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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]

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]

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]

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]

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]

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]

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]