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Protein misfolding and amyloid formation are implicated in the protein dysfunction, but the underlying mechanism remains to be clarified due to the lack of effective tools for detecting the transient intermediates. Sum frequency generation vibrational spectroscopy (SFG‐VS) has emerged as a powerful tool for identifying the structure and dynamics of proteins at the interfaces. In this review, we summarize recent SFG‐VS studies on the structure and dynamics of membrane‐bound proteins during misfolding processes. This paper first introduces the methods for determining the secondary structure of interfacial proteins: combining chiral and achiral spectra of amide A and amide I bands and combining amide I, amide II, and amide III spectral features. To demonstrate the ability of SFG‐VS in investigating the interfacial protein misfolding and amyloid formation, studies on the interactions between different peptides/proteins (islet amyloid polypeptide, amyloid β, prion protein, fused in sarcoma protein, hen egg‐white lysozyme, fusing fusion peptide, class I hydrophobin SC3 and class II hydrophobin HFBI) and surfaces such as lipid membranes are discussed. These molecular‐level studies revealed that SFG‐VS can provide a unique understanding of the mechanism of interfacial protein misfolding and amyloid formation in real time, in situ and without any exogenous labeling. [ABSTRACT FROM AUTHOR]

Chiroptical response, demonstrating chiral interaction between optical vortex and chiral structure, plays an important role in variety of fields like optics and material science. However, the flexibility and efficiency of chiral structure fabrication are limited due to mask requirement and a point‐by‐point constructing strategy. In this paper, a novel chiral lithography method is proposed that utilizes optical vortex phase beam shaping to achieve chiral structure processing with high efficiency and flexibility. By programming topological charges of the vortex phase, chiral structures with adjustable appearance, rotation, and chirality can be produced using femtosecond laser single pulse exposure. Transmittance measurements of fabricated chiral structures array confirm a 66% helical dichroism that is predicted by simulation. Moreover, with the aid of convolutional neural networks (CNN), an accuracy of 98% in Orbital Angular Momentum (OAM) recognition can be achieved. This chiral lithography method provides an alternative for chiral structure fabrication and holds promise in the development of chiral optics, optical communications, and next‐generation optical devices. [ABSTRACT FROM AUTHOR]

Fundamental studies of the interaction of chiral light with chiral matter are important for the development of techniques that allow handedness‐selective optical detection of chiral organic molecules. One approach to achieve this goal is the creation of a Fabry–Pérot cavity that supports eigenmodes with a desired electromagnetic handedness. This paper theoretically studies chiral Fabry–Pérot cavities with mirrors comprising 1D photonic crystal slabs made of van der Waals As2S3, a material with one of the highest known in‐plane anisotropies. By utilizing the anisotropy provided by As2S3, Fabry–Pérot cavities with constitutional and configurational chiralities are designed. It is demonstrated that in cavities with constitutional chirality, electromagnetic modes of left or right handedness exist due to the chirality of both mirrors, often referred to as handedness preserving mirrors in the literature. At the same time, cavities with configurational chirality support modes of both handednesses due to the chiral morphology of the entire structure, set by the twist angle between the optical axes of the upper and lower non‐chiral anisotropic mirrors. The developed chiral Fabry–Pérot cavities can be tuned to any distance between the mirrors by properly twisting them, making such systems a prospective platform for the coupling of chiral light with chiral matter. [ABSTRACT FROM AUTHOR]

The use of hierarchically structured materials as catalysts has been finding increasing application in the past years. For these catalytic systems, not only the nano‐scale matters: a high degree of order across multiple length scales, along with its control and analytical assessment, is of paramount importance to obtain innovative properties that can find application in catalysis. Most reviews dealing with hierarchically structured materials are concerned with the "bottom‐up" transfer of structural information along the different length scales, with special emphasis on the transmission of chirality. Due to their mesoscale size together with their complex behaviour, these systems are often susceptible to feel the effects of macroscopic forces, that can exert a "top‐down" control of their catalytic properties, so that an external stimulus, acting at the level of the supramolecular architecture of the catalyst, can ultimately determine the outcome of the catalyzed reaction at the molecular level. We review in this paper some recent reports that deal with the experimental implementation of this concept, either by using a mechanical force in a full range direct transmission to the reaction coordinate, or by means of a stepwise relay transmission from the macroscopic level (purely supramolecular chirality) to the nanoscopic one. We focus in this review on these multi‐length scale communication control effects, identifying the different mechanisms that are affecting the catalytic activity. [ABSTRACT FROM AUTHOR]

The reaction of trans‐[Pt(DMSO)2MeCl] with 2‐alkylsubstituted pyridines pyR affords a series of complexes of the type [Pt(pyR)(DMSO)MeCl]. These complexes are rare examples of organometallic square‐planar complexes having four different ligands. Of the three possible geometric isomers, only the trans(N,S)‐[Pt(pyR)(DMSO)MeCl] was observed in solution and isolated in the solid state. However, the lack of chirality typical to square planar geometry can be resolved in several ways one of which is described in this paper. 1H NMR studies reveal diastereotopicity of the DMSO methyls, as well as the CH2 protons in the ethyl‐ and neopentyl‐pyridine complexes and the methyls in the isopropyl‐pyridine derivative. This observation can be ascribed to restricted rotations around the Pt−N bond, thus resulting in the presence of planar chirality for these complexes. Additionally, large downfield shifts in the 1H NMR spectra of the α C−H protons in the pyridine substituents suggested the presence of Pt⋯H−C interactions, confirmed via single crystal X‐ray studies in the case of the isopropyl complex [Pt(pyip)(DMSO)MeCl] (4), which shows an apical Pt⋯H interaction with a short 2.585 Å distance. DFT calculations shed light into the stability of these complexes and the influence of the pyridine‐substituent on their chiral configuration. [ABSTRACT FROM AUTHOR]

An elliptical chiral split‐ring‐resonator‐based bilayer thin metasurface is introduced in this paper. The proposed metasurface realizes strong electromagnetic (EM) activity with asymmetric transmission in the K‐band of the microwave regime. The efficiency is more than 80% over a range of frequencies from 18.6 to 20.8 GHz. Angular stability up to 60° makes the structure robust for practical applications. The structure also exhibits a negative refractive index for circularly polarized wave due to the strong chirality factor. Polarization azimuth rotation angle of 90° and ellipticity of 0° reveal the pure EM/optical activity. Furthermore, the simulation and measured results also affirmed orthogonal pure linear polarization transformation. The proposed chiral metasurface finds applications in radar and satellite belonging to K‐band. [ABSTRACT FROM AUTHOR]

In this paper, an ultra‐wideband chirality selective metastructure absorber is proposed that enables differential absorption and reflection of circularly polarized waves in the terahertz (THz) range. The structure achieves circular dichroism (CD) by using asymmetrically split metal rings as fundamental meta‐atoms. Most critically, the high impedance surface and air‐resonant cavities are inserted separately in the meta‐atoms and dielectric substrate to enhance CD and broaden the bandwidth of absorption. The metastructure absorber can achieve more than 90% absorption of right circularly polarized waves at 0.675–1.244 THz, and it can maintain more than 90% reflection of left circularly polarized waves at 0.607–1.229 THz without changing the direction of rotation. Besides, its CD can reach more than 80% at 0.687–1.213 THz with a relative bandwidth of 55.3%. Spin‐selective absorption, which is closely related to breaking chiral symmetry, is investigated through power loss distribution, wide‐angle incidence, and scan parameter optimization. The proposed strategy is further validated in the THz band, and the polarization selection and manipulation techniques can be applied to chiral sensing/radio‐thermometry, circular polarization detectors/lasers, and molecular spectroscopy. [ABSTRACT FROM AUTHOR]

Recently, 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. [ABSTRACT FROM AUTHOR]

The recently discovered ferroelectric nematic (NF) liquid crystals (LCs) with over 0.04 C m−2 ferroelectric polarization and 104 relative dielectric constants, coupled with sub‐millisecond switching, offer potential applications in high‐power super capacitors and low voltage driven fast electro‐optical devices. This paper presents electrical, optical, and electro‐optical studies of a ferroelectric nematic LC material doped with commercially available chiral dopants. While the NF phase of the undoped LC is only monotropic, the chiral NF phase is enantiotropic, indicating a chirality induced stabilization of the polar nematic order. Compared to undoped NF material, a remarkable improvement of the electro‐optical switching time is demonstrated in the chiral doped materials. The color of the chiral mixtures that exhibit a selective reflection of visible light in the chiral NF phase, can be reversibly tuned by 0.02–0.1 V µm−1 in‐plane electric fields, which are much smaller than typically required in full‐color cholesteric LC displays and do not require complicated driving scheme. The fast switchable reflection color at low fields has potential applications for LC displays without backlight, smart windows, shutters, and e‐papers. [ABSTRACT FROM AUTHOR]

This paper presents an all‐dielectric chiral metasurface composed of an array of two‐layer distorted square structures with nanoholes. This metasurface can simultaneously generate dual‐band opposite chiral responses, which can be attributed to the bound states in the continuum (BICs) and the distorted chiral structure. By combining the BICs with chirality, a dual‐band chiral nonlinear metasurface and a chiral‐sensing method are proposed. The simulated results show that the third harmonic generation (THG) conversion efficiency can reach the order of 10−4 for two peaks with a peak‐pump intensity of approximately 5.3 GW cm−2 in the near‐infrared region. Moreover, the third‐harmonic circular dichroism for each peak can reach up to 0.99 and ‐0.94, respectively. Furthermore, it is theoretically demonstrated that this metasurface can be used for chiral sensing with high sensitivities. These results provide new insights for linear and nonlinear spin‐dependent applications. [ABSTRACT FROM AUTHOR]

Chirality has become an important research subject. The research areas associated with chirality are under substantial development. Meanwhile, graphene is a rapidly growing star material and has hard‐wired into diverse disciplines. Rational combination of graphene and chirality undoubtedly creates unprecedented functional materials and may also lead to great findings. This hypothesis has been clearly justified by the sizable number of studies. Unfortunately, there has not been any previous review paper summarizing the scattered studies and advancements on this topic so far. This overview paper attempts to review the progress made in chiral materials developed from graphene and their derivatives, with the hope of providing a systemic knowledge about the construction of chiral graphenes and chiral applications thereof. Recently emerging directions, existing challenges, and future perspectives are also presented. It is hoped this paper will arouse more interest and promote further faster progress in these significant research areas. [ABSTRACT FROM AUTHOR]

Comprehensive Summary The 21st century has witnessed a continuous evolution in the development of boron‐stereogenic chemistry. Since the 1990s, various innovations for the synthesis of tetracoordinate boron‐stereogenic compounds, which exhibited great potential applications, have been demonstrated by synthetic chemists. This paper reviews the significant progress and recent advances towards the assembly of enantioenriched boron‐stereogenic compounds, and hopes to shed light on new perspectives and inspire further research in this emerging field. [ABSTRACT FROM AUTHOR]

Deep understanding of structure–property relationship between packing of chiral building units and their chiroptical behaviors would significantly facilitate the rational design and fabrication of the emerging chiroptical materials such as circularly polarized luminescence (CPL) emissive materials. In this paper, we unveil the universal existence of supramolecular tilt helical superstructures in self‐assembled π‐conjugated amino acid derivatives. A series of coded amino acid methyl esters were conjugated to anthracene segments at N‐terminus, which afforded 21 and 31 symmetry supramolecular tilt chirality in solid‐states. Helical assemblies enabled diversified Cotton effects and CPL performances, which were in accordance with the tilted chirality between anthracene segments. Such correlation shows fine universality, whereby the chiroptical prediction could be realized. Furthermore, on top of charge‐transfer complexation, manipulation of CPL emission colors and handedness were realized. [ABSTRACT FROM AUTHOR]

This paper describes the syntheses of [2]rotaxanes comprising 23‐ and 26‐membered biphenyl crown ethers as the macrocyclic components and secondary ammonium ions as the dumbbell‐shaped components, and the locking of the dynamic axial chirality of the biphenyl moieties in these structures. Chiral high‐performance liquid chromatography (HPLC) revealed that our [2]rotaxane featuring the 26‐membered crown ether racemized at room temperature, but the racemization of the [2]rotaxane featuring the 23‐membered crown ether did not proceed at room temperature over a period of three days. After separation of the enantiomers of the [2]rotaxane incorporating the 23‐membered crown ether through chiral HPLC, we studied its racemization at elevated temperature. The rate of stereoinversion in dimethylsulfoxide (a polar solvent) was faster than that in o‐dichlorobenzene (a nonpolar solvent), and herein we discuss these kinetic parameters. [ABSTRACT FROM AUTHOR]

In common with other hindered structures containing two aromatic rings linked by a short tether, diarylamines may exhibit atropisomerism (chirality due to restricted rotation). Previous examples have principally been tertiary amines, especially those with cyclic scaffolds. Little is known of the structural requirement for atropisomerism in structurally simpler secondary and acyclic diarylamines. In this paper we describe a systematic study of a series of acyclic secondary diarylamines, and we quantify the degree of steric hindrance in the ortho positions that is required for atropisomerism to result. Through a detailed experimental and computational analysis, the role of each ortho‐substituent on the mechanism and rate of conformational interconversion is rationalised. We also present a simple predictive model for the design of configurationally stable secondary diarylamines. [ABSTRACT FROM AUTHOR]

In common with other hindered structures containing two aromatic rings linked by a short tether, diarylamines may exhibit atropisomerism (chirality due to restricted rotation). Previous examples have principally been tertiary amines, especially those with cyclic scaffolds. Little is known of the structural requirement for atropisomerism in structurally simpler secondary and acyclic diarylamines. In this paper we describe a systematic study of a series of acyclic secondary diarylamines, and we quantify the degree of steric hindrance in the ortho positions that is required for atropisomerism to result. Through a detailed experimental and computational analysis, the role of each ortho‐substituent on the mechanism and rate of conformational interconversion is rationalised. We also present a simple predictive model for the design of configurationally stable secondary diarylamines. [ABSTRACT FROM AUTHOR]

Supramolecular capsules can be used to change the activity and selectivity of a catalyst through the influence of the second coordination sphere, reminiscent of how enzymes control the selectivity of their processes. In enzymes, this approach is used to also control the enantioselectivity of reactions in which the active catalytic site is often not chiral but the second coordination sphere is. We are interested in the possibility to generate a chiral second coordination sphere around an otherwise achiral transition metal complex for asymmetric catalysis. In this paper we show that the ligand template approach can be used to generate a chiral second coordination sphere around a rhodium complex, which is used in asymmetric hydroformylation. [ABSTRACT FROM AUTHOR]

The detection and separation of medetomidine enantiomers from the complex biological matrices poses a great analytical challenge, especially in the field of forensic toxicology and pharmacology. Couple of researchers reported resolution of medetomidine using protein‐based chiral columns, but the reported method is quiet challenging and tedious to be employed for routine analysis. This research paper reported a method that enables the enantio‐separation of medetomidine by using polysaccharide cellulose chiral column. The use of chiralcel OJ‐3R column was found to have the highest potential for successful chiral resolution. Ammonium hydrogen carbonate was the ideal buffer salt for chiral liquid chromatography (LC) with electrospray ionization (ESI)+ mass spectrometry (MS) detection for the successful separation and detection of racemic compound. The method was linear over the range of 0 to 20 ng/mL in equine plasma and the inter‐day precisions of levomedetomidine, dexmedetomidine were 1.36% and 1.89%, respectively. The accuracy of levomedetomidine was in the range of 99.25% to 101.57% and that for dexmedetomidine was 99.17% to 100.99%. The limits of quantification for both isomers were 0.2 ng/mL. Recovery and matrix effect on the analytes were also evaluated. Under the optimized conditions, the validated method can be adapted for the identification and resolution of the medetomidine enantiomers in different matrices used for drug testing and analysis. [ABSTRACT FROM AUTHOR]

CNFET devices are preferred over CMOS devices for designing high‐speed digital circuits. This paper introduces a new technique Dual Chirality High‐speed Domino Logic (DCHSDL) for implementing low power and high‐speed domino circuits in CNFET technology. Simulations are carried out for 32 nm Stanford CNFET model in HSPICE for 2, 4, 8 and 16 input domino OR gates at a clock frequency of 200 MHz on a DC supply voltage of 0.9 V. The proposed domino technique shows maximum power reduction of 82.55% and maximum delay reduction of 57.97% compared to CPVT technique in CNFET technology at a frequency of 200 MHz. The proposed circuit shows maximum power reduction of 97.90% compared to its analogous circuit in CMOS technology for a 2‐input domino OR gate. The proposed technique shows maximum improvement of 1.05× to 1.63× in unity noise gain (UNG) compared to various existing techniques in CNFET technology at a frequency of 200 MHz. The 1‐bit Full Adder designed using the proposed technique shows a power reduction of 16.91% and a delay reduction of 23.64% compared to standard FDL 1‐bit Full Adder. [ABSTRACT FROM AUTHOR]

This paper describes the first diastereoselective synthesis of cyclic α‐aminophosphonic and α‐amino phosphonic acids from glycyl‐l‐proline 2,5‐diketopiperazine (S)‐6 prepared according to the usual peptide coupling procedures. The highlights of this contribution is the chemoselective reduction of the carbamate‐imide activated carbonyl group in the N‐Boc 2,5‐diketopiperazine (S)‐11 to generate the unstable hemiaminals (1R,8aS)‐12 and (1S,8aS)‐13, followed by the highly diastereoselective nucleophilic addition of trimethyl phosphite or dimethyl phenylphosphonite to the chiral carbenium ion (S)‐5. Acid hydrolysis of the phosphonate and phosphinate functionalities with simultaneous cleavage of the tert‐butyl carbamate protecting group led to the target compounds. The high diastereoselectivity in the nucleophilic addition of trivalent phosphorus to the chiral carbenium ion (S)‐5 is in agreement with our precedent reports. [ABSTRACT FROM AUTHOR]

Based on a CSD search, a meta‐analysis of 1179 structures of 19 natural amino acids H3NCαH(R)C′(O)O and their derivatives H3NCαH(R)C′(O)O(H/R/M), protonated, esterified, or coordinated at the carboxylic group, shows that the chirality chain with its two steps, established in the preceding paper for alanine, can be extended to natural amino acids. High diastereoselectivities are observed in the induction from the L configuration at Cα to the −ψ and +ψ conformations, which in turn distort the planar carboxylic group CαC′(Ocis)Otrans to asymmetric flat tetrahedra, showing that the chirality chain is an integral part of natural amino acids. [ABSTRACT FROM AUTHOR]

In a paper addressing the problem that the majority of chiral compounds crystallize as racemates instead of conglomerates, Jack Dunitz coined the expression 'Wallach's Rule'. The paper gives credit to Wallach's publication in Liebigs Annalen der Chemie in 1895, in which, among other work, a comparison of crystal density of racemates and their homochiral analogues was reported. Of the nine compounds investigated, eight showed higher densities for the racemates. Although Wallach was the only author of the Annalen paper, it was not Otto Wallach, but Theodore Liebisch, Wallach's colleague from the mineralogy institute in Göttingen at that time, who performed the experiments and reported these results. Short overviews about the CVs of the contemporaries Wallach and Liebisch, as well as Liebisch's postdoc Sommerfeld, are presented. It is discussed whether Wallach or Liebisch had the idea to study crystal densities and which one of the two scientists should be properly credited with proposing 'Wallach′s Rule'. [ABSTRACT FROM AUTHOR]

Two independent statistical models for evaluating the certainties of configurational assignments of compounds based on nuclear magnetic resonance (NMR) data are evaluated and compared. Both methods yield weights or probabilities with which two or more structure models (constitutional or configurational isomers or even conformers) could be differentiated based on experimental parameters. Although this paper focusses on the use of residual dipolar couplings (RDCs) for the differentiation of diastereomers, the concept can be expanded to any set of experimental NMR‐derived parameters. It is demonstrated that highly reliable configurational assignments crucially must depend on thorough statistical analysis, which is frequently neglected in the literature. [ABSTRACT FROM AUTHOR]

This paper describes the synthesis and characterization of 21 chiral monodentate ligands L, assembled of three building blocks utilizing amide bonds: a metal binding triphenylphosphine, a chiral cyclic diamine and an additional substituent for fine‐tuning the steric and/or electronic properties. Cis square‐planar metal complexes of RhI and PtII with ML2 stoichiometry have been prepared and characterized by spectroscopic methods (NMR, IR, UV‐Vis, CD) and DFT calculations. A key feature of the metal complexes is a prochiral metal coordination sphere and "backdoor induction" of chirality from a distant chiral source via an outer‐coordination sphere, well‐defined by aromatic stacking and hydrogen‐bonding. The rhodium complexes were used as catalysts in asymmetric hydrogenation of α,β‐dehydroamino acids with excellent yield and selectivity (up to 97 % ee), strongly supporting the "backdoor induction" hypothesis. Chiral information is transmitted from a distant chiral source to the prochiral coordination sphere by means of noncovalent interactions, resulting in up to 97 % ee in asymmetric hydrogenations. [ABSTRACT FROM AUTHOR]

Supramolecular structures of organic molecules on planar nanocarbon surfaces, such as highly oriented pyrolytic graphite (HOPG), have been extensively studied and the factors that control them are generally well‐established. In contrast, the properties of supramolecular structures on curved nanocarbon surfaces like carbon nanotubes remain challenging to predict and/or to understand. This paper reports an investigation into the first study of the supramolecular structures of 5,15‐bisdodecylporphyrin (C12P) on chiral, concentrated single‐walled carbon nanotubes (SWNTs; with right‐handed helix P‐ and left‐handed helix M‐) surfaces using STM. Furthermore, the study is the first of its kind to experimentally assign the absolute‐handedness chirality of SWNTs, as well as to understand their effect on the supramolecular structures of organic molecules on their surfaces. Interestingly, these SWNT enantiomers resulted in supramolecular structures of opposite chirality based on the handedness chirality. With molecular modelling, we predicted the absolute‐handedness chirality of SWNTs, before demonstrating this experimentally. By using the STM imaging technique, the single‐walled carbon nanotube (SWNT) absolute‐handedness of chirality has been experimentally investigated using supramolecular structures of porphyrin derivatives (C12P). Two opposite chiral supramolecular structures have been observed based on the SWNT enantiomers handedness of chirality (see figure). [ABSTRACT FROM AUTHOR]

The separation of chiral compounds is an interesting and important topic of research because these compounds are involved in some biological processes, fundamentally in human health. Among the various application fields where enantiomers are remarkable, drug analysis has to be considered. Most of the drugs contain enantiomers and very often one of the two isomers could be pharmacologically more active or even dangerous. Therefore, the separation of these compounds is very important. Among the different analytical techniques usually employed, capillary electrochromatography has demonstrated great capability in enantiomers resolution. The great potential of this electromigration technique stands mainly in its high efficiency due to the use of an electrosmotic flow (flat flow profile) and on the high selectivity because of the use of a stationary phase. Chiral separation can be obtained utilizing several chiral stationary phases including a polysaccharide derivative. The aim of this review paper is to summarize the main features of capillary electrochromatography and polysaccharide derivatives of chiral stationary phase. It also report examples of practical applications utilizing this approach. [ABSTRACT FROM AUTHOR]

Chiral polymers and chiral polymeric particles have emerged as a new and exciting field of research in recent years mainly due to their possibly applications in chiral chemistry. This paper reviews the present state of the art regarding production techniques for the synthesis and applications of chiral polymeric particles. The main methods for preparing of chiral polymeric particles such as: direct polymerization, emulsion, precipitation, and suspension polymerization of chiral monomers, are reviewed. Moreover, in this article we also present the use of chiral polymers as chiral templates for the synthesis of chiral mesoporous materials. In this review we highlighted the properties and parameters involved in the preparation of these chiral polymeric materials. The present review focuses mainly on the use of chiral polymer and chiral polymeric particles for enantioselective crystallization and enantioseparation. References of the most relevant literature published by various research groups are provided. Anyway, it is clear that chiral polymeric particles are a distinctive type of chiral nanomaterials that can find many new application in other fields like, chiral drug delivery systems, enantioselective catalysis. We hope that this review article will inspired new researchers in this field and will boost the research dealing on chiral polymeric particles especially in their implementation in new areas in chiral chemistry. [ABSTRACT FROM AUTHOR]

Abstract: This paper describes the peculiar co‐assembly supramolecular polymerization behavior of triphenylamine trisamide derivatives with d‐alanine (T‐ala) or glycine (T‐gly) moieties. Concentration and temperature‐dependent circular dichroism (CD) spectroscopy revealed that the heating curves of co‐assemblies obtained at various molar ratios of T‐ala to T‐gly exhibited two distinct transition temperatures. The first transition was due to the transformation from coiled helical bundles to single helical fibers without handedness. The second was due to a change from typical elongation to nucleation. These phenomena were confirmed by solvent‐dependent decoiling of coiled helical structures and concentration‐dependent morphological analysis. The two transitioning temperatures were dependent on the concentration of T‐ala in the co‐assemblies, suggesting that T‐ala concentration plays an important role in the formation of coiled helical bundles. Our study demonstrated the first observation of two distinct transition temperatures in supramolecular polymers. [ABSTRACT FROM AUTHOR]

The paper moves from a technological process developed in previous works to produce chiral honeycombs made of thin composite laminates. Such approach is applied in this work to manufacture the morphing ribs for a variable camber wing-box. The specifications for such components are obtained by developing a finite element model of a demonstrator, which is designed taking into account aeroelastic performances, structural, and technological issues. In the first part of the paper, the design of such a demonstrator is presented and the role of composite chiral ribs with auxetic behavior is outlined. Production, testing, and numerical studies of manufacturing trials are performed to assess the technological process applied to small-sized chiral units made of different materials, to investigate their mechanical properties, and to validate a numerical approach for design and analysis. A complete chiral composite rib is then produced and tests are carried out to verify the overall structural response and to validate the numerical approach. [ABSTRACT FROM AUTHOR]

In a recent paper [ Huang, Gog, Kim, Kasman, Said, Casa, Wieczorek, Hönnicke & Assoufid (2018). J. Appl. Cryst.51, 140–147], a description of the structure of quartz was given that is incorrect. There is a long history of such errors in publications describing the quartz structure. This was fully and correctly discussed in 1978 [ Donnay & Le Page (1978). Acta Cryst. A34, 584–594], and yet these errors still persist. In the present paper the description by Huang et al. is corrected and the seminal work of Donnay and Le Page revisited. [ABSTRACT FROM AUTHOR]

In this paper, we have studied the chiroptical properties of a family of o-oligo(phenyleneethynylene) ( o-OPE) derivatives with different steric hindrance. Experimental results show high dissymmetry factors (gabs and glum up to 1.1 × 10−2) and very similar electronic circular dichroism (ECD) and circularly polarized luminescence (CPL) for all the derivatives that make this basic o-OPE scaffold a robust pure organic emitter. Vibrational circular dichroism spectra are used to characterize conformational properties in solution. Density functional theory and time-dependent density functional theory calculations support experimental results also proving that ECD and CPL are almost exclusively linked to helical moiety and not to size or conformation of substituents. As chiroptical properties of these emitters are independent of substituents, this OPE scaffold can be used as basic skeleton for the design of sensing probes with high CPL efficiencies. [ABSTRACT FROM AUTHOR]

Chiral nematic mesoporous organosilica (CNMO) films are functionalized with a mixture of hydrophobic silanes and spiropyran compounds to create freestanding photochromic films that can be used for reversible photo­patterning. The mesoporosity and interconnected pore structure of the films imparted by the cellulose nanocrystal template enables a large cross-section of the material to be functionalized. Thus, the materials show intense absorption spectra from the tethered spiropyran and rapid color changes when the porous films are irradiated with UV or white light. The spiropyran-bound CNMO films behave as reversible sensors where metal binding to the spiropyran results in visible color changes detectable by the naked eye. These metals can be removed in the presence of ethanol and white light, regenerating the metal-free film. The proof-of-concept demonstrated in this paper may help to develop new photochromic displays, security features, and patterns. [ABSTRACT FROM AUTHOR]

Choosing the optimal catalyst for a new transformation is challenging because the ideal molecular requirements of the catalyst for one reaction do not always simply translate to another. Large groups at the 3,3′ positions of the binaphthol rings are important for efficient stereoinduction but if they are too large this can lead to unusual or poor results. By applying a quantitative steric assessment of the substituents at the 3,3′ positions of the binaphthol ring, we have systematically studied the effect of modulating this group on enantioselectivity for a wide range of reactions involving imines, and verified this analysis using ONIOM calculations. We have shown that in most reactions, the stereochemical outcome depends on both proximal and remote sterics. Summarising detailed calculations into a simple qualitative model identifies and explains the steric features required for high selectivity. This model is consistent with seventy seven papers reporting reactions (over 1000 transformations in total), and provides a straightforward decision tree for selecting the best catalyst. [ABSTRACT FROM AUTHOR]

The objective of this pen-and-paper study is to witness the emergence of stereoisomeric properties when comparing lower to higher families of homologs. Specifically, the study compares all acyclic hexanes (five constitutional isomers, a.k.a. regioisomers), all nine heptanes, all 18 octanes, all 35 nonanes, and all 75 decanes. The first part of the work examines the nature and number of stereoisomeric properties seen to emerge in chemical structures featuring one chiral center (i.e., enantiomerism) or two such centers, in which case more complex stereoisomeric features emerge (enantiomerism, diastereoisomerism, pseudoasymmetry, and meso-isomers). The first emergence of chirality (i.e., enantiomerism) occurred in some heptanes. Diastereoisomerism and meso-isomers appear with some octanes, while a pseudoasymmetric center exists in a decane regioisomer. The second part of the work is an attempt to rationalize the numbers of regioisomers, chiral centers, and stereoisomers as these numbers grow from one family of regioisomers to the higher ones. Far from being random, such increases prove regular and ordered. [ABSTRACT FROM AUTHOR]

This paper clarifies the relationship between the molecular structures of chiral nematic liquid crystals and the shift in their reflection spectrum resulting from contact with volatile organic compounds (VOCs). We also propose a mechanism to explain the red- or blue-shift in the peak wavelength upon contact with VOC vapor. Furthermore, enhancement of the sensitivity of this method of VOC detection is discussed. [ABSTRACT FROM AUTHOR]

Introduction of heterocycles into the helical skeleton of helicenes allows modulation of their redox, chiroptical, and photophysical properties. This paper describes the straightforward preparation and structural characterization by single-crystal X-ray diffraction of thiadiazole-[7]helicene, which was resolved into M and P enantiomers by chiral HPLC, together with its S-shaped double [4]helicene isomer, as well as the smaller congeners thiadiazole-[5]helicene and benzothiadiazole-anthracene. A copper(II) complex with two thiadiazole-[5]helicene ligands was structurally characterized, and it shows the presence of both M and P isomers coordinated to the metal center. The emission properties of the heterohelicenes are highly dependent on the helical turn, as the [7]- and [5]helicene are poorly emissive, whereas their isomers, that is, the S-shaped double [4]helicene and thiadiazole-benzanthracene, are luminescent, with quantum efficiencies of 5.4 and 6.5 %, respectively. DFT calculations suggest quenching of the luminescence of enantiopure [7]helicenes through an intersystem-crossing mechanism arising from the relaxed excited S1 state. [ABSTRACT FROM AUTHOR]

With the adsorption of larger molecules being increasingly tackled by surface scientists, the aspect of chirality often plays a role. This paper gives a topical review of molecular chirality at surfaces and gives a phenomenological overview of different aspects of adsorption and self-assembly of chiral and prochiral molecules and the principles of mirror-symmetry breaking at a surface. After a brief introduction into the history of molecular chirality and the important role it played for understanding the spatial structure of molecules, definitions of chirality are presented. Topics treated here are principle ways to create single chiral adsorbates, chiral ensembles, and monolayers by achiral molecules, adsorption of intrinsically chiral molecules at achiral and chiral surfaces, long-range symmetry breaking in two-dimensional (2D) crystals due to additional chiral bias, chiral restructuring of solid surfaces under the influence of chiral molecules, switching the handedness of adsorbates, and chirality at the liquid/air interface. An outlook onto further potential research directions and recommendations for further reading, including nonsurface-related sources of chiral topics completes this paper. [ABSTRACT FROM AUTHOR]

Enantiomerically pure diarylmethylamines are important building blocks in active pharmaceutical ingredients. Herein, we report a rhodium precatalyst with a chiral disulfoxide ligand that effects the 1,2-addition of arylboroxines to aromatic imines to give high yields and high enantioselectivities of these products. The present paper describes a system that is very simple, where the ease of synthesis of the chiral ligand is combined with low catalyst loadings and reaction conditions that do not need any additives or external base. [ABSTRACT FROM AUTHOR]

Homopolypeptide-based alignment media can induce different orientations of enantiomers as a result of their α-helical structures. This property enables the discrimination of enantiomers through anisotropic NMR parameters such as residual dipolar couplings (RDCs). In this paper, the enantiodiscriminating properties of two alignment media derived from polyglutamic acid derivatives - poly-γ-benzyl- L-glutamate (PBLG) and poly-γ-ethyl- L-glutamate (PELG) - are compared and discussed. The two analytes, isopinocampheol and β-pinene, are investigated, and the role of the lateral side chain of the homopolypeptide in the orientation process is examined. [ABSTRACT FROM AUTHOR]

One of the greatest challenges in modern chemical processing is to achieve enantiospecific control in chemical reactions using chiral media such as chiral mesoporous materials. Herein, we describe a novel and effective synthetic pathway for the preparation of enantioselective nanoporous carbon, based on chiral ionic liquids (CILs). CILs of phenylalanine (CIL(Phe)) are used as precursors for the carbonization of chiral mesoporous carbon. We employ circular dichroism spectroscopy, isothermal titration calorimetry (ITC), and chronoamperometry in order to demonstrate the chiral nature of the mesoporous carbon. The approach presented in this paper is highly significant for the development of a new type of chiral porous materials for enantioselective chemistry. In addition, it contributes significantly to our understanding of the structure and nature of chiral nanoporous materials and surfaces. [ABSTRACT FROM AUTHOR]

The best-known application of salen complexes is the use of a chiral ligand loaded with manganese to form the Jacobsen complex. This organometallic catalyst is used in the epoxidation of unfunctionalized olefins and can achieve very high selectivities. Although this application was proposed many years ago, the mechanism of oxygen transfer remains a question until now. In this paper, the epoxidation mechanism is investigated by an ab initio kinetic modeling study. First of all a proper DFT functional is selected that yields the correct ordering of the various spin states. Our results show that the epoxidation proceeds via a radical intermediate. If we start from the radical intermediate, these results can explain the experiments with radical probes. The subtle influences in the transition state using the full Jacobsen catalyst explain the product distribution observed experimentally. [ABSTRACT FROM AUTHOR]

In this paper, the use of clarithromycin lactobionate, a kind of antibiotic chiral selector, in combination with four neutral cyclodextrin derivatives (glucose-β-cyclodextrin, hydroxyethyl-β-cyclodextrin, methyl-β-cyclodextrin and hydroxypropyl-β-cyclodextrin) was reported for the first time. As a result, these dual systems gave much better resolution of nefopam (the Rs increased to 3.58, 2.72, 1.49 and 1.42, respectively) compared to the single systems. The effects of buffer pH and selector concentration on the separation of nefopam were also investigated. Additionally, some other basic drugs including metoprolol, atenolol, propranolol, bisoprolol, esmolol and ritodrine were tested for the investigation and evaluation of the enantiorecognition capability of the four dual systems. As expected, the synergistic effect was observed in four systems. Different results of these dual systems were also summarized. [ABSTRACT FROM AUTHOR]

This paper describes the synthesis of both polysubstituted oxazolo-pyrrolidinones and -piperidinones by a domino process. The methodology is based on the reaction between hydroxyl halogenoamides and Michael acceptors, which leads efficiently to bicyclic lactams. The process is compatible with unsymmetrical electron-withdrawing groups on the Michael acceptor, which allows the formation of two contiguous and fully controlled tertiary and quaternary stereocenters. In the case of tetrasubstituted Michael acceptors, two adjacent quaternary stereocenters are formed in good yield. Starting from ( R)-phenylglycinol derived amides results in the formation of enantioenriched bicyclic lactams in low to good yields and with high levels of stereoselectivity, thus greatly increasing the scope and interest of this strategy. The origins of chirality transfer and diastereoselectivity were studied by DFT calculations and have been attributed to a kinetic control in one of the last two steps of the reaction sequence. This selectivity is dependent upon both the substituents on the Michael acceptor and the sodium cation chelation. [ABSTRACT FROM AUTHOR]

This paper highlights a new concept on how to induce chirality in a hexaphenyl Geländer-type system. Bridging a terphenyl backbone with a considerably longer benzyl ether oligomer enforces a continuous twist of the molecule, while preventing an achiral meso form. By highlighting cross-coupling strategies and explored synthetic pathways, this report aims to serve as an Ariadne's thread for the synthesis of precisely functionalized, complex polyaromatic systems. The synthetic challenges and considerations required to access the designed target are outlined and solutions to each step of the assembly are presented. Encountered isomerizations are discussed as much as synthetic tools to access highly functionalized intermediates with multiorthogonal moieties. A strong focus is made on the employment of Suzuki-Miyaura protocols for the targeted connection of polyaromatic fragments and ultimately the desired oligomeric structure. [ABSTRACT FROM AUTHOR]

Chiral (ILs) have drawn more and more attention in separation science; however, only a few papers focused on the application of chiral ILs as chiral ligands in LE-CE. In this article, a novel amino acid ionic liquid (AAIL), tetramethylammonium L-hydroxyproline ([TMA][L-OH-Pro]), was first applied as a chiral ligand to evaluate its towards several aromatic in ligand-exchange (LE-CE) and ligand-exchange micellar electrokinetic capillary chromatography (LE-MEKC). In the LE-CE system, excellent separations were achieved for tryptophan (Rs = 3.03) and 3, 4-dihydroxyphenylalanine (DOPA) (Rs = 4.35). Several parameters affecting the enantioseparation were systematically investigated, including AAIL concentration, type and concentration of central metal ion, buffer pH, as well as applied voltage. The optimum separation was obtained with 60 mM AAIL containing 30 mM Cu (II) at pH 4.5. Additionally, an LE-MEKC system was established to further study the of [TMA][L-OH-Pro] towards selected analytes. As observed, the separations of the enantiomers of tryptophan, phenylalanine, and histidine were all improved compared to the LE-CE system. The results indicated that the application of AAILs as chiral ligands is a promising method in chiral separation science. Chirality 27:58-63, 2015. © 2014 Wiley Periodicals, Inc. [ABSTRACT FROM AUTHOR]

The exciton chirality method (ECM) is commonly recognized as one of the best approaches to assign the absolute configuration of biaryls. This paper reports the first exception to this method for a simple biaryl system. ECD and VCD measurements in combination with DFT (B3LYP/6-311G*), TDDFT (CAM-B3LYP/6-311G*), and Coupled-Cluster (RI-SCS-CC2) calculations were used to determine the absolute configurations of axially chiral BODIPY DYEmers. The ECM fails to predict the sign of the intense CD couplet at 500 nm of the 1,1′-coupled dimer. The odd behavior was rationalized by considering the strong transition magnetic dipole associated with the 500 nm transition, which leads to an unexpected dominance of the μm coupling at the expense of the μμ one in these compounds. This is the first case in which a strong μm coupling hampers the use of the ECM, but this behavior should not be restricted to the BODIPY chromophore. [ABSTRACT FROM AUTHOR]

ABSTRACT This paper reports on the occurrence, biosynthesis, metabolism, biological and toxicological profile, and assessment of the authenticity of linalool. The main biological properties of linalool - sedative, anxiolytic, analgesic, anticonvulsant, anti-inflammatory, local anaesthetic - are discussed in terms of the molecule's chirality influence, the mechanisms of activity and type of study ( in vitro, in vivo, clinical studies). Also, there is a discussion of the recent data on the skin sensitizing potential of linalool based on numerous scientific studies which have been performed in the last few years. Comments of the authenticity assessment of linalool are made considering the limitations imposed by the chemical structure, vegetal matrix or processing methods, but also from the perspective of the powerful and sophisticated analytical techniques available today (GC-C-IRMS, enantio-MDGC coupled to GC-C-IRMS, SNIF-NMR). Copyright © 2014 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

SUMMARY Because the permittivity, permeability, and chirality parameters of chiral metamaterials (CMMs) are frequency dependent, the wave equations that describe the characters of electromagnetic wave propagation in CMMs are presented and discretized on the basis of auxiliary differential equation technique in finite-difference time-domain method. The total-field/scattered-field, Mur's first-order absorbing and dielectric boundary conditions for CMMs slab are discussed in the paper. Numerical results show that the cross-polarized reflected coefficient of the CMMs slab is zero. Negative index of refraction phenomenon and optical property of giant optical activity in CMMs slabs are illustrated with 1D auxiliary differential equation-finite-difference time-domain method. The effects to positive or negative phase velocity caused by media parameters of CMMs are studied. Copyright © 2013 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

This paper reviews the present state of the catalytic enantioselective Reformatsky reaction. Advancements in asymmetric versions of this reaction have recently led to a considerable extension of its scope and applicability, principally due to the use of highly active chiral ligands and very specific reaction conditions. [ABSTRACT FROM AUTHOR]

This paper describes the synthesis and characterization of 5-(diphenylphosphanyl)isophthalic acid bioconjugates (Lig-[R]2). In addition to symmetrically disubstituted conjugates with amino acids, peptides or amines, a convenient one-pot, two-step procedure for the synthesis of conjugates bearing two different substituents is reported. The 28 prepared phosphanes were used as monodentate ligands in the rhodium(I)-catalyzed hydrogenation of 2-acetamidoacrylate and ( Z)-α-acetamidocinnamate. The ligand with the smallest side-chain substituents Lig-[Ala-OMe]2 ( 1a) revealed the highest selectivity, with up to 84 % ee. The catalysts presented herein are models of artificial metalloenzymes in which the outer-coordination sphere controls the selectivity in catalysis. The chirality of distant hydrogen-bonded amino acids is transmitted by 'backdoor induction' to the prochiral RhI center. [ABSTRACT FROM AUTHOR]