Chiral Metals Research Articles

Tandem Mass Spectrometry Approaches for Differentiation and Quantification Pidotimod and Its Three Isomers in the Gas Phase.

Pidotimod is a chiral drug that possesses two chiral centers, resulting in three isomeric impurities (analytes, A). This study employs electrospray ionization ion trap mass spectrometry (ESI-MS) through collision-induced dissociation (CID) to investigate the chiral recognition of pidotimod and its three isomers to eliminate chromatographic separation. Three approaches were explored: (1) Protonated molecules in CID exhibited discriminative potential for diastereomers, with the ability to distinguish between S,S and R,R configurations, albeit with an Rchiral value of ~1.8. However, differentiation between R,S and S,R configurations was not achievable. (2) Alkali adductions (lithium and sodium) only discerned diastereomers. The Rchiral values of the diastereomers obtained from alkali adduct ions were significantly lower than those obtained from protonated ions. (3) Therefore, a third approach was used to address the challenge of distinguishing between R,S and S,R configurations, including the introduction of chiral references (ref) and transition metals (MII) to form metal-bound complexes [MII(A)(ref)-H]+. Additionally, we synthesized a novel ligand, 4-(N-tert-butoxycarbonyl [Boc]-L-prolinamido)phenol (denoted as ligand A), by modifying N-t-Boc-L-Pro with 2-aminophenol, which, in combination with CuII and NiII, enabled simultaneous differentiation of all four isomers. CuII complexes exhibited significant chiral selectivity between R,S and S,R configurations. Density functional theory calculations were performed to further elucidate the stereodynamic behavior and stoichiometry of these ions in the gas phase. These calculations revealed the interaction energy and coordination sites of the precursor ions in the gas phase, correlating well with MS/MS experiment results. Additionally, the logarithm of the CuII complexes' characteristic fragment ion abundance ratio demonstrated a strong linear relationship with enantiomeric excess (ee). This study presents a novel strategy for chiral drug quality control that eliminates chromatographic separation.

Chiral topological metals with multiple types of quasiparticle fermions and large spin Hall effect in the SrGePt family materials

Chiral topological metals with multiple types of quasiparticle fermions and large spin Hall effect in the SrGePt family materials

Switching Chirality in Arrays of Shape-Reconfigurable Spindle Microparticles.

The giant circular photo-galvanic effect is realized in chiral metals when illuminated by circularly polarized light. However, the structure itself is not switchable nor is the crystal chirality in the adjacent chiral domains. Here spindle-shaped liquid crystalline elastomer microparticles that can switch from prolate to spherical to oblate reversibly upon heating above the nematic to isotropic transition temperature are synthesized. When arranged in a honeycomb lattice, the continuous shape change of the microparticles leads to lattice reconfiguration, from a right-handed chiral state to an achiral one, then to a left-handed chiral state, without breaking the translational symmetry. Accordingly, the sign of rotation of the polarized light passing through the lattices changes as measured by time-domain terahertz spectroscopy. Further, it can locally alter the chirality in the adjacent domains using near-infrared light illumination. The reconfigurable chiral microarrays will allow us to explore non-trivial symmetry-protected transport modes of topological lattices at the light-matter interface. Specifically, the ability to controllably create chiral states at the boundary of the achiral/chiral domains will lead to rich structures emerging from the interplay of symmetry and topology.

Current algebra approach to two-dimensional interacting chiral metals

We reinterpret the chiral $U(N)$ Wess-Zumino-Witten (WZW) model at level $k>1$ in $(1+1)$ dimensions as an interacting chiral metal in two space dimensions. In this reinterpretation, spatial translations along one of the spatial dimensions in the two-dimensional chiral metal arise from a generator of the $U(N)$ symmetry of the WZW model. The WZW model at $k=1$ is equivalent to Balents and Fisher's free chiral metal [L. Balents and M. P. A. Fisher, Phys. Rev. Lett. 76, 2782 (1996)]. Here, the $U(N)$ symmetry corresponds to the IR symmetry of a chiral Fermi gas with (half of a) Fermi surface, with $N$ equal to the number of points on the Fermi surface. We argue that exactly solvable interacting generalizations occur for levels $k>1$. Importantly, these interacting chiral metals maintain the $U(N)$ symmetry of the free system. We calculate two-point correlation functions of the single-particle fermion operator, the $U(1)$ number density, and current operators in these theories for general $k$. We find that interactions ($k>1$) produce $1/N$ corrections to scaling of the single-particle fermion operator as $N\ensuremath{\rightarrow}\ensuremath{\infty}$ and renormalize the amplitudes of the density and current two-point functions. This construction illustrates the ersatz Fermi liquid proposal of Else et al. [Phys. Rev. X 11, 021005 (2021)].

Chiral Josephson effect in double layers: The role of particle–hole duality

AbstractThe Josephson effect of inter‐layer s‐wave pairing in a double layer of two chiral metals with Josephson junctions along the direction is considered. Starting from the Bogoliubov de Gennes equations of electron–electron and electron–hole double layers, we employ the duality transformation between the two systems to determine the relation of the zero‐energy quasiparticle modes at a Josephson junction in both systems. The appearance of an exceptional point at zero energy is observed, where the four‐dimensional eigenspace coalesces to a two‐dimensional eigenspace. In the second part of the article, the coupling of the quasiparticle currents and the supercurrent is studied. The coupling is based on the quasiparticle charge conservation in the form of a continuity equation. Although the quasiparticle modes differ between the electron–electron and the electron–hole double layers, their corresponding currents are the same.

Chiral Crystals, Jack, Conductivity and Magnetism

AbstractRecently, the application of magnetic fields to chiral chemical systems has been rewarding. In a forward‐looking 1986 paper, ‘Chiral Metals?’, Wallis, Karrer, and Jack D. Dunitz forecast ‘that the limitation to proper symmetry elements in a chiral conductor could be associated with the emergence of new properties, those connected with interactions between applied electric and magnetic fields and their internal counterparts.’ This was a prescient remark, but it has become manifest in ways that would not have been foreseen in its details by the authors. Here are reviewed the development of chiral conductors broadly imagined by Dunitz and coworkers, based on enantiopure tetrathiafulvalene derivatives that restrict space groups to those that have only symmetry operations of the first kind, as well as the new emergent properties associated with the transport of electrons when magnetic fields are applied to chiral crystals among other systems. These include electrical magnetochiral anisotropy (eMChA), inverse electrical magnetochiral anisotropy (ieMChA), helimagnetism and chirality induced spin selectivity (CISS). The conclusion discussing the circumstances under which achiral TTF crystals becomes chiral, only seems to introduce an oxymoron.

Nonlocality of Electrically-Induced Spin Accumulation in Chiral Metals

Spin accumulation induced by an electric field in chiral electron system is investigated based on a linear response theory. It is shown that the spin response function has a spatially uniform component due to the chiral angular momentum generation effect, resulting in a nonlocal spin generation. The result suggests a scenario for nonlocal long-range spin transport in chiral metals reported experimentally recently.

Chiral metals and entrapped insulators in a one-dimensional topological non-Hermitian system

In this work, we study many-body ``steady states'' that arise in the non-Hermitian generalization of the noninteracting Su-Schrieffer-Heeger model at a finite density of fermions. We find that the hitherto known phase diagrams for this system, derived from the single-particle gap closings, in fact correspond to distinct nonequilibrium phases, which either carry finite currents or are dynamical insulators where particles are entrapped. Each of these have distinct quasiparticle excitations and steady-state correlations and entanglement properties. Looking at finite-sized systems, we further modulate the boundary to uncover the topological features in such steady states, particularly the emergence of leaky boundary modes. Using a variety of analytical and numerical methods, we develop a theoretical understanding of the various phases and their transitions, and we uncover the rich interplay of nonequilibrium many-body physics, quantum entanglement, and topology in a simple looking yet rich model system.

Anomalous Josephson Effect of s-Wave Pairing States in Chiral Double Layers.

We consider s-wave pairing in a double layer of two chiral metals due to interlayer Coulomb interaction and study the Josephson effect near a domain wall, where the sign of the order parameter jumps. The domain wall creates two evanescent modes at the exceptional zero-energy point, whose superposition is associated with currents flowing in different directions in the two layers. Assuming a toroidal geometry, the effective Josephson current winds around the domain walls, whose direction is determined by the phase difference of the complex coefficients of the superimposed zero-energy modes. Thus, the zero-energy mode is directly linked to a macroscopic current. This result can be understood as an interplay of the conventional Josephson current perpendicular and the edge current parallel to a domain wall in a double layer of two chiral metals. As a realization we suggest the surface of a ring-shaped topological insulator. The duality between electron-electron and electron-hole double layers indicates that this effect should also be observable in excitonic double layers.

Phase transitions between helices, vortices, and hedgehogs driven by spatial anisotropy in chiral magnets

Superpositions of spin helices can yield topological spin textures, such as two-dimensional vortices and skyrmions, and three-dimensional hedgehogs. Their topological nature and spatial dimensionality depend on the number and relative directions of the constituent helices. This allows mutual transformation between the topological spin textures by controlling the spatial anisotropy. Here we theoretically study the effect of anisotropy in the magnetic interactions for an effective spin model for chiral magnetic metals. By variational calculations for both cases with triple and quadruple superpositions, we find that the hedgehog lattices, which are stable in the isotropic case, are deformed by the anisotropy, and eventually changed into other spin textures with reduced dimension, such as helices and vortices. We also clarify the changes of topological properties by tracing the real-space positions of magnetic monopoles and antimonopoles as well as the emergent magnetic field generated by the noncoplanar spin textures. Our results suggest possible control of the topological spin textures, e.g., by uniaxial pressure and chemical substitution in chiral materials.

Correlation between Ferromagnetic Layer Easy Axis and the Tilt Angle of Self Assembled Chiral Molecules

The spin–spin interactions between chiral molecules and ferromagnetic metals were found to be strongly affected by the chiral induced spin selectivity effect. Previous works unraveled two complementary phenomena: magnetization reorientation of ferromagnetic thin film upon adsorption of chiral molecules and different interaction rate of opposite enantiomers with a magnetic substrate. These phenomena were all observed when the easy axis of the ferromagnet was out of plane. In this work, the effects of the ferromagnetic easy axis direction, on both the chiral molecular monolayer tilt angle and the magnetization reorientation of the magnetic substrate, are studied using magnetic force microscopy. We have also studied the effect of an applied external magnetic field during the adsorption process. Our results show a clear correlation between the ferromagnetic layer easy axis direction and the tilt angle of the bonded molecules. This tilt angle was found to be larger for an in plane easy axis as compared to an out of plane easy axis. Adsorption under external magnetic field shows that magnetization reorientation occurs also after the adsorption event. These findings show that the interaction between chiral molecules and ferromagnetic layers stabilizes the magnetic reorientation, even after the adsorption, and strongly depends on the anisotropy of the magnetic substrate. This unique behavior is important for developing enantiomer separation techniques using magnetic substrates.

Breakdown of Diffusion on Chiral Edges.

We show that dirty quantum Hall systems exhibit large hydrodynamic fluctuations at their edge that lead to anomalously damped charge excitations in the Kardar-Parisi-Zhang universality class ω≃ck-iDk^{3/2}. The dissipative optical conductivity of the edge is singular at low frequencies σ(ω)∼1/ω^{1/3}. These results are direct consequences of the charge continuity relation, the chiral anomaly, and thermalization on the edge-in particular translation invariance is not assumed. Diffusion of heat similarly breaks down, with a universality class that depends on whether the bulk thermal Hall conductivity vanishes. We further establish the theory of fluctuating hydrodynamics for surface chiral metals, where charge fluctuations give logarithmic corrections to transport.

Topological quantum properties of chiral crystals.

Chiral crystals are materials with a lattice structure that has a well-defined handedness due to the lack of inversion, mirror or other roto-inversion symmetries. Although it has been shown that the presence of crystalline symmetries can protect topological band crossings, the topological electronic properties of chiral crystals remain largely uncharacterized. Here we show that Kramers-Weyl fermions are a universal topological electronic property of all non-magnetic chiral crystals with spin-orbit coupling and are guaranteed by structural chirality, lattice translation and time-reversal symmetry. Unlike conventional Weyl fermions, they appear at time-reversal-invariant momenta. We identify representative chiral materials in 33 of the 65 chiral space groups in which Kramers-Weyl fermions are relevant to the low-energy physics. We determine that all point-like nodal degeneracies in non-magnetic chiral crystals with relevant spin-orbit coupling carry non-trivial Chern numbers. Kramers-Weyl materials can exhibit a monopole-like electron spin texture and topologically non-trivial bulk Fermi surfaces over an unusually large energy window.

Chiral metals as electrodes

Summary Chirality is one of the most fascinating issues in chemical researches. In this review, the development of chiral metals is summarized from the past to the present. Several very recent concepts for generating chiral metals, such as the design of chiral imprinted cavities at mesoporous metal surfaces, are also presented. The application of chiral metals as electrodes in the enantioselective recognition and asymmetric synthesis of chiral compounds reveals that these designer surfaces open up potential perspectives for the development of new materials for chiral technologies.

ChemInform Abstract: Conjugate Addition—Enantioselective Protonation Reactions

AbstractReview: [77 refs.

Conjugate addition-enantioselective protonation reactions.

The addition of nucleophiles to electron-deficient alkenes represents one of the more general and commonly used strategies for the convergent assembly of more complex structures from simple precursors. In this review the addition of diverse protic and organometallic nucleophiles to electron-deficient alkenes followed by enantioselective protonation is summarized. Reactions are first categorized by the type of electron-deficient alkene and then are further classified according to whether catalysis is achieved with chiral Lewis acids, organocatalysts, or transition metals.

Separation of catechin epimers by complexation using ion mobility mass spectrometry.

Ion mobility coupled with mass spectrometry provides a fast and repeatable method to separate catechin epimers by previous complexation with selected chiral modifiers and transition metals. Several combinations with chiral ligands such as D- and L-amino acids and/or additional metal cations, chiral crown ethers, tartaric acid and heptakis(2,6-di-O-methyl)-β-cyclodextrin were screened for their ability to affect the separation efficiency. The clusters having the form of [2M + D-amino acid + Cu(2+) - 3H](-) (M stands for (-)-epicatechin or (+)-catechin) showed improvement in stereodifferentiation between two epimeric catechins in comparison to the analysis of pure epimers, where no separation was observed or the separation was hampered by the formation of mixed dimer complexes. Among various examined D-amino acids only those possessing hydrophobic side chains induced the improvement of separation efficiency. The best peak-to-peak resolution (Rp-p) was determined to be 0.71 for [2M + D-Leucine + Cu(2+) - 3H](-) clusters.

Density of states in a two-dimensional chiral metal with vacancies.

We study quantum interference effects in a two-dimensional chiral metal (bipartite lattice) with vacancies. We demonstrate that randomly distributed vacancies constitute a peculiar type of chiral disorder leading to strong modifications of critical properties at zero energy as compared to those of conventional chiral metals. In particular, the average density of states diverges as ρ∝E(-1)|lnE|(-3/2) and the correlation length L(c)∝√[|lnE|] in the limit E→0. When the average density of vacancies is different in the two sublattices, a finite concentration of zero modes emerges and a gap in the quasiclassical density of states opens around zero energy. Interference effects smear this gap, resulting in exponentially small tails at low energies.

Berry phase mechanism for optical gyrotropy in stripe-ordered cuprates

Optical gyrotropy, the lifting of degeneracy between left and right circularly polarized light, can be generated by either time-reversal or chiral symmetry breaking. In the high-${T}_{c}$ superconductor La${}_{2\ensuremath{-}x}$Ba${}_{x}$CuO${}_{4}$ (LBCO), gyrotropy onsets at the same temperature as charge stripe order, suggesting that the rotation of the stripe direction from one plane to the next generates a helical pattern that breaks chiral symmetry. In order to further test this chiral stacking hypothesis it is necessary to develop an understanding of the physical mechanisms by which chirality generates gyrotropy. In this paper we show that, in chiral metals, optical gyrotropy is a consequence of Berry curvature in momentum space. We describe a physical picture showing that gyrotropy in chiral metals is closely related to the anomalous Hall effect in itinerant ferromagnets. We then calculate the magnitude of the gyrotropic response for a given Berry curvature using the semiclassical picture of anomalous velocity and Boltzmann transport theory. To connect this physical picture with experiment, we calculate the Berry curvature in two tight-binding models. The first model is motivated by the structure of LBCO and illustrates how gyrotropy is created when stripe perturbations are added to a simple cubic model. In the second model, we examine the dramatic enhancement of the gyrotropic coefficient when Rashba spin-orbit coupling is introduced. The magnitude of the rotation of polarization on reflection expected based on these models is calculated and compared with experimental data.

ChemInform Abstract: Asymmetric Catalysis with Bis(hydroxyphenyl)diamides/Rare‐Earth Metal Complexes

AbstractReview: ca. 200 refs.