Local Chirality Research Articles

X-ray circular dichroism measured by cross-polarization x-ray transient grating

Abstract Measuring natural circular dichroism in the x-ray regime to extract stereochemical information from chiral molecules in solution remains a challenge. This is primarily due to technical limitations of the existing synchrotron sources, which hinder access to measurements of local chirality by exploiting core hole electronic transitions. In response to this challenge, we propose an alternative approach: utilizing XFEL-based cross-polarization x-ray transient grating (XTG). This method provides an indirect means to measure x-ray circular dichroism (XCD). Notably, our findings reveal that the signal emerges only once the excited cores have undergone dephasing through relaxation. XTG is now routinely measured in the XUV regime and has recently been made available for hard x-rays. Free electron lasers now offer polarization controls, and XTG can be extended to various polarization states for the two pump beams, making XCD measured by XTG feasible with the current state-of-the-art technology.

Enantioselective optical trapping of chiral nanoparticles by tightly focused fractional vector beams

Enantiomers exhibit markedly different chemical properties although they have the same chemical structure. The identification and separation of enantiomers have been significant issues in biomedicine and chemistry. In this work, we proposed an optical method that selective trapping of enantiomers by using tightly focused fractional vector beams (FVBs). In our proposed model, such a focused beam forms multiple local optical chirality densities (OCDs) with opposite signs at the focal plane. We found that focused FVBs can stably trap the enantiomers at the local positions with the minimum or maximum OCD according to the handedness of enantiomers. The positions and numbers of the trapped enantiomers have a relationship with the fractional topological charge. These results indicate that tightly focused FVBs are an all-optical method capable of dynamic modulation and achieving precise and stable trapping of multiple pairs of enantiomers. Our findings have practical applications in the multi-throughput and multi-sample manipulation of chiral materials.

Local high chirality near exceptional points based on asymmetric backscattering

Abstract We investigate local high chirality inside a microcavity near exceptional points (EPs) achieved via asymmetric backscattering by two internal weak scatterers. At EPs, coalescent eigenmodes exhibit position-dependent and symmetric high chirality characteristics for a large azimuthal angle between the two scatterers. However, asymmetric mode field features appear near EPs, where two azimuthal regions in the microcavity classified by the scatterers exhibit different wave types and chirality. Such local mode field features are attributed to the symmetries of backscattering in direction and spatial distribution. The connections between the wave types, the symmetry of mode field distribution and different symmetries of backscattering near EPs are also discussed. Benefiting from the small size of weak scatterers, such microcavities with a high Q/V near EPs can be used to achieve circularly polarized quantum light sources and explore EP modified quantum optical effects in cavity quantum electrodynamics systems.

Emerging chiral two-dimensional materials.

Research into 2D materials has been growing with impressive speed since the discovery of graphene. Such layered materials with ultrathin morphologies and extreme aspect ratios currently display a vast range of properties; however, until recently a conspicuously missing property of 2D materials was global chirality. The situation has changed over the past few years with the implementation of several distinct types of ultrathin chiral 2D crystals. Here we offer a forward-looking perspective on this field to comprehend the fundamentals of global chirality in two dimensions and develop new directions. We specifically discuss the experimental achievements of the emerging chiral 2D materials with a focus on their design strategy, synthesis, structural characterization, fundamental physical properties and possible applications. We will highlight how the molecular-scale local chirality could be significantly transmitted and amplified throughout ultrathin single-crystalline 2D structures, resulting in distinctive global chirality that brings more sophisticated functions.

Achievement splitting for topological states with pseudospin in phase modulation by using gyromagnetic photonic crystals

As we know, valley-Hall kink states or pseudospin helical edge states are excited by polarized-momentum-locking [left-handed circular polarization (LCP) and right-handed circular polarization (RCP)] because the valley-Hall kink modes or pseudospin polarized modes have intrinsic and local chirality, which is difficult for these states to achieve phase modulation. Here we theoretically design and study a compatible topological photonic system with coexistence of photonic quantum Hall phase and pseudospin Hall phase, which is composed of gyromagnetic photonic crystals with a deformed honeycomb lattice containing six cylinders. A typical kind of hybrid topological waveguide states with pseudospin-characteristic, magnetic field-dependent, and strong robustness against backscattering and perfect electric conductor (PEC) is realized in the present system. Furthermore, we re-design a structure with intersection-liked, achieve splitting for one-way pseudospin quantum Hall edge states by using phase modulation. Robustness of the one-way pseudospin-quantum Hall edge states in splitting has been demonstrated as well. Additionally, PEC inserted in transport channel brings optical path difference in waveguide transmission, which would influence splitting for hybrid topological waveguide states in phase difference modulation. This work not only provides a new way for manipulation (i.e., phase modulation) of hybrid topological waveguide states in compatible topological photonic system from distinct topological classes but also has potential in various applications, such as sensing, signal processing, and on-chip communications.

Amplified linear and nonlinear chiral sensing assisted by anapole modes in hybrid metasurfaces

The interaction between chiral molecules and circularly polarized light is largely influenced by the local optical chirality density. This interaction prompts substantial demand of the design of nanophotonic platforms capable of enhancing such effects across large and accessible volumes. Such a magnification requires nanostructures that provide strong electric and magnetic field enhancements while preserving the phase relation of circular light. Dielectric nanostructures, particularly those able to support resonances, are ideal candidates for this task due to their capacity for high electric and magnetic field enhancements. On the other hand, efficient third harmonic generation requires strong electric field resonances within dielectric materials, a feature often boosted by incorporating plasmonic materials into hybrid systems. In this work, we numerically propose a coupled silicon disk-gold ring system that can exploit the anapole-induced field confinement to provide a broadband magnified circular dichroism under realistic conditions, reaching values up to a 230-fold enhancement. We also demonstrate that this structure can be employed as an efficient third harmonic generator, which, when integrated with chiral media, enables an 800-fold enhancement in circular dichroism. Furthermore, we show that pulsed illumination at intensities up to 10 GW/cm2 does not induce temperature increments that could potentially damage the samples. These findings suggest that this system can be a promising and versatile approach toward ultrasensitive chiral sensing.

Chiral Kirigami for Bend-Tolerant Reconfigurable Hologram with Continuously Variable Chirality Measures.

Despite the commonality of static holograms, the holography with multiple information layers and reconfigurable grey-scale images at communication frequencies remain a confluence of scientific challenges. One well-known difficulty is the simultaneous modulation of phase and amplitude of electromagnetic wavefronts with a high modulation depth. A less appreciated challenge is scrambling of the information and images with hologram bending. Here, this work shows that chirality-guided pixelation of plasmonic kirigami sheets enables tunable multiplexed holography at terahertz (THz) frequencies. The convex and concave structures with slanted Au strips exhibit gradual variations in geometries facilitating modulation of light ellipticity reaching 40deg. Real-time switching of 3D images of the letter "M" and the Mona Lisa demonstrates the possibility of complex grey-scale information content and importance of continuously variable mirror asymmetry. Microscale chirality measures of each pixel experiences little change with bending while retaining controllable reconfigurability upon stretching, which translates to remarkable resilience of chiral holograms to bending. Simplicity of their design with local chirality measures opens the door to information technologies with fault-tolerant THz encryption, wearable holographic devices, and new communication technologies.

Enantioselective Optical Trapping of Multiple Pairs of Enantiomers by Focused Hybrid Polarized Beams.

Enantiomers (opposite chiral molecules) usually exhibit different effects when interacting with chiral agents, thus the identification and separation of enantiomers are of importance in pharmaceuticals and agrochemicals. Here an optical approach is proposed to enantioselective trapping of multiple pairs of enantiomers by a focused hybrid polarized beam. Numerical results indicate that such a focused beam shows multiple local optical chirality of opposite signs in the focal plane, and can trap the corresponding enantiomers near the extreme value of optical chirality density according to the handedness of enantiomers. The number and positions of trapped enantiomers can be changed by altering the value and sign of polarization orders of hybrid polarized beams, respectively. The key to realizing enantioselective optical trapping of enantiomers is that the chiral optical force exerted on enantiomers in this focused field is stronger than the achiral optical force. The results provide insight into the optical identification and separation of multiple pairs of enantiomers and will find applications in chiral detection and sensing.

The Combination of the Azimuthally and Radially Polarized Beams: Helicity and Momentum Densities, Generation, and Optimal Chiral Light

Herein, the optical properties of the azimuthally radially polarized beam (ARPB), a superposition of an azimuthally polarized beam and a radially polarized beam, which can be tuned to exhibit maximum chirality at a given energy density, are investigated. This condition is called “optimal chiral light” since it represents the maximum possible local chirality at a given energy density. The transverse fields of an ARPB dominate in the transverse plane but vanish on the beam axis, where the magnetic and electric fields are purely longitudinal, leading to an optical chirality density and an energy density that stem solely from the longitudinal field components on the beam axis, where the linear and angular momentum densities vanish. The ARPB does not have a phase variation around the beam axis and nonetheless exhibits a power flow around the beam axis that causes a longitudinal orbital angular momentum density. Herein, a concise notation for the ARPB is introduced and field quantities are provided, especially for the optimally chiral configuration. The ARPB shows promise for precise 1D chirality probing and enantioseparation of chiral particles along the beam axis, relying solely on its longitudinal electric and magnetic fields. Herein, a setup is provided to generate ARPBs with controlled chirality and orbital angular momentum.

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.

Toward Consistent Physics-Based Modeling of Local Backbone Structures and Chirality Change of Proteins in Coarse-Grained Approaches.

A reliable representation of local interactions is critical for the accuracy of modeling protein structure and dynamics at both the all-atom and coarse-grained levels. The development of local (mainly torsional) potentials was focused on careful parametrization of the predetermined (usually Fourier) formulas rather than on their physics-based derivation. In this Perspective we discuss the state-of-the-art methods for modeling local interactions, including the scale-consistent theory developed in our laboratory, which implies that the coarse-grained torsional potentials inseparably depend on the virtual-bond angles adjacent to a given dihedral and that multitorsional terms should be considered. We extend the treatment to split the residue-based torsional potentials into the site-based regular and improper torsional potentials. These considerations are illustrated with the revised torsional potentials and improper-torsional potentials involving the l-alanine residue and the improper-torsional potential corresponding to serine-residue enantiomerization. Applications of the new approach in coarse-grained modeling and revising all-atom force fields are discussed.

Local chirality at exceptional points in optical whispering-gallery microcavities

Local chirality at exceptional points in optical whispering-gallery microcavities

X-ray and Optical Circular Dichroism as Local and Global Ultrafast Chiral Probes of [12]Helicene Racemization.

Chirality is a fundamental molecular property that plays a crucial role in biophysics and drug design. Optical circular dichroism (OCD) is a well-established chiral spectroscopic probe in the UV-visible regime. Chirality is most commonly associated with a localized chiral center. However, some compounds such as helicenes (Figure 1) are chiral due to their screwlike global structure. In these highly conjugated systems, some electric and magnetic allowed transitions are distributed across the entire molecule, and OCD thus probes the global molecular chirality. Recent advances in X-ray sources, in particular the control of their polarization and spatial profiles, have enabled X-ray circular dichroism (XCD), which, in contrast to OCD, can exploit the localized and element-specific nature of X-ray electronic transitions. XCD therefore is more sensitive to local structures, and the chirality probed with it can be referred to as local. During the racemization of helicene, between opposite helical structures, the screw handedness can flip locally, making the molecule globally achiral while retaining a local handedness. Here, we use the racemization mechanism of [12]helicene as a model to demonstrate the capabilities of OCD and XCD as time-dependent probes for global and local chiralities, respectively. Our simulations demonstrate that XCD provides an excellent spectroscopic probe for the time-dependent local chirality of molecules.

Chiral Luminescence Quantum Efficiency Engineered by Plasmonic Antennas

Chiral detection is critical for investigating many biological processes. We use numerical calculations to study the quantum efficiency (QE) of a chiral emitter modulated by plasmonic antennas. The chiral difference in QE is discovered when the chiral emitter is placed in the vicinity of the antenna. The chiral QE is position-dependent for symmetric and asymmetric antennas and can be modulated by designing chiral configurations. The local optical chirality and the coupled harmonic oscillator model can qualitatively explain the QE difference revealed by the numerical methods. That originates from the interference between resonant modes with different phases induced by chiral interactions, resulting in the different loss of coupled modes. Our results provide extended design ideas for enantioselective fluorescent recognition of chiral molecules.

Quantitative chirality in the binding of androgens to their receptor

Chirality is a binary yes/no molecular property that nevertheless can be described by a continuous chirality measure function. Chirality measure values can be understood as sensitive descriptors of molecular shape. In this study, we evaluated the role of quantitative chirality (measures) in binding of androgens to their receptor. We demonstrate that a simple Quantitative Structure-Activity Relationship equation correlating the binding affinity with the partial charges of pharmacophoric oxygen atoms is significantly improved upon introducing quantitative chirality descriptors as additional variables. In such models, the charge descriptors account for the strength of the formed hydrogen bonds. However, the picture is completed by the chirality measures that indirectly contain information on the geometries of the hydrogen bond networks and subtle differences in the van der Waals contacts connected with different local or global shapes of the molecules. The model case studied here (11 simple and very similar steroids) proves that both global and local chirality is important in the androgen binding to their receptors.

Bright near-infrared circularly polarized electrochemiluminescence from Au9Ag4 nanoclusters.

Metal nanoclusters are excellent electrochemiluminescent luminophores owing to their rich electrochemical and optical properties. However, the optical activity of their electrochemiluminescence (ECL) is unknown. Herein, we achieved, for the first time, the integration of optical activity and ECL, i.e., circularly polarized electrochemiluminescence (CPECL), in a pair of chiral Au9Ag4 metal nanocluster enantiomers. Chiral ligand induction and alloying were employed to endow the racemic nanoclusters with chirality and photoelectrochemical reactivity. S-Au9Ag4 and R-Au9Ag4 exhibited chirality and bright-red emission (quantum yield = 4.2%) in the ground and excited states. The enantiomers showed mirror-imaged CPECL signals at 805 nm owing to their highly intense and stable ECL emission in the presence of tripropylamine as a co-reactant. The ECL dissymmetry factor of the enantiomers at 805 nm was calculated to be ±3 × 10-3, which is comparable with that obtained from their photoluminescence. The obtained nanocluster CPECL platform shows the discrimination of chiral 2-chloropropionic acid. The integration of optical activity and ECL in metal nanoclusters provides the opportunity to achieve enantiomer discrimination and local chirality detection with high sensitivity and contrast.

Transport properties of dipole skyrmions in amorphous Fe/Gd multilayers

Chiral magnets are known to possess interesting electromagnetic properties that result from the coupling of electrons with nontrivial magnetic phases, such as particle-like magnetic spin textures termed skyrmions. So far, it is unclear how the local and global chirality of magnetic spin textures contributes to the electromagnetic transport responses that have so far been observed. In this work, we focus on unraveling the contributions in the field-dependent longitudinal resistivity response that arises from magnetic spin textures in a centrosymmetric Fe/Gd multilayer that exhibits an array of magnetic phases ranging from stripe, mixed stripe-skyrmion, skyrmion lattice, and disordered skyrmion. Using a combination of transport measurements and micromagnetic simulations, we demonstrate a domain wall chirality reconfiguration occurs as the domain morphology transitions from disordered stripe to skyrmion lattice phase under applied fields that is responsible for the interesting transport responses noted in the field-dependent longitudinal resistivity.

Activating magnetoelectric optical properties by twisting antiferromagnetic bilayers

Twisting in bilayers introduces structural chirality with two enantiomers, i.e., left- and right-hand bilayers, depending on the oriented twist angle. The interplay between this global chirality and additional degrees of freedom, such as magnetic ordering and the local octahedral chirality arising from the geometry of the bonds, can yield striking phenomena. In this work, we focus on collinear antiferromagnetic CrI$_3$ twisted homo-bilayers, which are characterized by a staggered octahedral chirality in each monolayer. Using symmetry analysis, density functional theory and tight-binding model calculations we show that layers twisting can lower the structural and magnetic point-group symmetries, thus activating pyroelectricity and the magneto-optical Kerr effect, which would otherwise be absent in untwisted antiferromagnetic homo-bilayers. Interestingly, both electric polarization and Kerr angle are controllable by the twist angle and their sign is reversed when switching from left- to right-twisted bilayers. We further unveil the occurrence of unconventional vortices with spin textures that alternate opposite chiralities in momentum space. These findings demonstrate that the interplay between twisting and octahedral chirality in magnetic bilayers and related van der Waals heterostructures represents an extraordinary resource for tailoring their physical properties for spintronic and optoelectronic applications.

Pair invariant mass to isolate background in the search for the chiral magnetic effect in Au + Au collisions at sNN=200 GeV

Quark interactions with topological gluon configurations can induce local chirality imbalance and parity violation in quantum chromodynamics, which can lead to the chiral magnetic effect (CME)—an electric charge separation along the strong magnetic field in relativistic heavy-ion collisions. The CME-sensitive azimuthal correlator observable (Δγ) is contaminated by background arising, in part, from resonance decays coupled with elliptic anisotropy (v2). We report here differential measurements of the correlator as a function of the pair invariant mass (minv) in 20–50% centrality Au+Au collisions at sNN=200 GeV by the STAR experiment at the BNL Relativistic Heavy Ion Collider. Strong resonance background contributions to Δγ are observed. At large minv where this background is significantly reduced, the Δγ value is found to be significantly smaller. An event-shape-engineering technique is deployed to determine the v2 background shape as a function of minv. We extract a v2-independent and minv-averaged signal Δγsig=(0.03±0.06±0.08)×10−4, or (2±4±5)% of the inclusive Δγ(minv>0.4 GeV/c2)=(1.58±0.02±0.02)×10−4, within pion pT=0.2–0.8 GeV/c and averaged over pseudorapidity ranges of −1<η<−0.05 and 0.05<η<1. This represents an upper limit of 0.23×10−4, or 15% of the inclusive result, at 95% confidence level for the minv-integrated CME contribution.Received 11 June 2020Revised 12 July 2022Accepted 12 August 2022DOI:https://doi.org/10.1103/PhysRevC.106.034908©2022 American Physical SocietyPhysics Subject Headings (PhySH)Research AreasParticle correlations & fluctuationsRelativistic heavy-ion collisionsNuclear Physics

Nonreciprocal Transport in Noncoplanar Magnetic Systems without Spin–Orbit Coupling, Net Scalar Chirality, or Magnetization

We propose a new mechanism of nonlinear nonreciprocal transport in magnetic systems. By considering a noncoplanar magnetic ordering on a bilayer triangular lattice, we clarify that a local scalar chirality degree of freedom is a source of nonreciprocal transport, which does not require any relativistic spin-orbit coupling, net scalar chirality, and net magnetization. We show a close relationship between the asymmetric band modulation and the nonreciprocal transport under the noncoplanar magnetic ordering based on the model-parameter dependences in the real-space picture.