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The dielectric properties of synclinic (ferroelectric SmC*) and anticlinic (antiferroelectric SmCA*) smectic liquid crystals composed of molecules of one chiral version (S) are presented and compared with properties of racemic mixture (R, S), showing SmC and SmCA phases. The racemic mixture completely loses its ferroelectric and antiferroelectric properties. Surprisingly, only one dielectric mode observed in the antiferroelectric SmCA* phase disappeared in the dielectric response of the racemic SmCA phase. Additionally, we observed that in the SmC phase, seen in the racemic mixture, the weak dielectric mode (named the X mode) is detected, which seems to be the continuation of the PL mode existing in the racemic SmCA. Moreover, this mode in the racemic SmC has nothing to do with the Goldstone mode, typical for the SmC* phase. This paper describes in detail the real and imaginary parts of dielectric permittivity in smectic phases for the enantiomer and racemate with and without a DC field, compares the properties of the X and PL modes, and discusses the full scheme of dielectric modes in enantiomer and racemate. [ABSTRACT FROM AUTHOR]

Manipulating plasmonic chirality has shown promising applications in nanophotonics, stereochemistry, chirality sensing, and biomedicine. However, to reconfigure plasmonic chirality, the strategy of constructing chiral plasmonic systems with a tunable morphology is cumbersome and complicated to apply for integrated devices. Here, we present a simple and effective method that can also manipulate chirality and control chiral light–matter interactions only via strong coupling between chiral plasmonic nanoparticles and excitons. This paper presents a chiral plexcitonic system consisting of L-shaped nanorod dimers and achiral molecule excitons. The circular dichroism (CD) spectra in our strong-coupling system can be calculated by finite element method simulations. We found that the formation of the chiral plexcitons can significantly modulate the CD spectra, including the appearance of new hybridized peaks, double Rabi splitting, and bisignate anti-crossing behaviors. This phenomenon can be explained by our extended coupled-mode theory. Moreover, we explored the applications of this method in enantiomer ratio sensing by using the properties of the CD spectra. We found a strong linear dependence of the CD spectra on the enantiomer ratio. Our work provides a facile and efficient method to modulate the chirality of nanosystems, deepens our understanding of chiral plexcitons in nanosystems, and facilitates the development of chiral devices and chiral sensing. [ABSTRACT FROM AUTHOR]

This paper explores and revisits in detail the formation and characterization of sugar-based aminonitriles, whose ultimate origin can be traced to the interaction of biomolecules with cyanide. Although the synthesis and spectroscopic data of 2-amino-aldononitriles were reported long ago, there are both contradictory and confusing results among the published data. We have now addressed this concern through an exhaustive structural elucidation of acylated 2-amino- and 2-alkyl(aryl)amino-2-deoxyaldonitriles using mass spectrometry and FT-IR, FT–Raman, and NMR spectroscopies. Several structures could be unambiguously determined through single-crystal X-ray diffraction, which allowed us to correct other misassignments. Moreover, this study unveils how steric and electronic effects influence the acylation outcome of the amino, (alkyl, aryl)amino, or acetamido group at C-2. The chirality at the latter, which was assigned tentatively through optical rotation correlation, and hence the preferential threo stereochemistry generated during the cyanohydrin synthesis of 2-amino-2-deoxy aldononitriles have now been established with confidence. [ABSTRACT FROM AUTHOR]

The generation of vector beams using metasurfaces is crucial for the manipulation of light fields and has significant application potential, ranging from classical physics to quantum science. This paper introduces a novel dielectric metasurface composed of quarter-wave plate (QWP) meta-atoms, known as a QWP metasurface, designed to generate focused vector beams (VBs) of Bell-like states under right circularly polarized illumination. The propagation phase imparted on both the co- and cross-polarized components of the output field constructs hyperbolic and helical phase profiles with topological charge lp, whereas the Pancharatnam–Berry (PB) phase acts only on the cross-polarized component to construct another helical phase profile with topological charge lg. Thus, the co- and cross-polarized components form two orthogonal vector vortex (VV) modes with topological charges lp and lp + lg, respectively. When the parameter conditions are satisfied by matching the incident polarization chirality σ and topological charges lp and lg, the focused VBs of Bell-like states are generated by simultaneously manipulating the two VV modes, in contrast to existing QWP metasurfaces. The polarization states of the generated VBs are manipulated using the initial orientation angle θ0 of the meta-atom. Overall, this research provides an innovative strategy for metasurface design, enhancing the functionality of metasurface devices for a broader range of application scenarios. [ABSTRACT FROM AUTHOR]

In this paper, we apply a numerical integration strategy recently developed for determining the deformation shapes of structures constituted by Cosserat rods, to predict the behavior of panto-cylinders. Panto-cylinders have, as microstructure, a set of two families of helicoidal beams interconnected by perfect or elastic joints. The pivot's free rotation axis is, in the reference configuration, orthogonal to the cylindrical surfaces spanned by the beams. We perform a series of numerical simulations looking for the mechanical parameters which exalt the chirality effects in the structure. For the performed compression, extensions, shear, and torsion tests, we find chiral deformation patterns with a dependence on the type of joint and its length. [ABSTRACT FROM AUTHOR]

Front cover: In establishing the left‐right axis of the body in Drosophila, a torsion‐like deformation of the cell occurs (cell chirality). Two myosin Is, Myo1D and Myo1C, are thought to be involved in this process, producing right‐handed and left‐handed cell chirality, respectively. A paper published in the May issue of this journal (Utsunomiya et al. (2024) Genes Cells 29: 380‐396, DOI: 10.1111/gtc.13110) reported that when these myosin Is were expressed in macrophages to observe their interactions with the membrane at the single‐molecule level, Myo1D exhibited mobility consistent with free diffusion, whereas Myo1C showed notably lower mobility. This picture, depicting two vortices in a strait, aptly illustrates their differences. Compared to the fast currents that produce the right‐handed vortex in the back, the currents of the left‐handed vortex in the foreground are docile. Designed by TRAIS Co., Ltd. (Kobe, Japan). [ABSTRACT FROM AUTHOR]

The NIR-activated bacteria-killing efficiencies of chiral CuS NPs depended on the excitation light polarization and the chiral configuration enhanced photothermal efficiency. Chiral CuS NPs which adsorb on or aggregate outside the bacteria or even enter the bacteria would increase the ambient temperature quickly under NIR illumination through the photothermal effect, which leads to the inactivation of proteins of bacteria. [Display omitted] • Chiral CuS nanoparticles showed enhanced NIR-activated bacteria-killing effect compared with achiral CuS nanoparticles under the same conditions. • These chiral CuS nanoparticles showed obvious chirality-related antibacterial effect. • Photothermal bacteria-killing tests of chiral CuS NPs "sealed" in PDMS demonstrated the individual influence of photothermal effect. As the drawbacks of antibiotics in treating bacterial infections emerged, physical methods such as near-infrared-activated (NIR-activated) bacterial killing, have attracted great interests for their advantages of no resistance, short action time and few side effects. In this manuscript, NIR-activated bacteria-killing performance of chiral copper sulphide nanoparticles (L-/ d -CuS NPs) was investigated using linearly polarized light (LPL) and circularly polarized light (CPL) as illumination sources, respectively. Chiral CuS NPs showed enhanced NIR-activated bacteria-killing effect compared with achiral CuS NPs under the same conditions. Moreover, these chiral CuS NPs showed obvious chirality-related antibacterial effect: the bacterial killing was more efficient under CPL activation, and L- and d -CuS NPs had higher antibacterial efficiency under left circularly polarized light (LCPL) and right circularly polarized light (RCPL), respectively. The possible mechanism of bacteria-killing performance for chiral CuS NPs was discussed in detailed. Photothermal bacteria-killing tests of chiral CuS NPs "sealed" in polydimethylsiloxane (PDMS) demonstrated the individual influence of photothermal effect. These observations in this paper could provide ideas for the potential applications of chiral nanostructures with enhanced photothermal effect in efficient bacterial killing. [ABSTRACT FROM AUTHOR]

Homochirality is an obvious feature of life on Earth. On the other hand, extraterrestrial samples contain largely racemic compounds. The same is true for any common organic synthesis. Therefore, it has been a perplexing puzzle for decades how these racemates could have formed enantiomerically enriched fractions as a basis for the origin of homochiral life forms. Numerous hypotheses have been put forward as to how preferentially homochiral molecules could have formed and accumulated on Earth. In this article, it is shown that homochirality of the abiotic organic pool at the time of formation of the first self-replicating molecules is not necessary and not even probable. It is proposed to abandon the notion of a molecular ensemble and to focus on the level of individual molecules. Although the formation of the first self-replicating, most likely homochiral molecule, is a seemingly improbable event, on a closer look, it is almost inevitable that some homochiral molecules have formed simply on a statistical basis. In this case, the non-selective leap to homochirality would be one of the first steps in chemical evolution directly out of a racemic "ocean". Moreover, most studies focus on the chirality of the primordial monomers with respect to an asymmetric carbon atom. However, any polymer with a minimal size that allows folding to a secondary structure would spontaneously lead to asymmetric higher structures (conformations). Most of the functions of these polymers would be influenced by this inherently asymmetric folding. Furthermore, a concept of physical compartmentalization based on rock nanopores in analogy to nanocavities of digital immunoassays is introduced to suggest that complex cell walls or membranes were also not required for the first steps of chemical evolution. To summarize, simple and universal mechanisms may have led to homochiral self-replicating systems in the context of chemical evolution. A homochiral monomer pool is deemed unnecessary and probably never existed on primordial Earth. [ABSTRACT FROM AUTHOR]

Various active materials exhibit strong spatio-temporal variability of their orientational order known as active turbulence, characterised by irregular and chaotic motion of topological defects, including colloidal suspensions, biofilaments, and bacterial colonies.In particular in three dimensions, it has not yet been explored how active turbulence responds to changes in material parameters and chirality.Here, we present a numerical study of three-dimensional (3D) active nematic turbulence, examining the influence of main material constants: (i) the flow-alignment viscosity, (ii) the magnitude and anisotropy of elastic deformation modes (elastic constants), and (iii) the chirality. Specifically, this main parameter space covers contractile or extensile, flow-aligning or flow tumbling, chiral or achiral elastically anisotropic active nematic fluids. The results are presented using time- and space-averaged fields of defect density and mean square velocity. The results also discuss defect density and mean square velocity as possible effective order parameters in chiral active nematics, distinguishing two chiral nematic states—active nematic blue phase and chiral active turbulence. This research contributes to the understanding of active turbulence, providing a numerical main phase space parameter sweep to help guide future experimental design and use of active materials. Active turbulence is a dynamic state of active nematics that is in three dimensions realized as a network of reconfiguring and proliferating disclination lines. This work explores the scaling properties of active turbulence with material constants and the chirality-driven transition from a chiral active turbulence to an active blue phase. [ABSTRACT FROM AUTHOR]

Chiral multiferroics offer remarkable capabilities for controlling quantum devices at multiple levels. However, these materials are rare due to the competing requirements of long-range orders and strict symmetry constraints. In this study, we present experimental evidence that the coexistence of ferroelectric, magnetic orders, and crystallographic chirality is achievable in hybrid organic-inorganic perovskites [(R/S)-β-methylphenethylamine]2CuCl4. By employing Landau symmetry mode analysis, we investigate the interplay between chirality and ferroic orders and propose a novel mechanism for chirality transfer in hybrid systems. This mechanism involves the coupling of non-chiral distortions, characterized by defining a pseudo-scalar quantity, ξ = p ⋅ r (p represents the ferroelectric displacement vector and r denotes the ferro-rotational vector), which distinguishes between (R)- and (S)-chirality based on its sign. Moreover, the reversal of this descriptor's sign can be associated with coordinated transitions in ferroelectric distortions, Jahn-Teller antiferro-distortions, and Dzyaloshinskii-Moriya vectors, indicating the mediating role of crystallographic chirality in magnetoelectric correlations. Chiral multiferroics are rare materials. Here the authors report that ferroelectric, magnetic orders, and chirality coexist in copper hybrid perovskites and reveal a hybrid-improper chiral transfer mechanism by defining a pseudo-scalar order parameter. [ABSTRACT FROM AUTHOR]

Chiral mono- and bis-(thio)urea supramolecular organocatalysts were studied in the enantioselective vinylogous addition reaction of 2-trimethylsilyloxyfuran (TMSOF) to carbonylic compounds; the corresponding chiral γ-hydroxymethyl-butenolides are obtained in good yields and with high enantiomeric excesses. The catalyst structure, as well as the reaction conditions, strongly influence the efficiency of the reaction. The conformational features of mono(thio)urea catalysts 2 and 3 and bis(thio)urea catalysts 7 and 8 were investigated by DFT calculations along with the structure of their complexes with benzaldehyde. Natural Bond Orbital (NBO) and Non-Covalent Interaction (NCI) calculations provided useful information concerning the activating H-bonding interactions in the complexes. [ABSTRACT FROM AUTHOR]

Tröger's base analogs (TBAs) and their derivatives are versatile, Λ-shaped, tetracyclic chiral building blocks utilized in numerous fields of research. Although various methods for the enantiopurification of TBAs have been demonstrated in the literature, none has achieved it with the use of metal–organic frameworks (MOFs). This investigation introduces a convenient and scalable method to obtain enantiopure TBAs with the formation and digestion of a chiral MOF composed of fully recoverable and non-hazardous starting materials, namely, cyclodextrin-based metal–organic framework (CD-MOF). [ABSTRACT FROM AUTHOR]

With this report, the space group of [ Z n (N a l) (D A C H) 2 ] C l is corrected ( N a l : nalidixic acid mono-anion; D A C H : diaminocyclohexane) from its wrong description in the literature. In the correct, non-centrosymmetric space group P 1 , the crystal structure is well ordered and the stereochemistry is correct. Crystallographic tools to recognize the correct symmetry are described. This work encourages experienced and inexperienced scientists to remain critical about the output of automatic, black-box crystallographic software. [ABSTRACT FROM AUTHOR]

The structure of skyrmion and spiral solutions, investigated within the phenomenological Dzyaloshinskii model of chiral magnets near the ordering temperatures, is characterized by the strong interplay between longitudinal and angular order parameters, which may be responsible for experimentally observed precursor effects. Within the precursor regions, additional effects, such as pressure, electric fields, chemical doping, uniaxial strains and/or magnetocrystalline anisotropies, modify the energetic landscape and may even lead to the stability of such exotic phases as a square staggered lattice of half-skyrmions, the internal structure of which employs the concept of the "soft" modulus and contains points with zero modulus value. Here, we additionally alter the stiffness of the magnetization modulus to favor one- and two-dimensional modulated states with large modulations of the order parameter magnitude. The computed phase diagram, which omits any additional effects, exhibits stability pockets with a square half-skyrmion lattice, a hexagonal skyrmion lattice with the magnetization in the center of the cells parallel to the applied magnetic field, and helicoids with propagation transverse to the field, i.e., those phases in which the notion of localized defects is replaced by the picture of a smooth but more complex tiling of space. We note that the results can be adapted to metallic glasses, in which the energy contributions are the same and originate from the inherent frustration in the models, and chiral liquid crystals with a different ratio of elastic constants. [ABSTRACT FROM AUTHOR]

Chirality constitutes an inherent attribute of nature. The catalytic asymmetric synthesis of molecules with central, axial, and helical chirality is a topic of intense interest and is becoming a mature field of research. However, due to the difficulty in synthesis and the lack of a prototype, less attention has been given to planar chirality arising from the destruction of symmetry on a single planar ring. Herein, we report the catalytic asymmetric synthesis of planar-chiral dianthranilides, a unique class of tub-shaped eight-membered cyclic dilactams. This protocol is enabled by cinchona alkaloid-catalyzed (dynamic) kinetic resolution. Under mild conditions, various C2- or C1-symmetric planar-chiral dianthranilides have been readily prepared in high yields with excellent enantioselectivity. These dianthranilides can serve as an addition to the family of planar-chiral molecules. Its synthetic value has been demonstrated by kinetic resolution of racemic amines via acyl transfer, enantiodivergent synthesis of the natural product eupolyphagin, and preliminary antitumor activity studies. Chirality has long fascinated chemists, but asymmetric synthesis has largely focused on central, axial, and helical chirality to date. Here, the authors synthesize dianthranilides with planar chirality, via cinchona alkaloid-catalyzed (dynamic) kinetic resolution. [ABSTRACT FROM AUTHOR]

Magnetic frustration, realized in the special geometrical arrangement of localized spins, often promotes topologically nontrivial spin textures in the real space and induces significantly large unconventional Hall responses. This spin Berry curvature effect in itinerant frustrated magnets mainly works with a static spin order, limiting the effective temperature range below the magnetic transition temperature and yielding the typical anomalous Hall conductivity below ~ 103 Ω−1cm−1. Here we show that an ultraclean triangular-lattice antiferromagnet PdCrO2 exhibits a large anomalous Hall conductivity up to ~ 106 Ω−1cm−1 in the paramagnetic state, which is maintained far above the Neel temperature (TN) up to ~ 4TN. The reported enhancement of anomalous Hall response above TN is attributed to the skew scattering of highly mobile Pd electrons to fluctuating but locally-correlated Cr spins with a finite spin chirality. Our findings point at an alternative route to realizing high-temperature giant anomalous Hall responses, exploiting magnetic frustration in the ultraclean regime. Magnetic frustration of spins often leads to nontrivial spin textures and anomalous Hall responses, but typically below the magnetic transition temperature. The authors observe a giant unconventional anomalous Hall conductivity in the triangularlattice antiferromagnet PdCrO2 well above its Neel temperature, attributed to spin cluster skew scattering. [ABSTRACT FROM AUTHOR]

In this study, the design and asymmetric synthesis of a series of chiral targets of orientational chirality were conducted by taking advantage of N-sulfinylimine-assisted nucleophilic addition and modified Sonogashira catalytic coupling systems. Orientational isomers were controlled completely using alkynyl/alkynyl levers [C(sp)-C(sp) axis] with absolute configuration assignment determined by X-ray structural analysis. The key structural element of the resulting orientational chirality is uniquely characterized by remote through-space blocking. Forty examples of multi-step synthesis were performed, with modest to good yields and excellent orientational selectivity. Several chiral orientational amino targets are attached with scaffolds of natural and medicinal products, showing potential pharmaceutical and medical applications in the future. [ABSTRACT FROM AUTHOR]

The development of turn-based inhibitors of protein–protein interactions has attracted considerable attention in medicinal chemistry. Our group has synthesized a series of peptides derived from an amino-functionalized ferrocene to investigate their potential to mimic protein turn structures. Detailed DFT and spectroscopic studies (IR, NMR, CD) have shown that, for peptides, the backbone chirality and bulkiness of the amino acid side chains determine the hydrogen-bond pattern, allowing tuning of the size of the preferred hydrogen-bonded ring in turn-folded structures. However, their biological potential is more dependent on their lipophilicity. In addition, our pioneering work on the chiroptical properties of aminoferrocene-containing peptides enables the correlation of their geometry with the sign of the CD signal in the absorption region of the ferrocene chromophore. These studies have opened up the possibility of using aminoferrocene and its derivatives as chirooptical probes for the determination of various chirality elements, such as the central chirality of amino acids and the helicity of peptide sequences. [ABSTRACT FROM AUTHOR]

Background. The present article investigates the reciprocal action of specific medium effects on electromagnetic waves propagation. The object of study is a moving dielectric, which at rest already demonstrate bianisotropic properties, i. e., it is a synthetic material, e. g., chiral media with Ω-particles. Bianisotropic material equations are the most general for describing the effects of electromagnetic waves interaction with complex medium. Studying and analyzing them is proving to be a notable scientific problem. Natural bianisotropy is a property of simple media under special conditions (state of motion, internal currents and diffusion processes), whereas artificial bianisotropy is an inherent property of the synthetic material itself (composite material, material with different metaparticles). Aim. The main goal of the work is to generalize the already available data. On it basis, then, obtain analytical expressions, which can be effectively used for the experiments designing, creating new computational techniques for solving direct and inverse electromagnetic diffraction problems. Methods. In this paper, analytical methods are applied to obtain the resulting close-form expressions. Results. Three classes of effects have been identified that have a significant reciprocal effect on each other: gyrotropy, spatial dispersion, and temporal dispersion. In this article it was shown that the gyrotropy of the medium has not only a simple additive effect, but under some, specific conditions, can be related to the system emergence. Conclusion. The reciprocal action of the spatial dispersion of the moving chiral medium, generally has different scales in range. Temporal dispersion was investigated, which does not have a simple additive property, because even an isotropic medium acquires fundamentally new material properties of bianisotropy when it moves.

Developing facile and direct synthesis routes for enantioselective construction of cyclic π-conjugated molecules is crucial. However, originate chirality from the distorted structure around heptagon-containing polyarenes is largely overlooked, the enantioselective construction of all-carbon heptagon-containing polyarenes remains a challenge. Herein, we present a highly enantioselective synthesis route for fabricating all carbon heptagon-containing polyarenes via palladium-catalyzed carbene-based cross–coupling of benzyl bromides and N-arylsulfonylhydrazones. A wide range of nonplanar, saddle-shaped tribenzocycloheptene derivatives are efficiently prepared in high yields with excellent enantioselectivities using this approach. In addition, stereochemical stability experiments show that these saddle-shaped tribenzocycloheptene derivatives have high inversion barriers. Developing facile and direct synthesis routes for enantioselective construction of cyclic π-conjugated molecules is crucial but the chirality orginiating from the distorted structure around heptagon-containing polyarenes is largely overlooked. Herein the authors present a highly enantioselective synthesis for fabrication of all carbon heptagon-containing polyarenes via palladium-catalyzed carbene-based cross–coupling of benzyl bromides and N-arylsulfonylhydrazones. [ABSTRACT FROM AUTHOR]

Carbon nanotubes (CNTs) are of interest in various industries owing to their high aspect ratio, electrical conductivity, and other properties. By maximizing the number of CNTs in their solvents or matrices, the electrical and mechanical performance in applications such as batteries, sensors, and transistors can be enhanced. However, the hydrophobicity of CNTs' surface induces aggregation that adversely impacts their performance. To overcome this obstacle, many researchers have been designing novel dispersants with performances exceeding that of existing commercial dispersants. This article reviews contemporary studies on CNT dispersants from 2015 to 2022, along with the comprehensive features of CNTs depending on their chirality, number of walls, synthesis methods, and functionalization. Studies of CNT dispersants are primarily organized according to whether aqueous or organic solvents are used. This review article provides a clear perspective of CNT dispersants development today and how to design new CNT dispersants depending on the solvents. A conclusion is given to identify major challenges to the implementation of CNT dispersion and an outlook on future avenues of research. [ABSTRACT FROM AUTHOR]

The contributions of magnetohydrodynamic (MHD) vortexes to chiral electrodeposition in a vertical magnetic field were theoretically examined based on the three-generation model of the 2D nucleus, 3D nucleus, and screw dislocation; for the vortexes to rotate in the second and third-generation, the kinematic viscosity must be at least 10−18 and 10−30 times lower than the ordinary value in the first generation, i.e., almost equal to zero. This implies that the ionic vacancy created on the electrode surface works as an atomic-scale lubricant. At the same time, the vortexes played three roles: promotion and suppression of nucleation, and transport of the chirality from the upper generation to the lower generation through precessional motion. Then, the rule of the chirality transfer was established, and finally, the relationship between the chiral activity and magnetic field was clarified in the presence and absence of chloride ions. [ABSTRACT FROM AUTHOR]

For radially extended Bessel modes, the helicity density distributions of magnetic fields associated with relativistic electron vortex beams are investigated for first time in the literature. The form of the distribution is defined by the electron beam's cylindrically symmetric density flux, which varies with the winding number ℓ and the electron spin. Different helicity distributions are obtained for different signs of the winding number ± ℓ , confirming the chiral nature of the magnetic fields associated with the electron vortex beam. The total current helicity for the spin-down state is smaller than that of the spin-up state. The different fields and helicities associated with opposite winding numbers and/or spin values will play an important role in the investigation of the interaction of relativistic electron vortices with matter and especially chiral matter. A comparison of the calculated quantities with the corresponding ones in the case of non-relativistic spin-polarized electron beams is performed. [ABSTRACT FROM AUTHOR]

The kagome metals AV3Sb5 (A = K, Rb, Cs) present an ideal sandbox to study the interrelation between multiple coexisting correlated phases such as charge order and superconductivity. So far, no consensus on the microscopic nature of these states has been reached as the proposals struggle to explain all their exotic physical properties. Among these, field-switchable electric magneto-chiral anisotropy (eMChA) in CsV3Sb5 provides intriguing evidence for a rewindable electronic chirality, yet the other family members have not been likewise investigated. Here, we present a comparative study of magneto-chiral transport between CsV3Sb5 and KV3Sb5. Despite their similar electronic structure, KV3Sb5 displays negligible eMChA, if any, and with no field switchability. This is in stark contrast to the non-saturating eMChA in CsV3Sb5 even in high fields up to 35 T. In light of their similar band structures, the stark difference in eMChA suggests its origin in the correlated states. Clearly, the V kagome nets alone are not sufficient to describe the physics and the interactions with their environment are crucial in determining the nature of their low-temperature state. [ABSTRACT FROM AUTHOR]

Recent years have seen rapid development of descriptor generation based on representation learning of extremely diverse molecules, especially those that apply natural language processing (NLP) models to SMILES, a literal representation of molecular structure. However, little research has been done on how these models understand chemical structure. To address this black box, we investigated the relationship between the learning progress of SMILES and chemical structure using a representative NLP model, the Transformer. We show that while the Transformer learns partial structures of molecules quickly, it requires extended training to understand overall structures. Consistently, the accuracy of molecular property predictions using descriptors generated from models at different learning steps was similar from the beginning to the end of training. Furthermore, we found that the Transformer requires particularly long training to learn chirality and sometimes stagnates with low performance due to misunderstanding of enantiomers. These findings are expected to deepen the understanding of NLP models in chemistry. There has been limited research on how NLP models comprehend diverse chemical structures despite its popularity. Here, the authors examine the learning process of Transformer for chemical structures and show inherent issues for chirality recognition. [ABSTRACT FROM AUTHOR]

Controlling chromophore chirality in three‐dimensional space is crucial for understanding the structure–chiroptical relationship. Such control enables the prediction of ideal materials for use in chiral photonic applications. In this study, optically active multipyrene systems are synthesized on peptoids. Pyrene‐based chiral submonomers, (S)‐ and (R)‐1‐pyrenylethylamine (s1pye and r1pye), are successfully incorporated into peptoids as the respective (S)‐ and (R)‐N‐(1‐pyrenylethyl)glycine (Ns1pye and Nr1pye) units. NMR spectroscopy revealed length‐ and N‐acetylation‐dependent conformational homogeneity enhancement in solution, stabilizing cis‐amides in Ns1pye‐containing peptoids. The X‐ray crystal structure of Ns1pye tetramer displayed a polyproline type‐I (PPI)‐like helix. All of the pyrene‐related absorptions are circular dichroism (CD) active, and the CD signal related to the long‐axis‐polarized transition increased with helical stabilization. Intramolecular excimer generation yielded significant circularly polarized luminescence (CPL) in the excimer emission region. Early‐stage peptoids emitted left‐handed CPL, but upon acquiring a PPI‐like helix character, CPL handedness became inverted. The CPL dissymmetry factor (glum) was comparable or superior (10−2) to that of chiral organic dyes (10−5–10−2). This new class of helical pyrene‐containing peptoids provides a CPL‐active intramolecular excimer, modulating optical activity through peptoid secondary structure homogeneity. [ABSTRACT FROM AUTHOR]

We study the Rényi entanglement entropies along the massless renormalisation group flow that connects the tricritical and critical Ising field theories. Similarly to the massive integrable field theories, we derive a set of bootstrap equations, from which we can analytically calculate the twist field form factors in a recursive way. Additionally, we also obtain them as a non-trivial 'roaming limit' of the sinh-Gordon theory. Then the Rényi entanglement entropies are obtained as expansions in terms of the form factors of these branch point twist fields. We find that the form factor expansion of the entanglement entropy along the flow organises in two different kind of terms. Those that couple particles with the same chirality, and reproduce the entropy of the infrared Ising theory, and those that couple particles with different chirality, which provide the ultraviolet contributions. The massless flow under study possesses a global ℤ2 spin-flip symmetry. We further consider the composite twist fields associated to this group, which enter in the study of the symmetry resolution of the entanglement. We derive analytical expressions for their form factors both from the bootstrap equations and from the roaming limit of the sinh-Gordon theory. [ABSTRACT FROM AUTHOR]

Light engineering of correlated states in topological materials provides a new avenue of achieving exotic topological phases inaccessible by conventional tuning methods. Here we demonstrate a light control of correlation gaps in a model charge-density-wave (CDW) and polaron insulator (TaSe4)2I recently predicted to be an axion insulator. Our ultrafast terahertz photocurrent spectroscopy reveals a two-step, non-thermal melting of polarons and electronic CDW gap via the fluence dependence of a longitudinal circular photogalvanic current. This helicity-dependent photocurrent reveals continuous ultrafast phase switches from the polaronic state to the CDW (axion) phase, and finally to a hidden Weyl phase as the pump fluence increases. Additional distinctive attributes aligning with the light-induced switches include: the mode-selective coupling of coherent phonons to the polaron and CDW modulation, and the emergence of a non-thermal chiral photocurrent above the pump threshold of CDW-related phonons. The demonstrated ultrafast chirality control of correlated topological states here holds large potentials for realizing axion electrodynamics and advancing quantum-computing applications. The charge-density-wave Weyl semimetal (TaSe4)2I is a candidate for an axion insulator, however it may be obscured by polaron physics. Here, using ultrafast terahertz photocurrent spectroscopy, the authors realize phase switches from the polaronic state, to the charge density wave phase, and to the Weyl phase. [ABSTRACT FROM AUTHOR]

In neurodegenerative diseases, polymorphism and supramolecular assembly of β-sheet amyloids are implicated in many different etiologies and may adopt either a left- or right-handed supramolecular chirality. Yet, the underlying principles of how sequence regulates supramolecular chirality remains unknown. Here, we characterize the sequence specificity of the central core of amyloid-β 42 and design derivatives which enable chirality inversion at biologically relevant temperatures. We further find that C-terminal modifications can tune the energy barrier of a left-to-right chiral inversion. Leveraging this design principle, we demonstrate how temperature-triggered chiral inversion of peptides hosting therapeutic payloads modulates the dosed release of an anticancer drug. These results suggest a generalizable approach for fine-tuning supramolecular chirality that can be applied in developing treatments to regulate amyloid morphology in neurodegeneration as well as in other disease states. Assembly of amyloids is important in neurodegenerative diseases, but there is limited understanding of how supramolecular chirality is controlled. Here, the authors report the design of peptide derivatives that allow chirality inversion at biologically relevant temperatures. [ABSTRACT FROM AUTHOR]

The construction of N–N axially chiral motifs is an important research topic, owing to their wide occurrence in natural products, pharmaceuticals and chiral ligands. One efficient method is the atroposelective dihydropyrimidin-4-one formation. We present herein a direct catalytic synthesis of N–N atropisomers with simultaneous creation of contiguous axial and central chirality by oxidative NHC (N-heterocyclic carbenes) catalyzed (3 + 3) cycloaddition. Using our method, we are able to synthesize structurally diverse N–N axially chiral pyrroles and indoles with vicinal central chirality or bearing a 2,3-dihydropyrimidin-4-one moiety in moderate to good yields and excellent enantioselectivities. Further synthetic transformations of the obtained axially chiral pyrroles and indoles derivative products are demonstrated. The reaction mechanism and the origin of enantioselectivity are understood through DFT calculations. N–N axially chiral motifs are of synthetic interest due to their presence in natural products, pharmaceuticals, and chiral ligands. Here, the authors develop a direct catalytic synthesis of N–N atropisomers with simultaneous creation of contiguous axial and central chirality by oxidative NHC catalyzed (3 + 3) cycloaddition. [ABSTRACT FROM AUTHOR]

A family of transition metal complexes of meso‐aryl‐2‐aza‐21‐carbaporphyrin (N‐confused porphyrin, NCP) derivatives acting as ortho‐metallating ligands for ruthenium(II), rhodium(III), and iridium(III) is synthesized and characterized by XRD, spectroscopic, and electrochemical methods. The chirality of these systems is shown by the separation of the enantiomers and analyzed by circular dichroism and DFT. A preliminary catalytic study indicates the activity of the iridium(III) ortho‐metallated complexes in the N‐heterocyclization of primary amines with diols. [ABSTRACT FROM AUTHOR]

Coalescence of [60]fullerenes potentially produces hypothetical nanocarbon assemblies with non-naturally occurring topologies. Since the discovery of [60]fullerene in 1985, coalesced [60]fullerene oligomers have only been observed as transient species by transmission electron microscopy during an oligomerization process under a high electron acceleration voltage. Herein, we showcase the rational synthesis of covalent assemblies consisting of inherently chiral open-[60]fullerenes. The crystallographic analyses unveiled double-caged structures of non-conjugated and conjugated inter-[60]fullerene hybrids, in which the two [60]fullerene cages are bounds to each other through a covalent linkage. The former one further assembles via a heterochiral recognition so that four carbon cages are arranged in a tetrahedral manner both in solution and solid state. Reflecting radially-conjugated double π-surface nature, the inter-[60]fullerene conjugate exhibits strong electronic communication in its reduced states, intense absorption behavior, and chiroptical activity with a dissymmetry factor of 0.21 (at 674 nm) which breaks the record for known chiral organic molecules. Inter-fullerene conjugates are non-naturally occurring carbon allotropes. Here the authors report on the chemical synthesis and solid-state structure of three inter-[60]fullerene hybrids with inherent chirality. [ABSTRACT FROM AUTHOR]

Recently, the formation of chiral materials by the self-organization of achiral small molecules has attracted much attention. How can we obtain chirality without a chiral source? Interesting approaches, such as mechanical rotation, circularly polarized light, and asymmetric reaction fields, have been used. We describe recent research developments in supramolecular chirality in liquid crystals, focusing primarily on our group's experimental results. We present the following concepts in this review. Spontaneous mirror symmetry breaking in self-assembled achiral trimers induces supramolecular chirality in the soft crystalline phase. Two kinds of domains with opposite handedness exist in non-equal populations. The dominant domain is amplified to produce a homochiral state. Chirality is transferred to a polymer film during the polymerization of achiral monomers by using the homochiral state as a template. Finally, we discuss how the concepts obtained from this liquid crystal research relate to the origin of homochirality in life. [ABSTRACT FROM AUTHOR]

The streamlines of the energy flux (Poynting vectors) and chirality flux as well as the intensity of the electric field around various plasmonic nanostructures (nanocube, nanocuboid, nanotriangle, hexagonal nanoplate and bowtie nanoantenna) induced by a circularly polarized (CP) or linearly polarized (LP) light were studied theoretically. The boundary element method combined with the method of moment was used to solve a set of surface integral equations, based on the Stratton–Chu formulation, for analyzing the highly distorted electromagnetic (EM) field in the proximity of these nanostructures. We discovered that the winding behavior of these streamlines exhibits versatility for various modes of the surface plasmon resonance of different nanostructures. Recently, using plasmonic nanostructures to facilitate a photochemical reaction has gained significant attention, where the hot carriers (electrons) play important roles. Our findings reveal a connection between the flow pattern of energy flux and the morphology of the photochemical deposition around various plasmonic nanostructures irradiated by a CP light. For example, numerical results exhibit vertically helical streamlines of the Poynting vector around an Au nanocube and transversely twisted-roll streamlines around a nanocuboid. Additionally, the behaviors of the winding energy and chirality fluxes at the gap and corners of a plasmonic bowtie nanoantenna, implying a highly twisted EM field, depend on the polarization of the incident LP light. Our analysis of the streamlines of the Poynting vector and chirality flux offers an insight into the formation of plasmon-enhanced photocatalysis. [ABSTRACT FROM AUTHOR]

The dielectric properties of synclinic (ferroelectric SmC*) and anticlinic (antiferroelectric SmCA*) smectic liquid crystals composed of molecules of one chiral version (S) are presented and compared with properties of racemic mixture (R, S), showing SmC and SmCA phases. The racemic mixture completely loses its ferroelectric and antiferroelectric properties. Surprisingly, only one dielectric mode observed in the antiferroelectric SmCA* phase disappeared in the dielectric response of the racemic SmCA phase. Additionally, we observed that in the SmC phase, seen in the racemic mixture, the weak dielectric mode (named the X mode) is detected, which seems to be the continuation of the PL mode existing in the racemic SmCA. Moreover, this mode in the racemic SmC has nothing to do with the Goldstone mode, typical for the SmC* phase. This paper describes in detail the real and imaginary parts of dielectric permittivity in smectic phases for the enantiomer and racemate with and without a DC field, compares the properties of the X and PL modes, and discusses the full scheme of dielectric modes in enantiomer and racemate.

This paper explores and revisits in detail the formation and characterization of sugar-based aminonitriles, whose ultimate origin can be traced to the interaction of biomolecules with cyanide. Although the synthesis and spectroscopic data of 2-amino-aldononitriles were reported long ago, there are both contradictory and confusing results among the published data. We have now addressed this concern through an exhaustive structural elucidation of acylated 2-amino- and 2-alkyl(aryl)amino-2-deoxyaldonitriles using mass spectrometry and FT-IR, FT–Raman, and NMR spectroscopies. Several structures could be unambiguously determined through single-crystal X-ray diffraction, which allowed us to correct other misassignments. Moreover, this study unveils how steric and electronic effects influence the acylation outcome of the amino, (alkyl, aryl)amino, or acetamido group at C-2. The chirality at the latter, which was assigned tentatively through optical rotation correlation, and hence the preferential threo stereochemistry generated during the cyanohydrin synthesis of 2-amino-2-deoxy aldononitriles have now been established with confidence.

Humans always identify persons through their characteristics, salient attributes, and these attributes' locations on the body. Most person re-identification methods focus on global and local features corresponding to the former two discriminations, cropping person images into horizontal strips to obtain coarse locations of body parts. However, discriminative clues corresponding to location differences cannot be discovered, so persons with similar appearances are often confused because of their alike components. To address the above problem, we introduce pixel-wise relative positions for the invariance of their orientations in viewpoint changes. To cope with the scale change of relative position, we combine relative positions with self-attention modules that perform on multi-level features. Moreover, in the data augmentation stage, mirrored images are given new labels due to the conversion of the relative position along a horizontal orientation and change in visual chirality. Extensive experiments on four challenging benchmarks demonstrate that the proposed approach shows its superiority and effectiveness in discovering discriminating features. [ABSTRACT FROM AUTHOR]