-CPL to an aqueous solution containing Ag+ and citrate ions. Achiral or racemic Ag nanoparticles with anisotropic geometry are deposited on a glass plate by photochemical electron transfer from citrate to Ag+ in the initial phase. The deposited nanoparticles are grown into chiral structures under CPL via generation of an electric field with chiral distributions. An achiral Ag nanoplate array was also grown under 600–700 nm CPL into chiral nanostructure arrays on the basis of hot electron reduction of Ag+.

Narushenie kiral'noy simmetrii i neodnorodnye sostoyaniya v deformirovannykh ferromagnetikakh

The general form of chiral terms associated with deformation of a ferromagnet is determined. The possibility of a transition from the helical state to the vortex state is demonstrated for a ferromagnetic rod subjected to elastic torsional strain. In the case of a single screw dislocation, the formation of the skyrmion state due to elastic strains and the helical distribution of magnetization induced by strains in the dislocation core is indicated. The conditions in which a transition from one chiral magnetization distribution to another distribution in an ensemble of identical dislocations are determined.

Ultrafast phonon diffuse scattering as a tool for observing chiral phonons in monolayer hexagonal lattices

At the 2D limit, hexagonal systems such as monolayer transition metal dichalcogenides (TMDs) and graphene exhibit unique coupled spin and momentum-valley physics (valley pseudospin) owing to broken spatial inversion symmetry and strong spin-orbit coupling. Circularly polarized light provides the means for pseudospin-selective excitation of excitons (or electrons and holes) and can yield momentum-valley polarized populations of carriers that are the subject of proposed valleytronic applications. The chirality of these excited carriers has important consequences for the available relaxation/scattering pathways, which must conserve (pseudo)angular momentum as well as energy. One available relaxation channel that satisfies these constraints is coupling to chiral phonons. Here, we show that chiral carrier-phonon coupling following valley-polarized photoexcitation is expected to lead to a strongly valley-polarized chiral phonon distribution when this relaxation mechanism is dominant. This momentum valley phonon polarization is directly measurable using ultrafast phonon diffuse scattering techniques. Using ab initio calculations, we show how the dynamic phonon occupations and valley anisotropy determined by nonequilibrium observations can provide a new window on the physical processes that drive carrier valley depolarization in monolayer TMDs.

Lithography‐Free Fabrication of Terahertz Chiral Metamaterials and Their Chirality Enhancement for Enantiomer Sensing

AbstractChiral metamaterials comprise a promising platform for advanced optoelectronic and biomedical applications. However, conventional fabrication via lithography is limited by its complexity and high cost. Herein, the lithography‐free fabrication of terahertz chiral metamaterials and their enhancement for sensing the chirality of biocrystal enantiomers is presented. Chiral Au microstrip patterns (CHAMs) in a saw‐tooth shape are fabricated by combining two‐step buckling processes and glancing‐angle deposition. Non‐superimposable geometric chirality is achieved by controlling the tilt angle between the asymmetric and biaxial strain axes and the selective area deposition of the Au layers by using the shadow effect. The manufactured chiral metamaterials show mirror‐shaped terahertz circular dichroism (TCD) signals in the range of 0.2–2.5 THz. Coupling of the induced electric and magnetic dipoles to the chiral‐shaped Au surfaces results in effective optical chirality enhancement. Finite‐difference time‐domain computational simulations reveal the homogeneous distribution of optical chirality with an absolute maximum of 2.24 in the near field. Summing the TCD signals for enantiomeric cystine biocrystals onto the chiral metamaterials shows an ≈7‐fold amplification in magnitude. This enhancement can be attributed to the synergistic effects of superchiral field enhancement and the electromagnetic resonance between the CHAMs and biocrystals.

Creating Chiral Plasmonic Nanostructures Using Chiral Light in a Solution and on a Substrate: The Near‐Field and Hot‐Electron Routes

AbstractCan chiral light induce chiral shapes in nanocrystals in a diluted solution? So far, it has been unclear whether it could be and, if such, under which conditions it may occur. By using realistic models of plasmonic nanocrystals, this work shows that the imprinting of 3D chirality on nanocrystals in solution by circularly polarized light (CPL) is possible. Such 3D‐chiral patterns originate from the electromagnetic retardation effect. This work investigates the formation of chiral spatial distributions of the near fields and hot electrons produced by CPL in both substrate and solution settings. Anisotropic nanocrystals with sharp edges and tips are preferable for inducing 2D and 3D chirality because of the formation of chiral hot‐spot patterns on them. The 2D g‐factors are always much higher than the 3D ones. In addition, 3D‐chiral imprinting on spherical nanocrystals is impossible. With linearly polarized light (LPL), one can create chiral nanocrystals on a substrate, not in a solution. This study provides the principles for emerging technologies to create chiral nanostructures using CPL and LPL illuminations.

One-step separation of high-purity single-chirality single-wall carbon nanotubes using sodium hyodeoxycholate

Chirality separation of single-wall carbon nanotubes (SWCNTs) is key to enabling applications in single photon sources, optoelectronic devices and bioimaging, and it generally requires multiple separation steps to obtain single chirality species with the desired purity. In this work, we report the use of a novel sodium hyodeoxycholate (SHC) surfactant for separation of single-chirality SWCNTs. The results demonstrated that chirality-selective adsorption and desorption of SWCNTs on a gel column can be achieved readily by modulating the concentrations of the SHC-based mixed surfactants. Through an optimized one-step procedure, single-chirality (6,5) SWCNTs were successfully separated, and the chirality purity was estimated to be 97% by using a spectroscopic approach, exceeding most reported purities for traditional surfactant-based one- or multiple-step separations. Due to the ultrahigh chirality resolution of the present method, the (6,5) SWCNTs can also be effectively separated from different SWCNT materials with various diameter or chirality distributions, even from materials containing very few (6,5) SWCNTs. The high-purity chirality separation demonstrated in this work lays an important foundation for the industrial production and applications of single-chirality SWCNTs.