Chiral Switch Research Articles

Visible‐Light‐Actuated Bidirectional Photochromism in Chiral Nanostructures with Multi‐Degree of Freedom

AbstractCholesteric liquid crystals (CLCs) with chiral nanostructures take on great significance in light modulation for optical devices, especially involving the features of circularly polarized and dynamic structural colors. However, on‐demand self‐assembly by photoprogramming still remains a challenge that is ascribed to the unpredictable variation of the helical superstructures in the existing CLCs induced by light‐driven chiral switches. Here, novel binary chiral systems are designed to construct visible‐light‐actuated CLCs with multi‐degrees of freedom, including adjustable circular polarization, bidirectional photochromism, and manipulable photonic bands. Such systems consist of an o‐fluoroazobenzene‐containing chiral switch and an inert chiral dopant, whose interaction dominates the strategies of chiral cooperation or conflict to determine the CLC handedness as well as shift direction of the selective reflection. Particularly, the precise tuning range of the structural color is tailored by programmable helical twisting power to enable diverse paradigms of light‐actuated patterning. The unprecedented quantitative manipulation of circularly polarized structural colors offers unique photonic attributes for applications in information encoding and multiplexed communication.

Tunable and strong circular dichroism metamaterial absorber based on gold-VO2 hybrid structure

The existing terahertz chiral absorber faces a series of issues, including low efficiency, un-tunable absorption, and complex structure. We present a chiral metamaterial absorber integrated with gold and phase-change material vanadium dioxide (VO2) to address the issues above. Our designed metamaterial absorber’s maximum circular dichroism (CD) value, as an ideal chirality-selective meta-absorber, reaches 0.95 when VO2 behaves as a metallic state. However, when VO2 is in the insulator state, the CD value is merely 0.003. Notably, the intrinsic mechanisms of the CD effect are revealed by analyzing the difference in electromagnetic response under left-handed circularly polarized (LCP) and right-handed circularly polarized (RCP) illumination. The designed chiral metamaterial absorber supports the free switching of the CD signal between ‘on’ and ‘off’ states by continuously adjusting the conductivity of VO2 with a CD value ranging from 0 to 0.95. Moreover, the absorption performance of chiral metamaterials is affected by geometric parameters and the angle of incidence. To evaluate the capability of chiral structure in biosensing, three typical avian influenza viruses are sensed by detecting changes in their resonant frequencies and CD values. Finally, the presented chiral-selective absorber with phase-change materials has an important reference value in the terahertz range for constructing chiral light detectors, chiral thermal switching, biosensors, and tunable chiral photonics.

The Death of the Strategy of Classical Chiral Switches Is an Exaggeration

The Death of the Strategy of Classical Chiral Switches Is an Exaggeration

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.

A Multiresponsive Ferrocene-Based Chiral Overcrowded Alkene Twisting Liquid Crystals.

The reversible modulation of chirality has gained significant attention not only for fundamental stereochemical studies but also for numerous applications ranging from liquid crystals (LCs) to molecular motors and machines. This requires the construction of switchable molecules with (multiple) chiral elements in a highly enantioselective manner, which is often a significant synthetic challenge. Here, we show that the dimerization of an easily accessible enantiopure planar chiral ferrocene-indanone building block affords a multi-stimuli-responsive dimer (FcD) with pre-determined double bond geometry, helical chirality, and relative orientation of the two ferrocene motifs in high yield. This intrinsically planar chiral switch can not only undergo thermal or photochemical E/Z isomerization but can also be reversibly and quantitatively oxidized to both a monocationic and a dicationic state which is associated with significant changes in its (chir)optical properties. Specifically, FcD acts as a chiral dopant for cholesteric LCs with a helical twisting power (HTP) of 13 µm-1 which, upon oxidation, drops to near zero, resulting in an unprecedently large redox-tuning of the LC reflection color by up to 84 nm. Due to the straightforward stereoselective synthesis, FcD, and related chiral switches, are envisioned to be powerful building blocks for multi-stimuli-responsive molecular machines and in LC-based materials.

Controllable perfect chiral optical response in planar metasurfaces empowered by quasi-bound states in the continuum

Chiral metasurfaces with strong chirality and high quality factors (Q-factors) have become essential components for achieving strong light-matter interactions and have a wide range of applications in chiral lasers, detectors, etc. However, current schemes primarily focus on enhancing the chiral response and Q-factor, with limited consideration of their modulability and flexibility. In this paper, we present a chiral a-Si metasurface that can support multiple symmetry-protected bound states in the continuum (BIC). The perfect extrinsic and intrinsic chiral responses (circular dichroism exceeding 0.99), with ultra-high Q-factors, are achieved by utilizing quasi-BICs induced by illumination symmetry and in-plane symmetry breaking. The circular dichroism value and the transmittance of the two circular polarization states can be arbitrarily controlled by adjusting the structural parameters. Furthermore, the feasibility of achieving dynamic modulation of chiral response is demonstrated based on the a-Si-graphene hybrid metasurface. Our research offers an approach to the design of controllable planar optical chirality, which also provides promising avenues for applications in spin-selective bio-detection, electrically tunable chiral switching, and chiral lasers.

Beta2-adrenergic agonist salbutamol exhibits enantioselective disposition in skeletal muscle of lean young men following oral administration.

Salbutamol is a common short-acting beta2-adrenergic agonist used in treatment of asthma and exercise-induced bronchoconstriction but also possesses anabolic and metabolic actions in skeletal muscle. As a chiral compound, salbutamol is a racemic 1:1 mixture of two enantiomers, (R)-salbutamol and (S)-salbutamol, which exhibit divergent pharmacokinetic and pharmacodynamic actions. Despite salbutamol being available for decades, information on the enantioselective disposition of salbutamol enantiomers in human skeletal muscle is absent. In this study, we determined concentrations of (R)-salbutamol and (S)-salbutamol by UHPLC-MS/MS in arterial plasma and vastus lateralis muscle samples from 12 lean young men 2½ and 7 h following ingestion of 24 mg oral salbutamol. Mean (range) arterial plasma concentrations were 10-fold higher (p < 0.001) for (S)-salbutamol than (R)-salbutamol, being 33(9-62) and 49(30-84) ng·mL-1 for (S)-salbutamol and 4 (1-6) and 4 (2-5) ng·mL-1 for (R)-salbutamol 2½ and 7 h following administration, respectively, reflecting faster elimination of the (R)-enantiomer. Mean (range) muscle concentrations were higher (p < 0.001) for (S)-salbutamol than (R)-salbutamol 2½h (0.17 [0.1-0.26] vs. 0.04 [0.02-0.06]) and 7 h (0.31 [0.21-0.46] vs. 0.06 [0.04-0.12] ng·mgd.w. -1) after administration. However, muscle:plasma partition coefficient was two-fold higher (p < 0.001) for (R)-salbutamol than (S)-salbutamol 7 h following administration. These observations demonstrate that oral salbutamol exhibits enantioselective disposition in systemic circulation and muscle favoring the (S)-enantiomer but with higher relative partitioning of the (R)-enantiomer in skeletal muscle. Furthermore, the concentration-time profiles of salbutamol enantiomers are different in skeletal muscle and systemic circulation following oral ingestion. These findings have implications for the application of chiral switch (R)-salbutamol in doping control.

Chiral Switches of Tramadol Hydrochloride, a Potential Psychedelic Drug-Past and Future.

The chiral opioid analgesic tramadol was patented (1962) as a cis- and trans-racemates mixture. A first chiral switch led to the (±)-cis-(1RS,2RS) racemate, patented and approved as Tramal (1980), preferred over the (+)-cis-(1R,2R)-enantiomer. Consecutive chiral switches of (±)-cis-tramadol to (+)-cis-(1R,2R)-tramadol/salts were patented. This Viewpoint calls for developing (+)-cis-(1R,2R)-tramadol medicines and recognizing tramadol medicines as potential psychedelics to overcome the spreading tramadol crisis.

Multiple Chirality Switching of a Dye‐Grafted Helical Polymer Film Driven by Acid &amp; Base

AbstractA stimuli‐responsive multiple chirality switching material, which can regulate opposed chiral absorption characteristics, has great application value in the fields of optical modulation, information storage and encryption, etc. However, due to the rareness of effective functional systems and the complexity of material structures, developing this type of material remains an insurmountable challenge. Herein, a smart polymer film with multiple chirality inversion properties was fabricated efficiently based on a newly‐designed acid &amp; base‐sensitive dye‐grafted helical polymer. Benefited from the cooperative effects of various weak interactions (hydrogen bonds, electrostatic interaction, etc.) under the aggregated state, this polymer film exhibited a promising acid &amp; base‐driven multiple chirality inversion property containing record switchable chiral states (up to five while the solution showed three‐state switching) and good reversibility. The creative exploration of such a multiple chirality switching material can not only promote the application progress of current chiroptical regulation technology, but also provide a significant guidance for the design and synthesis of future smart chiroptical switching materials and devices.

Multiple Chirality Switching of a Dye-Grafted Helical Polymer Film Driven by Acid & Base.

A stimuli-responsive multiple chirality switching material, which can regulate opposed chiral absorption characteristics, has great application value in the fields of optical modulation, information storage and encryption, etc. However, due to the rareness of effective functional systems and the complexity of material structures, developing this type of material remains an insurmountable challenge. Herein, a smart polymer film with multiple chirality inversion properties was fabricated efficiently based on a newly-designed acid & base-sensitive dye-grafted helical polymer. Benefited from the cooperative effects of various weak interactions (hydrogen bonds, electrostatic interaction, etc.) under the aggregated state, this polymer film exhibited a promising acid & base-driven multiple chirality inversion property containing record switchable chiral states (up to five while the solution showed three-state switching) and good reversibility. The creative exploration of such a multiple chirality switching material can not only promote the application progress of current chiroptical regulation technology, but also provide a significant guidance for the design and synthesis of future smart chiroptical switching materials and devices.

Inducing and Switching the Handedness of Polyacetylenes with Topologically Chiral [2]Catenane Pendants

AbstractTo explore the chirality induction and switching of topological chirality, poly[2]catenanes composed of helical poly(phenylacetylenes) (PPAs) main chain and topologically chiral [2]catenane pendants are described for the first time. These poly[2]catenanes with optically active [2]catenanes on side chains were synthesized by polymerization of enantiomerically pure topologically chiral [2]catenanes with ethynyl polymerization site and/or point chiral moiety. The chirality information of [2]catenane pendants was successfully transferred to the main chain of polyene backbones, leading to preferred‐handed helical conformations, while the introduction of point chiral units has negligible effect on the overall helices. More interestingly, attributed to unique dynamic feature of the [2]catenane pendants, these polymers revealed dynamic response behaviors to solvents, temperature, and sodium ions, resulting in the fully reversible switching on/off of the chirality induction. This work provides not only new design strategy for novel chiroptical switches with topologically chiral molecules but also novel platforms for the development of smart chiral materials.

Inducing and Switching the Handedness of Polyacetylenes with Topologically Chiral [2]Catenane Pendants.

To explore the chirality induction and switching of topological chirality, poly[2]catenanes composed of helical poly(phenylacetylenes) (PPAs) main chain and topologically chiral [2]catenane pendants are described for the first time. These poly[2]catenanes with optically active [2]catenanes on side chains were synthesized by polymerization of enantiomerically pure topologically chiral [2]catenanes with ethynyl polymerization site and/or point chiral moiety. The chirality information of [2]catenane pendants was successfully transferred to the main chain of polyene backbones, leading to preferred-handed helical conformations, while the introduction of point chiral units has negligible effect on the overall helices. More interestingly, attributed to unique dynamic feature of the [2]catenane pendants, these polymers revealed dynamic response behaviors to solvents, temperature, and sodium ions, resulting in the fully reversible switching on/off of the chirality induction. This work provides not only new design strategy for novel chiroptical switches with topologically chiral molecules but also novel platforms for the development of smart chiral materials.

Topologically protected entanglement switching around exceptional points

The robust operation of quantum entanglement states is crucial for applications in quantum information, computing, and communications1–3. However, it has always been a great challenge to complete such a task because of decoherence and disorder. Here, we propose theoretically and demonstrate experimentally an effective scheme to realize robust operation of quantum entanglement states by designing quadruple degeneracy exceptional points. By encircling the exceptional points on two overlapping Riemann energy surfaces, we have realized a chiral switch for entangled states with high fidelity. Owing to the topological protection conferred by the Riemann surface structure, this switching of chirality exhibits strong robustness against perturbations in the encircling path. Furthermore, we have experimentally validated such a scheme on a quantum walk platform. Our work opens up a new way for the application of non-Hermitian physics in the field of quantum information.

Host–guest complexation‐induced chirality switching of pillararenes by perylene diimide‐based hexagonal metallacages

AbstractChirality in confined nanospaces has brought some new insights into chirality transfer, amplification, and chiroptical properties. However, chirality switching, which is a common phenomenon in biological systems, has never been realized in confined environments. Herein, we report a type of hexagonal metallacages that shows good host–guest interactions with ethoxy pillar[5]arene and pillar[6]arene, as confirmed by single‐crystal X‐ray analysis. Importantly, when a chiral pillar[5]arene‐based molecular universal joint (MUJ) is used as the guest, the host–guest complexation would drive the alkyl ring of the MUJ flip from outside to inside the cavity of its pillar[5]arene unit, which enables the configuration change along with the chirality inversion of the MUJ. Moreover, the host–guest complexation facilitates the chirality transfer from guests to hosts, giving circularly polarized luminescence to the system. This study provides a unique metallacage‐pillararene recognition motif for the chirality switching of planar chiral pillararenes, which will promote the construction of host–guest systems with tunable chirality for advanced applications.

Utilizing topological invariants for encoding and manipulating chiral phonon devices

As a fundamental degree of freedom, phonon chirality is expected to promote the development of quantum information technology just like electron spin. Currently, central to this area is the realization of efficient transmission and control of chiral information. In this paper, we propose an approach by integrating topological theory, leveraging topologically invariant Chern numbers, to encode hexagonal lattice systems. Our investigation reveals the presence of topologically protected chiral interface states within the shared band gaps of both trivial and non-trivial system units. By precisely modulating the magnetic field distribution within the encoding system, we can effectively manipulate the topological pathways. Building upon this framework, we design and implement a chiral phonon three-port device. Through dynamic calculations, we demonstrate the transmission process of chiral information, showcasing the chiral phonon switching effect and logical OR operation. Our findings not only establish a fundamental mechanism for the manipulation and control of phonon chiral information but also provide a promising direction for research in harnessing chirality degrees of freedom in practical applications.

Dynamical encircling of multiple exceptional points in anti-PT symmetry system

Exceptional points (EPs) in non-Hermitian systems have turned out to be at the origin of many intriguing effects with no counterparts in Hermitian cases. A typically interesting behavior is the chiral mode switching by dynamically winding the EP. Most encircling protocols focus on the two-state or parity-time (PT) symmetry systems. Here, we propose and investigate the dynamical encircling of multiple EPs in an anti-PT-symmetric system, which is constructed based on a one-dimensional lattice with staggered lossy modulation. We reveal that dynamically encircling the multiple EPs results in the chiral dynamics via multiple non-Hermiticity-induced nonadiabatic transitions, where the output state is always on the lowest-loss energy sheet. Compared with the PT-symmetric systems that require complicated variation of the gain/loss rate or on-site potentials, our system only requires modulations of the couplings which can be readily realized in various experimental platforms. Our scheme provides a route to study non-Hermitian physics by engineering the EPs and implement novel photonic devices with unconventional functions.

Chiral structures in azobenzene‐containing systems: Construction, regulation, and application

AbstractChirality is a fundamental property in nature, which is essential for the existence and survival of living organisms. Smart responsive chiroptical materials have garnered increasing attention due to their unique structural characteristics and potential applications. Among these, azobenzene (Azo), as a typical photoresponsive chromophore, plays a crucial role in constructing and controlling chiral structures. The unique cis‐trans isomerization, liquid crystallinity, and other physicochemical properties allow for a wide range of tunability in stimuli‐responsive chiroptical materials. Herein, we review the research studies in the field of chiral/achiral Azo building blocks for multilevel chiral generation as well as chiral switching, and summarize the recent advances on the applications of the chiral Azo structures from micro to macro levels. Finally, we aim to provide an overview of the potential challenges and new research opportunities for the development of novel smart responsive chiroptical materials.

Multichannel focused higher-order Poincaré sphere beam generation based on a dielectric geometric metasurface

Focused vector beams (VBs) are important topic in the areas of light field manipulation. Geometric metasurfaces provide a convenient platform to facilitate the generation of focused VBs. In this study, we propose a dielectric geometric metasurface to generate multichannel focused higher-order Poincaré sphere (HOP) beams. With identical meta-atoms of half-wave plate, the metasurface comprises two sub-metasurfaces, and each of them includes two sets of rings related to Fresnel zones. For meta-atoms on each set of rings, the hyperbolic geometric phase profile is configured so that the mirror-symmetrical position-flip of the off-axis focal point is enabled under the chirality switch of the illuminating circular polarization. With the design of helical geometric phase profiles for the two sets of rings, a sub-metasurface generate two HOP beams at the symmetrical two focal points. The performance of the two sub-metasurfaces enables the metasurface with four sets of rings to generate the array of four HOP beams. The proposed method was validated by theoretical analyses, numerical simulation and experimental conduction. This research would be significant in miniaturizing and integrating optical systems involving applications of VB generations and applications.

CHIRAL SWITCHING CONTROL OF PHARMACEUTICAL SUBSTANCES

Objective: The aim of this study was to demonstrate that chiral switching should be recognized as a widespread phenomenon that extends beyond the production of pure enantiomeric drugs. Methods: To investigate the optical activity of substances from various chemical classes, enantiomers of chiral compounds (Sigma-Aldrich, USA) were chosen: valine and its racemic form (D-valine, L-valine, and racemic valine with optical purity ≥ 99%), L-ascorbic acid (content ≥ 99%), carbohydrates (D-glucose, D-galactose, L-galactose, contents ≥ 99.5%). Solutions were prepared using deuterium-depleted water (DDW–"light" water, D/H=4 ppm), natural deionized high-ohmic water (BD, D/H=140 ppm), and heavy water (99.9% D2O; Sigma-Aldrich). Optical activity was measured using the Atago POL-1/2 polarimeter. Results: One of the components in the racemic medication mixture can act as an inert agent, exhibit toxicity, or undergo undesirable biotransformation mechanisms, resulting in the formation of products with unknown properties. It has been established that a change in the deuterium/protium (D/H) ratio in water leads to a change in the equilibrium and kinetic characteristics of optically active compounds across various chemical classes, such as amino acids, carboxylic acids, and carbohydrates. An inequality was observed in the absolute values of the optical rotation of the L-and D-isomers of valine and galactose, depending on the D/H isotope ratio. The impact of chiral water clusters on optical rotation accounts for the sudden shift in the specific rotation of dilute solutions (less than 0.5%) of L-ascorbic acid in water, based on the D/H ratio. The influence of the isotopic composition of water was confirmed by studying the temperature-dependent mutarotation kinetics of D-glucose and L-and D-galactose in Arrhenius coordinates. The mutarotation process in natural high-resistivity water is characterized by an activation energy (Ea) of 40.8±1.4 kJ mol-1, while in deuterium-depleted water, Ea = 63.6±3.5 kJ mol-1. This results in a kinetic isotope effect for deuterium (KIED) of 1.6. Conclusion: Methodological approaches have been developed to control chiral switching based on the isotopic composition of water in vivo and in vitro. The study of changes in the optical activity of hierarchical structures in the human body, the influence of solvent properties on the mechanisms of optical rotation, as well as the use of KIED values, can be utilized to monitor various chiral transitions in vitro and living organisms.

Magnetic exchange interactions at the proximity of a superconductor

Interfacing magnetism with superconductivity gives rise to a wonderful playground for intertwining key degrees of freedom: Cooper pairs, spin, charge, and spin–orbit interaction, from which emerge a wealth of exciting phenomena, fundamental in the nascent field of superconducting spinorbitronics and topological quantum technologies. Magnetic exchange interactions (MEIs), being isotropic or chiral such as the Dzyaloshinskii–Moriya interactions, are vital in establishing the magnetic behavior at these interfaces as well as in dictating not only complex transport phenomena, but also the manifestation of topologically trivial or non-trivial objects. Here, we propose a methodology enabling the extraction of the tensor of MEI from electronic structure simulations accounting for superconductivity. We apply our scheme to the case of a Mn layer deposited on Nb(110) surface and explore proximity-induced impact on the MEI. The latter are weakly modified by a realistic electron-phonon coupling. However, tuning the superconducting order parameter, we unveil potential change of the magnetic order accompanied with chirality switching, as induced by the interplay of spin-orbit interaction and Cooper pairing. Owing to its simple formulation, our methodology can be readily implemented in state-of-the-art frameworks capable of tackling superconductivity and magnetism. We thus foresee implications in the simulations and prediction of topological superconducting bits as well as of cryogenic superconducting hybrid devices involving magnetic units.