Chiral Nature Research Articles

Chiral Recognition for Chromatography and Membrane-Based Separations: Recent Developments and Future Prospects.

With the rapid development of global industry and increasingly frequent product circulation, the separation and detection of chiral drugs/pesticides are becoming increasingly important. The chiral nature of substances can result in harm to the human body, and the selective endocrine-disrupting effect of drug enantiomers is caused by differential enantiospecific binding to receptors. This review is devoted to the specific recognition and resolution of chiral molecules by chromatography and membrane-based enantioseparation techniques. Chromatographic enantiomer separations with chiral stationary phase (CSP)-based columns and membrane-based enantiomer filtration are detailed. In addition, the unique properties of these chiral resolution methods have been summarized for practical applications in the chemistry, environment, biology, medicine, and food industries. We further discussed the recognition mechanism in analytical enantioseparations and analyzed recent developments and future prospects of chromatographic and membrane-based enantioseparations.

Spin-orbit torque switching of chiral magnetization across a synthetic antiferromagnet

The interfacial Dzyaloshinskii-Moriya interaction (DMI) holds promises for design and control of chiral spin textures in low-dimensional magnets with efficient current-driven dynamics. Recently, an interlayer DMI has been found to exist across magnetic multilayers with a heavy-metal spacer between magnetic layers. This opens the possibility of chirality in these three-dimensional magnetic structures. Here we show the existence of the interlayer DMI in a synthetic antiferromagnetic multilayer with both inversion and in-plane asymmetry. We analyse the interlayer DMI’s effects on the magnetization and the current-induced spin-orbit torque (SOT) switching of magnetization through a combination of experimental and numerical studies. The chiral nature of the interlayer DMI leads to an asymmetric SOT switching of magnetization under an in-plane magnetic field. Our work paves the way for further explorations on controlling chiral magnetizations across magnetic multilayers through SOTs, which can provide a new path in the design of SOT devices.

Degradation of o-Chloranil Using Nanocrystalline-Cellulose/TiO2 Composites via a Solar Photocatalytic Route

ABSTRACT Water pollution by organic pollutants is a continuous and increasing problem of global concern. In this paper, we developed a nanocrystalline cellulose (NCC) and titania (TiO2) based nanocomposite for the photocatalytic degradation of o-chloranil via aqueous wet impregnation. Different NCC loadings (10, 20, 40, and 80%) were used, and several analytical and microscopy techniques characterised the NCC/TiO2 catalyst. The efficiency of TiO2 as a photo-catalyst was enhanced through the chiral nematic nature and potential charge carrier capacity of NCC, which lowered the rate of electron recombination. The NCC/TiO2 material was used in the solar-driven photo-degradation of o-chloranil (3,4,5,6-tetrachloro-1,2-benzoquinone), a by-product of a commonly used pesticide. The successful decomposition of o-chloranil led to the successful identification of three breakdown products, namely 2,3-dichloro-4,5-dioxohex-2-enedoic acid (DCA), 2,3-dioxosuccinic acid (DSA) and oxalic acid (OA). The 20% NCC/TiO2 catalyst was found to be optimum and showed excellent degradation and mineralisation of o-chloranil within 2 hours (~90% degradation after 2 hours or 0.00920 mols of the total 0.0102 mols). The degradation products were analysed and identified using GC-MS. The photo-catalyst offers many benefits, including ease of preparation, a low cost-factor, and high stability with no loss of activity. Keywords: nanocrystalline cellulose; o-chloroanil; photocatalyst; photo-degradation; titania

Valence-shell photoelectron circular dichroism of ruthenium(III)-tris-(acetylacetonato) gas-phase enantiomers.

Chiral transition-metal complexes are of interest in many fields ranging from asymmetric catalysis and molecular materials science to optoelectronic applications or fundamental physics including parity violation effects. We present here a combined theoretical and experimental investigation of gas-phase valence-shell photoelectron circular dichroism (PECD) on the challenging open-shell ruthenium(III)-tris-(acetylacetonato) complex, Ru(acac)3. Enantiomerically pure Δ- or Λ-Ru(acac)3, characterized by electronic circular dichroism (ECD), were vaporized and adiabatically expanded to produce a supersonic beam and photoionized by circularly-polarized VUV light from the DESIRS beamline at Synchrotron SOLEIL. Photoelectron spectroscopy (PES) and PECD experiments were conducted using a double imaging electron/ion coincidence spectrometer, and compared to density functional theory (DFT) and time-dependent DFT (TDDFT) calculations. The open-shell character of Ru(acac)3, which is not taken into account in our DFT approach, is expected to give rise to a wide multiplet structure, which is not resolved in our PES signals but whose presence might be inferred from the additional striking features observed in the PECD curves. Nevertheless, the DFT-based assignment of the electronic bands leads to the characterisation of the ionized orbitals. In line with other recent works, the results confirm that PECD persists independently on the localization and/or on the achiral or chiral nature of the initial orbital, but is rather a probe of the molecular potential as a whole. Overall, the measured PECD signals on Ru(acac)3, a system exhibiting D3 propeller-type chirality, are of similar magnitude compared to those on asymmetric-carbon-based chiral organic molecules which constitute the vast majority of species investigated so far, thus suggesting that PECD is a universal mechanism, inherent to any type of chirality.

Pharmacokinetics of Mephedrone Enantiomers in Whole Blood after a Controlled Intranasal Administration to Healthy Human Volunteers.

Mephedrone, which is one of the most popular synthetic cathinones, has one chiral centre and thus exists as two enantiomers: R-(+)-mephedrone and S-(−)-mephedrone. There are some preliminary data suggesting that the enantiomers of mephedrone may display enantioselective pharmacokinetics and exhibit different neurological effects. In this study, enantiomers of mephedrone were resolved via chromatographic chiral recognition and the absolute configuration was unambiguously determined by a combination of elution order and chiroptical analysis (i.e., circular dichroism). A chiral liquid chromatography tandem mass spectrometry method was fully validated and was applied to the analysis of whole blood samples collected from a controlled intranasal administration of racemic mephedrone hydrochloride to healthy male volunteers. Both enantiomers showed similar kinetics, however, R-(+)-mephedrone had a greater mean Cmax of 48.5 ± 11.9 ng/mL and a longer mean half-life of 1.92 ± 0.27 h compared with 44.6 ± 11.8 ng/mL and 1.63 ± 0.23 h for S-(−)-mephedrone, respectively. Moreover, R-(+)-mephedrone had a lower mean clearance and roughly 1.3 times greater mean area under the curve than S-(−)-mephedrone. Significant changes in the enantiomeric ratio over time were observed, which suggest that the analytes exhibit enantioselective pharmacokinetics. Even though the clinical significance of this finding is not yet fully understood, the study confirms that the chiral nature, and consequently the enantiomeric purity of mephedrone, can be a crucial consideration when interpreting toxicological results.

Topological Strain-Induced Regioselective Linker Elimination in a Chiral Zr(IV)-Based Metal-Organic Framework

Summary Zr-carboxylate metal-organic frameworks (MOFs) are structurally robust materials, in part due to their strong coordination bonds. The regioselective Zr–O bond cleavage and formation between 3D architectures are thus challenging and are heretofore unexplored. In this work, by introducing highly flexible 18-crown-6-ether functionalities into a homochiral Zr-MOF, we report an unprecedented topology transition in which a 4,10-connected framework undergoes a rapid solid-state transition into a thermodynamically more stable 4,8-connected analog by a regioselective-linker-elimination under ambient conditions. The transition process was unambiguously unraveled by single-crystal and powder X-ray diffraction studies, and we proposed a possible transition mechanism based on various control experiments and theoretical calculations. The excellent chemical stability and substantially expanded porosity and pore apertures endowed the transformed chiral MOF with an exceptional capacity for the enantioadsorptive and solid-phase extractive separation of the racemic drug molecule of lansoprazole with 98% ee and 93% ee, respectively.

Helically Grooved Gold Nanoarrows: Controlled Fabrication, Superhelix, and Transcribed Chiroptical Switching

Plasmonic chiroptical materials, coupled by chirality and surface plasmons, have been attracting great interest due to their potential applications, such as photonics, chiral recognition, asymmetri...

Flat Bands in Magic-Angle Vibrating Plates.

Twisted bilayer graphene develops quasiflat bands at specific "magic" interlayer rotation angles through an unconventional mechanism connected to carrier chirality. Quasiflat bands are responsible for a wealth of exotic, correlated-electron phases in the system. In this Letter, we propose a mechanical analog of twisted bilayer graphene made of two vibrating plates patterned with a honeycomb mesh of masses and coupled across a continuum elastic medium. We show that flexural waves in the device exhibit vanishing group velocity and quasiflat bands at magic angles in close correspondence with electrons in graphene models. The strong similarities of spectral structure and spatial eigenmodes in the two systems demonstrate the chiral nature of the mechanical flat bands. We derive analytical expressions that quantitatively connect the mechanical and electronic models, which allow us to predict the parameters required for an experimental realization of our proposal.

Chirality in [formula omitted]Pm

One of the enticing manifestations of broken symmetries in atomic nuclei is the chiral doublet bands. We investigate such bands in 136Pm and 138Pm, to understand the underlying geometries and their correlations with the single-particle configurations. We identify such correlations leading to vibrational or static nature of chirality. Chirality withstands higher spins in 136Pm, unlike 138Pm. Our present calculations for 138Pm, confirm the newly assigned spin and parity 9+ state as band-head of the yrast band, based on {πh11/2⊗νh11/2} configuration.

Extraction of the valence transversity distributions from SIDIS data

The transversity distribution for $u$ and $d$ quarks is usually extracted from data on spin asymmetries in Semi Inclusive Deep Inelastic Scattering (SIDIS): however, due to its chiral odd nature, it has to be coupled to another chiral odd function, typically the Collins or the di-hadron fragmentation function. A recent suggestion of considering SIDIS data involving ratios of spin asymmetries and avoiding a knowledge of the Collins function, is briefly discussed. New measurements, involving ratios of cross sections, are suggested. They would allow a direct extraction of the transversity ratio, $h_1^{d_V}/h_1^{u_V}$. Numerical estimates are given.

Rapid detection of chiral drug ephedrine using erythrosin B for the resonance Rayleigh scattering probe.

Ephedrine (EH) and pseudoephedrine (PEH), which are chiral enantiomers commonly used clinically, have different pharmacological actions and treatment effects due to their chiral nature. In the presence of Pd2+ , the reaction system of Ery B (erythrosin B)-Pd2+ has a strong resonance Rayleigh scattering (RRS) intensity. Adding EH into this system reduced the RRS intensity, but PEH could not produce this phenomenon. The chiral recognition of these enantiomers could be achieved according to this spectral difference. At the same time, reduction in RRS strength of the reaction system is proportional to the concentration of EH. Under optimized conditions, the linear range is 40-960 ng/ml, and the detection limit is 3.9 ng/ml. A new method for the rapid detection of EH enantiomers can be established. Based on this assay, a new method for the determination of the chiral enantiomers of EH and PEH can be developed.

Molecular Logic of Prokaryotic Surface Layer Structures.

Most prokaryotic cells are encased in a surface layer (S-layer) consisting of a paracrystalline array of repeating lattice-forming proteins. S-layer proteins populate a vast and diverse sequence space, performing disparate functions in prokaryotic cells, including cellular defense, cell-shape maintenance, and regulation of import and export of materials. This article highlights recent advances in the understanding of S-layer structure and assembly, made possible by rapidly evolving structural and cell biology methods. We underscore shared assembly principles revealed by recent work and discuss a common molecular framework that may be used to understand the structural organization of S-layer proteins across bacteria and archaea.

Novel ureido-dihydropyridine scaffolds as theranostic agents

In this work, the synthesis of interesting urea derivatives 5 based on 1,4-dihydropyridines 3 is described for the first time. Considering that both families exhibit potential as drugs to treat various diseases, their activity as anticancer agents has been evaluated in HeLa (cervix), Jurkat (leukaemia) and A549 (lung) cancer cell lines as well as on healthy mice in vivo.In general, whereas 1,4-dihydropyridines show a moderate cytotoxic activity, their urea analogues cause an extraordinary increase in their antiproliferative activity, specially towards HeLa cells. Because of the chiral nature of these compounds, enantiomerically enriched samples were also tested, showing different cytotoxic activity than the racemic mixture. Although the reason is not clear, it could be caused by a complex amalgam of physical and chemical contributions.The studied compounds also exhibit luminescent properties, which allow performing a biodistribution study in cancer cells. They have emission maxima between 420 and 471 nm, being the urea derivatives in general red shifted. Emission quenching was observed for those compounds containing a nitro group (3e,f and 5e,f). Fluorescence microscopy showed that 1,4-dihydropyridines 3a and 3g localised in the lysosomes, in contrast to the urea derivatives 5h that accumulated in the cell membrane. This different distribution could be key to explain the differences found in the cytotoxic activity and in the mechanism of action. Interestingly, a preliminary in vivo study regarding the acute toxicity of some of these compounds on healthy mice has been conducted, using a concentration up to 7200 times higher than the corresponding IC50 value. No downgrade in the welfare of the tested mice was observed, which could support their use in preclinical tumour models.

Multiple-scattering approach for multi-spin chiral magnetic interactions: application to the one- and two-dimensional Rashba electron gas

Various multi-spin magnetic exchange interactions (MEI) of chiral nature have been recently unveiled. Owing to their potential impact on the realisation of twisted spin-textures, their future implication in spintronics or quantum computing is very promising. Here, I address the long-range behavior of multi-spin MEI on the basis of a multiple-scattering formalism implementable in Green functions based methods such as the Korringa–Kohn–Rostoker (KKR) Green function framework. I consider the impact of spin–orbit coupling (SOC) as described in the one- (1D) and two-dimensional (2D) Rashba model, from which the analytical forms of the four- and six-spin interactions are extracted and compared to the well known bilinear isotropic, anisotropic and Dzyaloshinskii–Moriya interactions (DMI). Similarly to the DMI between two sites i and j, there is a four-spin chiral vector perpendicular to the bond connecting the two sites. The oscillatory behavior of the MEI and their decay as function of interatomic distances are analysed and quantified for the Rashba surfaces states characterizing Au surfaces. The interplay of beating effects and strength of SOC gives rise to a wide parameter space where chiral MEI are more prominent than the isotropic ones. The multi-spin interactions for a plaquette of N magnetic moments decay like simplifying to for equidistant atoms, where d is the dimension of the mediating electrons, qF the Fermi wave vector, L the perimeter of the plaquette while P is the product of interatomic distances. This recovers the behavior of the bilinear MEI, , and shows that increasing the perimeter of the plaquette weakens the MEI. More important, the power-law pertaining to the distance-dependent 1D MEI is insensitive to the number of atoms in the plaquette in contrast to the linear dependence associated with the 2D MEI. Furthermore, the N-dependence of qF offers the possibility of tuning the interactions amplitude by engineering the electronic occupation.

Collinear electroweak radiation in antenna parton showers

We present a first implementation of collinear electroweak radiation in the Vincia parton shower. Due to the chiral nature of the electroweak theory, explicit spin dependence in the shower algorithm is required. We thus use the spinor-helicity formalism to compute helicity-dependent branching kernels, taking special care to deal with the gauge relics that may appear in computation that involve longitudinal polarizations of the massive electroweak vector bosons. These kernels are used to construct a shower algorithm that includes all possible collinear final-state electroweak branchings, including those induced by the Yang–Mills triple vector boson coupling and all Higgs couplings, as well as vector boson emissions from the initial state. We incorporate a treatment of features particular to the electroweak theory, such as the effects of bosonic interference and recoiler effects, as well as a preliminary description of the overlap between electroweak branchings and resonance decays. Some qualifying results on electroweak branching spectra at high energies, as well as effects on LHC physics are presented. Possible future improvements are discussed, including treatment of soft and spin effects, as well as issues unique to the electroweak sector.

Meron-like topological spin defects in monolayer CrCl3

Noncollinear spin textures in low-dimensional magnetic systems have been studied for decades because of their extraordinary properties and promising applications derived from the chirality and topological nature. However, material realizations of topological spin states are still limited. Employing first-principles and Monte Carlo simulations, we propose that monolayer chromium trichloride (CrCl3) can be a promising candidate for observing the vortex/antivortex type of topological defects, so-called merons. The numbers of vortices and antivortices are found to be the same, maintaining an overall integer topological unit. By perturbing with external magnetic fields, we show the robustness of these meron pairs and reveal a rich phase space to tune the hybridization between the ferromagnetic order and meron-like defects. The signatures of topological excitations under external magnetic field also provide crucial information for experimental justifications. Our study predicts that two-dimensional magnets with weak spin-orbit coupling can be a promising family for realizing meron-like spin textures.

Super-chiral vibrational spectroscopy with metasurfaces for high-sensitive identification of alanine enantiomers

Chiral nature of an enantiomer can be characterized by circular dichroism (CD) spectroscopy, but such a technique usually suffers from weak signal even with a sophisticated optical instrument. Recent demonstrations of plasmonic metasurfaces showed that chiroptical interaction of molecules can be engineered, thereby greatly simplifying a measurement system with high sensing capability. Here, by exploiting super-chiral field in a metasurface, we experimentally demonstrate high-sensitive vibrational CD spectroscopy of alanine enantiomers, the smallest chiral amino acid. Under linearly polarized excitation, the metasurface consisting of an array of staggered Au nano-rods selectively produces the left- and right-handed super-chiral fields at 1600 cm−1, which spectrally overlaps with the functional group vibrations of alanine. In the Fourier-transform infrared spectrometer measurements, the mirror symmetric CD spectra of D- and L-alanine are clearly observed depending on the handedness of the metasurface, realizing the reliable identification of small chiral molecules. The corresponding numerical simulations reveal the underlying resonant chiroptical interaction of plasmonic modes of the metasurface and vibrational modes of alanine. Our approach demonstrates a high-sensitive vibrational CD spectroscopic technique, opening up a reliable chiral sensing platform for advanced infrared inspection technologies.

Nonreciprocity of spin waves in noncollinear magnets due to the Dzyaloshinskii-Moriya interaction

Broken inversion symmetry in combination with the spin-orbit interaction generates a finite Dzyaloshinskii-Moriya interaction (DMI), which can induce noncollinear spin textures of chiral nature. The DMI is characterized by an interaction vector whose magnitude, direction and symmetries are crucial to determine the stability of various spin textures, such as skyrmions and spin spirals. The DMI can be measured from the nonreciprocity of spin waves in ferromagnets, which can be probed via inelastic scattering experiments. In a ferromagnet, the DMI can modify the spin-wave dispersion, moving its minimum away from the $\Gamma$ point. Spin waves propagating with opposite wavevectors are then characterized by different group velocities, energies and lifetimes, defining their nonreciprocity. Here, we address the case of complex spin textures, where the manifestation of DMI-induced chiral asymmetries remains to be explored. We discuss such nonreciprocal effects and propose ways of accessing the magnitude and direction of the DMI vectors in the context of spin-polarized or spin-resolved inelastic scattering experiments. We show that only when a periodic magnetic system has finite net magnetization, that is, when the vector sum of all magnetic moments is nonzero, can it present a total nonreciprocal spin-wave spectrum. However, even zero-net-magnetization systems, such as collinear antiferromagnets and cycloidal spin spirals, can have spin-wave modes that are individually nonreciprocal, while the total spectrum remains reciprocal.

High-spin doublet band structures in odd–odd $$^{194-200}$$Tl isotopes

The basis space in the triaxial projected shell model (TPSM) approach is generalized for odd-odd nuclei to include two-neutron and two-proton configurations on the basic one-neutron coupled to one-proton quasiparticle state. The generalization allows to investigate odd-odd nuclei beyond the band crossing region and as a first application of this development, high-spin band structures recently observed in odd-odd $^{194-200}$Tl isotopes are investigated. In some of these isotopes, the doublet band structures observed after the band crossing have been conjectured to arise from the spontaneous breaking of the chiral symmetry. The driving configuration of the chiral symmetry in these odd-odd isotopes is one-proton and three-neutrons rather than the basic one-proton and one-neutron as already observed in many other nuclei. It is demonstrated using the TPSM approach that energy differences of the doublet bands in $^{194}$Tl and $^{198}$Tl are, indeed, small. However, the differences in the calculated transition probabilities are somewhat larger than what is expected in the chiral symmetry limit. Experimental data on the transition probabilities is needed to shed light on the chiral nature of the doublet bands.

Modulation of a Supramolecular Figure-of-Eight Strip Based on a Photoswitchable Stiff-Stilbene.

The preparation, assembly and dynamic properties of photoswitchable bisphosphine ligands based on the stiff‐stilbene scaffold are reported. Directional bonding and coordination‐induced assembly allow complexation of these ligands with palladium(II), resulting in the formation of discrete metallo‐supramolecular entities. While the Z isomer forms a simple bidentate metallo‐macrocycle, an intricate double helicate figure‐of‐eight dimer is observed with the E ligand. Topologically 3D complexes can thus be obtained from 2D ligands. Upon irradiation with UV light, isomerization of the ligands allows control of the architecture of the formed complexes, resulting in a light‐triggered modulation of the supramolecular topology. Furthermore, a mechanistic investigation unveiled the dynamic nature of the helicate chirality, where a transmission of motion from the palladium centers yields an „eight‐to‐eight“ inversion.