Chiral Signatures Research Articles

Dual Signature of Chirality Induced Spin Selectivity through Spontaneous Resolution of 2D Metal–Organic Frameworks

AbstractThe Chiral‐Induced Spin Selectivity (CISS) effect has emerged as a fascinating phenomenon within the realm of electron's spin manipulation, showcasing a unique interplay between electron's spin and molecular chirality. Subsequent to its discovery, researchers have been actively involved in exploring the new chiral molecules as effective spin filters. In the realm of observing the CISS effect, the conventional approach has mandated the utilization of two distinct enantiomers of chiral molecules. However, this present study represents a significant advancement by demonstrating the ability to control both spin states of electrons in a single system. In this work, we have demonstrated the preparation of chiral metal–organic frameworks (MOFs) via a “spontaneous resolution” process, obviating the requirement for chiral sources. This resulted in the production of chiral crystals exhibiting opposite handedness (1P and 1M) and these crystals were subsequently employed as a new class of spin filters based on CISS effect. Remarkably, this work signifies the first instance of achieving dual signature of spin selectivity from a single and exclusively achiral system through a spontaneous resolution process. This holds immense potential as it facilitates the production of two distinct spin‐filtering materials from a unified system. Furthermore, we investigated the contact potential differences (CPD) of these chiral crystals and, for the first time, associated it with the preferential spin transport properties. Our findings revealed a correlation between the CPD and the chirality of the crystals, as well as the magnetization orientations of the ferromagnetic substrate, which can be elucidated by the CISS effect. In overall, the significant findings achieved using these robust and easily synthesized MOF crystals without the requirement for chiral medium represent a crucial advancement in enhancing the effectiveness of spin filtering materials to produce spintronic devices.

Dual Signature of Chirality Induced Spin Selectivity through Spontaneous Resolution of 2D Metal-Organic Frameworks.

The Chiral-Induced Spin Selectivity (CISS) effect has emerged as a fascinating phenomenon within the realm of electron's spin manipulation, showcasing a unique interplay between electron's spin and molecular chirality. Subsequent to its discovery, researchers have been actively involved in exploring the new chiral molecules as effective spin filters. In the realm of observing the CISS effect, the conventional approach has mandated the utilization of two distinct enantiomers of chiral molecules. However, this present study represents a significant advancement by demonstrating the ability to control both spin states of electrons in a single system. In this work, we have demonstrated the preparation of chiral metal-organic frameworks (MOFs) via a "spontaneous resolution" process, obviating the requirement for chiral sources. Remarkably, this work signifies the first instance of achieving dual signature of spin selectivity from a single and exclusively achiral system through a spontaneous resolution process. This holds immense potential as it facilitates the production of two distinct spin-filtering materials from a unified system. In overall, the significant findings achieved using these robust and easily synthesized MOF crystals without the requirement for chiral medium represent a crucial advancement in enhancing the effectiveness of spin filtering materials to produce spintronic devices.

Magnetic symmetries of terbium tetraboride (TbB4) revealed by resonant x-ray Bragg diffraction

A recent experimental study of TbB4 at a low temperature using resonant x-ray Bragg diffraction implies a magnetic symmetry not found in any other rare-earth tetraboride. The evidence for this assertion is a change in the intensity of a TbB4 Bragg spot on reversing the handedness (chirality) of the primary x-ray beam [R. Misawa, K. Arakawa, T. Yoshioka, H. Ueda, F. Iga, K. Tamasaku, Y. Tanaka, and T. Kimura, ]. It reveals a magnetic chiral signature in TbB4 that is forbidden in phases of rare-earth tetraborides known to date, as the previous magnetic symmetries are parity-time (PT) symmetric with anti-inversion present in the magnetic crystal class. Misawa appeal to a PT-symmetric diffraction pattern to interpret their interesting diffraction patterns. In addition to the use of symmetry that does not permit a chiral signature, calculated patterns impose cylindrical symmetry on Tb sites with no justification. We review magnetic symmetries for TbB4 consistent with a published neutron powder diffraction pattern and susceptibility measurements. On the basis of this information, noncollinear antiferromagnetic order exists below a temperature ≈44 K with no ferromagnetic component. Our symmetry-informed patterns encapsulate Tb electronic degrees of freedom in terms of multipoles consistent with established sum rules for dichroic signals. The investigated symmetry templates are noncentrosymmetric, noncollinear antiferromagnetic constructions with propagation vector k=(0,0,0). An inferred chiral signature for a parity-even absorption event has an interesting composition. There is the anticipated product of Tb axial dipoles and chargelike quadrupoles (from Templeton-Templeton scattering). Beyond this contribution, though, symmetry allows a product of dipoles in the chiral signature. A predicted change in the intensity of a Bragg spot with rotation of the crystal about the reflection vector (an azimuthal angle scan) can be tested in future experiments. Likewise contributions to Bragg diffraction patterns from Tb anapoles and higher-order Dirac multipoles. Published by the American Physical Society 2024

Active chiral flows in the separating wall during cell division.

Material flow in the actomyosin cortex of a cell, during cell division, has been found to be chiral in nature. It has been attributed to active chiral torques generated in the actomyosin cortex. Here, we explore the possible signature of such chirality during the growth of the intra-cellular membrane partition, which physically divides the cell into two compartments. We use standard hydrodynamic theory of active gel to predict possible chiral flow structures in the growing partition. While the flows in the growing annular-shaped membrane partition is believed to be radial, it can also develop non-zero azimuthal velocity components (rotation) due to chirality. We show that the direction of rotation (clock or anti-clockwise) will not solely be decided by the signof the active chiral torque but also by the relative strengths of rotational viscosity and flow coupling parameter.

Exploration of the intracellular chiral metabolome in pediatric BCP-ALL: a pilot study investigating the metabolic phenotype of IgH locus aberrations.

Aberrations in the immunoglobulin heavy chain (IgH) locus are associated with poor prognosis in pediatric precursor B-cell acute lymphoblastic leukemia (BCP-ALL) patients. The primary objective of this pilot study is to enhance our understanding of the IgH phenotype by exploring the intracellular chiral metabolome. Leukemia cells were isolated from the bone marrow of BCP-ALL pediatric patients at diagnosis. The samples' metabolome and transcriptome were characterized using untargeted chiral metabolomic and next-generation sequencing transcriptomic analyses. For the first time D- amino acids were identified in the leukemic cells' intracellular metabolome from the bone marrow niche. Chiral metabolic signatures at diagnosis was indicative of a resistant phenotype. Through integrated network analysis and Pearson correlation, confirmation was obtained regarding the association of the IgH phenotype with several genes linked to poor prognosis. The findings of this study have contributed to the understanding that the chiral metabolome plays a role in the poor prognosis observed in an exceptionally rare patient cohort. The findings include elevated D-amino acid incorporation in the IgH group, the emergence of several unknown, potentially enantiomeric, metabolites, and insights into metabolic pathways that all warrant further exploration.

Magnetic properties of Sohncke-type Pb(TiO) Cu4(PO4)4 exposed by resonant x-ray Bragg diffraction

The enantiomorphous (chiral) crystal class of Sohncke-type Pb(TiO)Cu4(PO4)4 permits the rotation of the plane of polarization of light (optical activity). Copper ions participate in noncollinear antiferromagnetic order below a temperature ≈ 7 K, with magnetoelectric and piezomagnetic effects permitted. Crystal and magnetic symmetries of Pb(TiO)Cu4(PO4)4 are fully incorporated in calculated resonant x-ray Bragg diffraction patterns that are successfully compared with existing limited experimental data [Misawa , ]. Specifically, there is additional intensity of a Bragg spot (a chiral signature) from circular polarization (helicity) in the primary beam of x rays. The chiral signature is shown to arise from Cu axial magnetic dipoles, with the prospect of future experiments revealing interference between magnetic dipoles and (Templeton-Templeton) chargelike quadrupoles. An expression for the additional intensity used by Misawa does not respect magnetic symmetry, and our symmetry-informed answer overturns their principal conclusions about chirality and magnetic order. Dirac quadrupoles and octupoles are potentially strong sources of diffraction when the reflection vector is parallel to the unique direction in the tetragonal lattice. Notably, a Dirac quadrupole is a parity- and time-odd atomic multipole unlike a multisite spin entity previously mentioned in the context of Pb(TiO)Cu4(PO4)4 [Kimura , ]. Published by the American Physical Society 2024

Hexabromocyclododecanes in soils, plants, and sediments from Svalbard, Arctic: Levels, isomer profiles, chiral signatures, and potential sources

This study investigated the occurrence, stereoisomeric behavior, and potential sources of hexabromocyclododecanes (HBCDs) in topsoil and terrestrial vegetation from Svalbard and ocean sediment samples from Kongsfjorden, an open fjord on the west coast of Spitsbergen. The mean levels of total concentrations (Σ3HBCDs) were comparable to those in other remote regions and were lower than those in source regions. Elevated proportions of α-HBCD with an average of 41% in the terrestrial samples and 25% in ocean sediments compared to those in commercial products (10–13% for α-HBCD) were observed, implying isomerization from γ- to α-HBCD in the Arctic environment. In addition, the extensive deviations of enantiomeric fractions (EFs) from the racemic values reflected the effect of biotransformation on HBCD accumulation. Linear correlation analysis, redundancy analysis, and back-trajectory were combined to infer possible HBCD sources, and the results showed the important role of global production and long-range environmental transport (LRET) for the entry of HBCDs into the Arctic at an early stage. To the best of our knowledge, this study represents the first report on the diastereoisomer- and enantiomer-specific profiles of HBCDs in the Arctic terrestrial environment and sheds light on the transport pathways and environmental fate for more effective risk management related to HBCDs in remote regions.

Red Circularly Polarized Luminescence from Dimeric H-Aggregates of Acridine Orange by Chiral Induction.

Understanding the mechanism of chirality transfer from a chiral surface to an achiral molecule is essential for designing molecular systems with tunable chiroptical properties. These aspects are explored herein using l- and d-isomers of alkyl valine amphiphiles, which self-assemble in water as nanofibers possessing a negative surface charge. An achiral chromophore, acridine orange, upon electrostatic binding on these surfaces displays mirror-imaged bisignated circular dichroism and red-emitting circularly polarized luminescence signals with a high dissymmetry factor. Experimental and computational investigations establish that the chiroptical properties emerge from surface-bound asymmetric H-type dimers of acridine orange, further supported by fluorescence lifetime imaging studies. Specifically, atomistic molecular dynamics simulations show that the experimentally observed chiral signatures have their origin in van der Waals interactions between acridine orange dimers and the amphiphile head groups as well as in the extent of solvent exposure of the chromophore.

A Relationship between the Molecular Parity-Violation Energy and the Electronic Chirality Measure.

When the weak forces producing parity-violating effects are taken into account, there is a tiny energy difference between the total electronic energies of two enantiomers (ΔEPV), which might be the key to understanding the evolution of the biological homochirality. We focus on the electronic chirality measure (ECM), a powerful descriptor based on the electronic charge density, for quantifying the chirality degree of a molecule, in a representative set of chiral molecules, together with their EPV energies. Our results show a novel, strong, and positive correlation between ΔEPV and ECM, supporting a subtle interplay between the weak forces acting within the nuclei of a given molecule and its chirality. These findings suggest that experimental investigations for molecular parity violation detection should consider molecules with ECM values as large as possible and may support that a chiral signature is imprinted on life by fundamental physics via the parity-violating weak interactions.

Identification of Species-Specific Prey Uptake and Biotransformation of Chiral Polychlorinated Biphenyls (PCBs) in Riparian and Aquatic Food Webs.

The atropisomeric enrichment of chiral polychlorinated biphenyls (PCBs) can trace the movement of PCBs through food webs, but it is a challenge to elucidate the prey uptake and stereoselective biotransformation of PCBs in different species. The present study investigated the concentrations and enantiomer fractions (EFs) of chiral PCBs in invertebrates, fishes, amphibians, and birds. Chiral PCB signature was estimated in total prey for different predators based on quantitative prey sources. The nonracemic PCBs in snakehead (Ophiocephalus argus) were mainly from prey. EFs of PCBs in amphibians and birds were mainly influenced by biotransformation, which showed enrichment of (+)-CBs 132 and 135/144 and different enantiomers of CBs 95 and 139/149. Biomagnification factors (BMFs) of chiral PCBs were higher than 1 for amphibians and passerine birds and lower than 1 for kingfisher (Alcedo atthis) and snakehead. BMFs were significantly correlated with EFs of chiral PCBs in predators and indicative of atropisomeric enrichment of PCBs across different species. Trophic magnification factors (TMFs) were higher in the riparian food web than in the aquatic food web because of the high metabolism capacity of chiral PCBs in aquatic predators. The results highlight the influences of species-specific prey sources and biotransformation on the trophic dynamics of chiral PCBs.

Induced photoelectron circular dichroism onto an achiral chromophore

An achiral chromophore can acquire a chiral spectroscopic signature when interacting with a chiral environment. This so-called induced chirality is documented in electronic or vibrational circular dichroism, which arises from the coupling between electric and magnetic transition dipoles. Here, we demonstrate that a chiroptical response is also induced within the electric dipole approximation by observing the asymmetric scattering of a photoelectron ejected from an achiral chromophore in interaction with a chiral host. In a phenol–methyloxirane complex, removing an electron from an achiral aromatic π orbital localised on the phenol moiety results in an intense and opposite photoelectron circular dichroism (PECD) for the two enantiomeric complexes with (R) and (S) methyloxirane, evidencing the long-range effect (~5 Å) of the scattering chiral potential. This induced chirality has important structural and analytical implications, discussed here in the context of growing interest in laser-based PECD, for in situ, real time enantiomer determination.

Toward coherent anti‐Stokes Raman scattering‐Raman optical activity for reaction monitoring in organocatalysis: Chiral vibrational signatures of the two atropisomers (R)‐ and (S)‐MOM‐BINOL in solution

AbstractCoherent anti‐Stokes Raman scattering‐Raman optical activity (CARS‐ROA) is a coherent version of spontaneous ROA spectroscopy, the latter being a well‐established chirally sensitive vibrational spectroscopic technique. A central major advantage of heterodyne‐detected CARS‐ROA over ROA is the drastic reduction of acquisition times from several hours to approximately 1 min due to the high ratio of the chiral Raman signal relative to the achiral CARS background. Here, we present the first demonstration of heterodyne‐detected CARS‐ROA of chiral molecules dissolved in an achiral solvent by using an experimental setup built from a conventional broadband CARS spectrometer. Specifically, the two atropisomers (R/S) of 2,2′‐Bis(methoxymethoxy)‐1,1′‐binaphthyl, a methoxymethyl (MOM) bis‐protected derivative of 1,1′‐Bi‐2‐naphthol (BINOL), dissolved in the achiral organic solvent dichloromethane (DCM) were characterized by employing ~1 ps, 1 mW of pump pulses and ~60 fs, 10 mW of Stokes pulses within approximately 4‐min acquisition time. MOM‐BINOL is an important precursor for the synthesis of a great variety of many chiral auxiliaries including binaphthyl phosphoric acids, which are an important class of chiral organocatalysts used in asymmetric reactions. Overall, this work is a first step toward kinetic reaction monitoring in organocatalysis by coherent ROA providing the necessary short acquisition times.

Synthesis and Chiroptical Properties of a Chiral Isotopologue of syn-Cryptophane-B.

We report the synthesis and absolute configuration (AC) of a chiral isotopologue of syn-cryptophane-B. Low chiral signatures were measured by polarimetry and electronic circular dichroism, whereas most significant chiroptical effects were observed by vibrational circular dichroism (VCD) and Raman optical activity (ROA). The comparison of experimental VCD and ROA spectra with those predicted by DFT calculations allows the determination of the AC of the two enantiomers as (-)589-MP-syn-2 and (+)589-PM-syn-2.

Switchable chiral transport in charge-ordered kagome metal CsV3Sb5

When electric conductors differ from their mirror image, unusual chiral transport coefficients appear that are forbidden in achiral metals, such as a non-linear electric response known as electronic magnetochiral anisotropy (eMChA)1–6. Although chiral transport signatures are allowed by symmetry in many conductors without a centre of inversion, they reach appreciable levels only in rare cases in which an exceptionally strong chiral coupling to the itinerant electrons is present. So far, observations of chiral transport have been limited to materials in which the atomic positions strongly break mirror symmetries. Here, we report chiral transport in the centrosymmetric layered kagome metal CsV3Sb5 observed via second-harmonic generation under an in-plane magnetic field. The eMChA signal becomes significant only at temperatures below {T}^{{prime} }approx 35 K, deep within the charge-ordered state of CsV3Sb5 (TCDW ≈ 94 K). This temperature dependence reveals a direct correspondence between electronic chirality, unidirectional charge order7 and spontaneous time-reversal symmetry breaking due to putative orbital loop currents8–10. We show that the chirality is set by the out-of-plane field component and that a transition from left- to right-handed transport can be induced by changing the field sign. CsV3Sb5 is the first material in which strong chiral transport can be controlled and switched by small magnetic field changes, in stark contrast to structurally chiral materials, which is a prerequisite for applications in chiral electronics.

Topological soliton metacrystals

Designing metamaterials with the required band structure, topology and chirality using nano-fabrication technology revolutionise modern science. The approach of this work to the metamaterial theme is, however, different. We report that a periodic sequence, i.e., metacrystal, of the dissipative optical solitons rotating in a ring microresonator acts as an effective metamaterial in the radio to terahertz frequency range. The metacrystal unit cell consists of the bound pair of solitons, where the inter-soliton distance is used as a control parameter. We investigate the soliton metacrystal band structure and topological properties. The latter is confirmed by the π steps experienced by the crystal phonons’ geometrical (Zak) phase. Furthermore, we found the phononic edge states in the metacrystals with defects made by removing several solitons. Optical frequency combs corresponding to the soliton metacrystals hide the spectral butterfly pattern serving as a signature of the spatio-temporal chirality and bearing a resemblance to the natural occurrences of chirality.

Chiral signatures of polychlorinated biphenyls in serum from e-waste workers and their correlation with hydroxylated metabolites.

Elevated concentrations of polychlorinated biphenyls (PCBs) found in environmental media and biota from typical e-waste dismantling sites have raised concerns regarding their human body burden and potential negative health effects. In the present study, the enantiomeric compositions of three typical chiral congeners (PCB-95, PCB-132, and PCB-149) were measured in 24 serum samples from e-waste workers by using gas chromatography coupled to triple quadrupole tandem mass spectrometry. The mean enantiomer fractions (EFs) of chiral congeners in serum from the workers were 0.655±0.103, 0.679±0.164, and 0.548±0.095 for PCB-95, PCB-132, and PCB-149, respectively. The (+) enantiomers of PCB-95, PCB-132, and PCB-149 were enantioselectively enriched in serum. Significant positive correlations were observed between the EF of the chiral congener PCB-95 and the total concentration of OH-PCBs, suggesting that EF values of chiral PCBs could be used to indicate the extent of biological metabolism. In addition, the EF of PCB-95 in serum samples increased with increasing work duration of the e-waste workers, thus demonstrating the usefulness of EF values of chiral PCBs as tracers of human exposure to PCBs. Because of the enantioselective enrichment of (+) enantiomers of PCB-95, PCB-132, and PCB-149, further studies are needed to explore the metabolism and toxicity of chiral contaminants in humans.

Polar Chirality in BiFeO3 Emerging from A Peculiar Domain Wall Sequence

AbstractTopological states are currently gathering intensive investigation in condensed matter physics due to their potential as configurable electronic devices for the future era coined “topotronics.” Beyond numerous breakthroughs in magnetism over the past decade, a new paradigm is emerging with the proposal of topologically protected objects in ferroelectric materials. Recently, ferroelectric skyrmions and vortices are observed in PbTiO3/SrTiO3 superlattices, opening the path toward ultra‐small topological objects with low‐power electric‐field control. Here, the observation of chiral polar windings in a single epitaxial thin film, triggered by its self‐organized stripe domain pattern arrangement, is reported. Combining resonant elastic X‐ray scattering and scanning transmission electron microscopy, signatures of polar chirality in epitaxial BiFeO3 thin films corroborated with a complex ferroelectric domain wall structure are shown. The net chirality suggests that domain walls induce a polar rotation through a small path alternating with an unexpected long path at every second domain wall. In addition, scanning probe microscopy reveals singularities associated to this peculiar domain wall structure. These results bring new insights into the unexpected complexity of standard striped‐domain BiFeO3 thin films and open questions as for the driving force of this polar chirality.

Induced Chirality in Halide Perovskite Clusters through Surface Chemistry.

Chiroptical properties are of interest for various applications, including structure determination, polarized photodetectors, and spintronics. Inducing chiroptical activity into semiconductors is challenging because of difficulties in creating asymmetric crystal structures. One promising method is to use chirality transfer by deploying chiral organic molecules as capping ligands for nanocrystals. Experimentally, chiral-capped nanocrystals show emergent chiroptical signatures, but the mechanisms for chirality transfer remain unclear. Here we utilize atomistic modeling using time-dependent density functional theory calculations to explore chirality transfer in CsPbX3 (X = Cl, I) clusters capped with chiral diaminocyclohexane (DACH) enantiomers. When DACH enantiomers are bound to the cluster surface, the perovskite optical transitions gain chiral signatures. This observed chirality transfer is best rationalized by chiral molecular dipole-cluster transition dipole coupling. With multiple DACH molecules bound to the cluster surface, anisotropy factors are found to increase proportionally to the surface ligand density, providing mechanistic insight toward improving chiroptical functionality in semiconductor nanomaterials.

A Systematic Review on Distribution and Ecological Risk Assessment for Chiral Pharmaceuticals in Environmental Compartments

Chiral pharmaceuticals are an important class of environmental pollutants. Monitoring studies have shown the non-racemic presence of these contaminants in wastewater, sludge and the receiving environment. This review describes the role of chirality in the environment, especially the distribution and toxicities of enantiomers of chiral pharmaceuticals. In the first part, a systematic overview of their distribution in various environmental matrices and the main application of chiral signatures as chemical markers of water contamination are discussed. Available studies mainly focus on four drug groups including NSAIDs, β-blockers, antidepressants and illicit drugs due to their environmental pseudopersistence and ecotoxicological effects. In the second part, a summary of the enantiospecific toxicity data reported for chiral pharmaceuticals is provided. These data are of high value to improve the accuracy of environmental risk assessments in future works. Enantioselective toxicity towards aquatic organisms have been established for ten out of 36 chiral pharmaceuticals measured and detected in wastewater or surface water samples. Their enantioselective biodegradation and ecotoxicity make the risk assessment process highly recommended. The results provided in this review work support the need for new approaches to more accurately determine the toxicological risks associated to the stereochemistry of environmental contaminants.

Diffraction of helical x-rays by optically active achiral crystals

Four crystal classes are optically active yet not chiral (non-enantiomorphic). Corresponding Bragg diffraction patterns calculated for circularly polarized (helical) x-rays tuned to an atomic resonance prove that angular anisotropy in the distribution of electrons create spots not indexed on the chemical structure (defined by a space group derived from Thomson scattering by perfect spheres of charge). Templeton-Templeton scattering, as it is usually called, of helical x-rays is quantified in terms of a chiral signature defined as the partial diffracted intensity hallmarked by x-ray helicity. Our electric dipole - electric dipole (E1-E1) chiral signature for a space group in the optically active crystal class D2d affords a complete interpretation in terms of copper quadrupoles of diffraction data collected on copper metaborate [E. N. Ovchinnikova et al., J. Synchrotron Rad. 28, 1455 (2021)]. An example of a chiral signature derived from a parity-odd resonance event (E1-E2) is included in our study. It is firmly established that tuning the energy of x-rays to an atomic resonance enhances the intensity of inherently weak Templeton-Templeton scattering and renders space-group forbidden Bragg spots element specific. Our chiral signature as a function of rotation about the reflection vector (azimuthal-angle scan) is specific to position multiplicity, Wyckoff letter and symmetry in a favourable space group.