Chiral Orientations Research Articles

Structure Sensitive Reaction Kinetics of Chiral Molecules on Intrinsically Chiral Surfaces.

Enantiospecific heterogeneous catalysis utilizes chiral surfaces to resolve enantiomers via structure sensitive surface chemistry. The catalyst design challenge is the identification of chiral surface structures that maximize enantiospecificity. Herein, we develop data driven models for the enantiospecificity of tartaric acid reactions on chiral Cu(hkl)R&S surfaces. Measurements of enantiospecific rate constants were obtained by using curved Cu(hkl)R&S surfaces that enable kinetic measurements on hundreds of chiral surface orientations. One model uses feature vectors derived from generalized coordination numbers to capture the local structure around Cu atoms exposed by the Cu(hkl)R&S surfaces. The second model introduces the use of chiral cubic harmonic functions to capture the symmetry constraints of the face-centered cubic Cu structure. The model using 58 generalized coordination numbers has a fitting error similar to that of the model using only 5 cubic harmonic functions. The two models predict maxima in the enantiospecificity on surfaces with very similar surface orientations. The models developed in this work are applicable for any enantiospecific reaction happening on any chiral material with a cubic lattice structure, opening the way to understanding the surface structure sensitivity of the enantiospecific reaction kinetics.

Templated Growth of a Homochiral Thin Film Oxide.

Chiral surfaces are of growing interest for enantioselective adsorption and reactions. While metal surfaces can be prepared with a wide range of chiral surface orientations, chiral oxide surface preparation is more challenging. We demonstrate the chirality of a metal surface can be used to direct the homochiral growth of a thin film chiral oxide. Specifically, we study the chiral "29" copper oxide, formed by oxidizing a Cu(111) single crystal at 650 K. Surface structure spread single crystals, which expose a continuous distribution of surface orientations as a function of position on the crystal, enable us to systematically investigate the mechanism of chirality transfer between the metal and the surface oxide with high-resolution scanning tunneling microscopy. We discover that the local underlying metal facet directs the orientation and chirality of the oxide overlayer. Importantly, single homochiral domains of the "29" oxide were found in areas where the Cu step edges that templated growth were ≤20 nm apart. We use this information to select a Cu(239 241 246) oriented single crystal and demonstrate that a "29" oxide surface can be grown in homochiral domains by templating from the subtle chirality of the underlying metal crystal. This work demonstrates how a small degree of chirality induced by slight misorientation of a metal surface (∼1 sites/20 nm2) can be amplified by oxidation to yield a homochiral oxide with a regular array of chiral oxide pores (∼75 sites/20 nm2). This offers a general approach for making chiral oxide surfaces via oxidation of an appropriately "miscut" metal surface.

Detecting Crystallographic Lattice Chirality using Resonant Inelastic X-ray Scattering

The control and detection of crystallographic chirality is an important and challenging scientific problem. Chirality has wide ranging implications from medical physics to cosmology including an intimate but subtle connection in magnetic systems, for example Mn1−xFexSi. X-ray diffraction techniques with resonant or polarized variations of the experimental setup are currently utilized to characterize lattice chirality. We demonstrate using theoretical calculations the feasibility of indirect K –edge bimagnon resonant inelastic X-ray scattering (RIXS) spectrum as a viable experimental technique to distinguish crystallographic handedness. We apply spin wave theory to the recently discovered √5 × √5 vacancy ordered chalcogenide Rb0.89Fe1.58Se2 for realistic X-ray experimental set up parameters (incoming energy, polarization, Bragg angle, and experimental resolution) to show that the computed RIXS spectrum is sensitive to the underlying handedness (right or left) of the lattice. A Flack parameter definition that incorporates the right- and left- chiral lattice RIXS response is introduced. It is shown that the RIXS response of the multiband magnon system RbFeSe arises both from inter- and intra- band scattering processes. The extinction or survival of these RIXS peaks are sensitive to the underlying chiral lattice orientation. This in turn allows for the identification of the two chiral lattice orientations.

Quadrupole moments in chiral materialDyFe3(BO3)4observed by resonant x-ray diffraction

By means of circularly polarized x-ray beam at Dy L3 and Fe K absorption edges, the chiral structure of the electric quadrupole was investigated for a single crystal of DyFe3(BO3)4 in which both Dy and Fe ions are arranged in spiral manners. The integrated intensity of the resonant x- ray diffraction of space-group forbidden reflections 004 and 005 is interpreted within the electric dipole transitions from Dy 2p3 to 5d and Fe 1s to 4p, respectively. We have confirmed that the 2 handedness of the crystal observed at Dy L3 and Fe K edges is consistent with that observed at Dy M5 edge in the previous study. By analyzing the azimuth scans of the diffracted intensity, the electronic quadrupole moments of Dy 5d and Fe 4p are derived. The temperature profiles of the integrated intensity of 004 at the Dy L3 and the Fe K edges are similar to those of Dy-O and Fe-O bond lengths, while that at the Dy M5 edge does not. The results indicate that the helix chiral orientations of quadrupole moments due to Dy 5d and Fe 4p electrons are more strongly affected by the crystal fields than Dy 4f.

Polarization contrast of nanoscale waveguides in high harmonic imaging

The optical polarization response of a structured material is one of its most significant properties, carrying information about microscopic anisotropies as well as chiral features and spin orientations. Polarization analysis is therefore a key element of imaging and spectroscopy techniques throughout the entire spectrum. In the case of extreme ultraviolet (EUV) radiation, however, both the preparation and detection of well-defined polarization states remain challenging. As a result, polarization-sensitive EUV microscopy based on table-top sources has not yet been realized, despite its great potential, for example, in nanoscale magnetic imaging. Here, we demonstrate polarization contrast in coherent diffractive imaging using high harmonic radiation and investigate the polarization properties of nanoscale transmission waveguides. We quantify the achievable polarization extinction ratio for different waveguide geometries and wavelengths. Our results demonstrate the utility of slab waveguides for efficient EUV polarization control and illustrate the importance of considering polarization contrast in the imaging of nanoscale structures.

Graphenylene Nanotubes

A new type of carbon nanotube, based on the graphenylene motif, is investigated using density functional and tight-binding methods. Analogous to conventional graphene-based nanotubes, a two-dimensional graphenylene sheet can be "rolled" into a seamless cylinder in armchair, zigzag, or chiral orientations. The resulting nanotube can be described using the familiar (n,m) nomenclature and possesses 4-, 6-, and 12-membered rings, with three distinct bond lengths, indicating a nonuniform distribution of the electron density. The dodecagonal rings form pores, 3.3 Å in diameter in graphenylene, which become saddle-shaped paraboloids in smaller-diameter nanotubes. Density functional theory predicts zigzag nanotubes to be small-band gap semiconductors, with a generally decreasing band gap as the diameter increases. Interestingly, the calculations predict metallic characteristics for armchair nanotubes with small diameters (<2 nm), and small-band gap semiconducting characteristics for larger-diameter ones. Graphenylene nanotubes with indices mod(n-m,3) = 0 exhibit a band gap approximately equal to that of armchair graphenylene nanotubes with comparable diameter.

Phase modulation using different orientations of a chiral nematic in liquid crystal over silicon devices

ABSTRACTModulation of the intensity of light by high quality reflective micro-displays is predominantly carried out by liquid crystal over silicon (LCoS) spatial light modulator (SLM) technology for applications such as pico-projectors. Wider use of these devices, in applications such as computer-generated holography and optical correlation, is limited by their phase modulation ability and illumination polarisation state dependence. These devices rely on planar or twisted nematic liquid crystals to modulate the light, but due to their viscoelastic properties they are inherently slow. Research into the use of the polymer stabilised blue phase has already shown that it can offer high speed phase modulation. However, other chiral nematic orientations are yet to be compared in LCoS devices. In this article, we demonstrate that polymer-stabilised chiral nematic liquid crystal electro-optical effects can offer phase modulation in silicon backplane devices. The uniform standing helix and focal conic textures are shown to be independent of the input light polarisation state and the uniform lying helix is shown to be polarisation dependent. These optical responses are then compared with that of the blue phase to identify a suitable orientation for further development in LCoS technology in order to find a high-speed, full phase modulating material.

Experimentally Engineering the Edge Termination of Graphene Nanoribbons

The edges of graphene nanoribbons (GNRs) have attracted much interest due to their potentially strong influence on GNR electronic and magnetic properties. Here we report the ability to engineer the microscopic edge termination of high-quality GNRs via hydrogen plasma etching. Using a combination of high-resolution scanning tunneling microscopy and first-principles calculations, we have determined the exact atomic structure of plasma-etched GNR edges and established the chemical nature of terminating functional groups for zigzag, armchair, and chiral edge orientations. We find that the edges of hydrogen-plasma-etched GNRs are generally flat, free of structural reconstructions, and terminated by hydrogen atoms with no rehybridization of the outermost carbon edge atoms. Both zigzag and chiral edges show the presence of edge states.

Degradation of CYANEX 301 in Contact with Nitric Acid Media

The nature of the degradation product obtained upon contacting CYANEX 301 (bis(2,4,4-trimethylpentyl)dithiophosphinic acid) with nitric acid has been elucidated and found to be a disulfide derivative. The first step to the degradation of CYANEX 301 in toluene has been studied using 31P{1H} NMR after being contacted with nitric acid media. The spectrum of the degradation product exhibits a complex multiplet around δP = 80 ppm. A succession of purifications of CYANEX 301 has resulted in single crystals of the acidic form and the corresponding ammonium salt. Unlike the original CYANEX 301, which consists of a complex diastereomeric mixture displaying all possible combinations of chiral orientations at the 2-methyl positions, the purified crystals were shown by single-crystal X-ray diffraction to be racemates, containing 50:50 mixtures of the [R;R] and [S;S] diastereomers. The comparison between the 31P {1H} NMR spectra of the degradation products resulting from the diastereomerically pure CYANEX 301 and the original diastereomeric mixture has elucidated the influence of the isomeric composition on the multiplicity of the 31P {1H} NMR peak. These NMR data indicate the initial degradation leads to a disulfide-bridged condensation product displaying multiple resonances due to phosphorus–phosphorus coupling, which is caused by the inequivalence of the two P atoms as a result of their different chirality. A total of nine different NMR resonances, six of which display phosphorus–phosphorus coupling, could be assigned, and the identity of the peaks corresponding to phosphorus atoms coupled to each other was confirmed by 31P {1H} homodecoupled NMR analysis.

Enhancing Enantioselectivity of Electrodeposited CuO Films by Chiral Etching

The enantioselectivity of electrodeposited CuO with a chiral orientation is enhanced if the CuO is first etched in a solution of tartaric acid. Electrochemical quartz crystal microbalance studies show that CuO(11̄1̄) electrodeposited from l-tartrate etches faster in l-tartaric acid, whereas CuO(11̄1̄) electrodeposited from d-tartrate etches faster in d-tartaric acid. The enantioselectivity is probed by cyclic voltammetry. The proposed mechanism differentiates between chiral orientation and chiral surface. The enhancement of enantioselectivity of the films with chiral orientations is attributed to an increase in the chiral surface area of the etched CuO films.

Enantiospecific electrodeposition of chiral CuO films on Cu(1 1 0) from aqueous Cu(II) tartrate and amino acid complexes

CuO films were anodically electrodeposited onto Cu(1 1 0) single crystals from alkaline solutions of Cu(II) complexed with tartrate, alanine, valine, and glycine. In all cases the films were epitaxial, exhibiting varying amounts of the chiral orientations (1 1 0) and ( 1 ¯ 1 ¯ 0 ). The enantiomeric excess (ee) of the chiral electrodeposition process was determined by X-ray pole figure analysis. The CuO films deposited from d-tartrate solution exhibited a (1 1 0) out-of-plane orientation with an ee of 61%, while films grown from l-tartrate exhibited a ( 1 ¯ 1 ¯ 0 ) orientation with an ee of 77%. The CuO film deposited from achiral meso-tartrate had essentially equal amounts of both chiral orientations. Epitaxial CuO films deposited from d-alanine and d-valine both gave ( 1 ¯ 1 ¯ 0 ) orientation with ee's of 40 and 65%, respectively, while CuO films deposited from l-alanine and l-valine gave (1 1 0) orientations with ee's of 39 and 67%, respectively. Films obtained from a glycine solution showed roughly equal amounts of both chiral orientations.

Special effects of ortho-isopropylphenyl groups. Diastereoisomerism in platinum(ii) and palladium(ii) complexes of helically chiral PAr3 ligands

The coordination chemistry of the four phosphines, P{C6H3(o-CH3)(p-Z)}3 where Z = H (1a) or OMe (1b) and P{C6H3(o-CHMe2)(p-Z)}3 Z = H (1c) or OMe (1d) with platinum(II) and palladium(II) is reported. Mononuclear complexes trans-[PdCl2L2](L = 1a,b) and trans-[PtCl2L2](L = 1a-c) have been prepared and the crystal structures of trans-[PdCl2(1b)2] and trans-[PtCl2(1c)2] as their dichloromethane solvates have been determined. The structures show that in these complexes, the ligands adopt g+ g+ a conformations. Examination of the Cambridge Structural Database confirms this to be one of only two conformer types that tri-o-tolylphosphines adopt and the only viable conformer in 4 and 6 coordinate complexes. The binuclear complexes trans-[Pd2Cl4L2](L = 1c,d) are formed even when an excess of the bulky 1c,d is used in the synthesis and the crystal structure of trans-[Pd2Cl4(1c)2] as its chloroform solvate is reported. Reaction of [PtCl2(NCBu(t))2] with 1b-d in refluxing toluene gave the cycloplatinated species [Pt2Cl2(L - H)2] where L - H is phosphine 1b-d deprotonated at one of the ortho-methyl carbon atoms. Variable temperature 31P and 1H NMR spectroscopy reveals that all the complexes reported are fluxional. The processes are analysed in terms of restricted P-C and P-M rotations that give rise to diastereoisomeric rotamers because of the helically chiral orientations of the aryl substituents. For the complexes of the bulky ligands 1c,d, rotation about the P-C bond is slow on the NMR timescale even up to 75 degrees C. The crystal structure of the cyclometallated complex [Pt2Cl2(1d - H)2] has been determined.

Enantiospecific Electrodeposition of Chiral CuO Films from Copper(II) Complexes of Tartaric and Amino Acids on Single-Crystal Au(001)

Chiral films of CuO were electrochemically deposited onto achiral Au(001) using chiral precursors such as tartaric acid and the amino acids alanine and valine to complex the Cu(II). The chirality of the electrodeposited films was dictated by the chiral solution precursor. X-ray diffraction pole figures and azimuthal scans, in conjunction with stereographic projections, were used to determine the absolute configuration and enantiomeric excess of the chiral CuO films. CuO films grown from l-tartaric acid have a (11̄1̄) orientation with an enantiomeric excess of 95%, while the films grown from d-tartaric acid have a (1̄11) orientation with an enantiomeric excess of 93%. CuO films grown from chiral amino acids have two types of chiral orientations, each showing lower enantiomeric excess compared with the films deposited from tartaric acid. The films grown from l-alanine and l-valine solution have an excess of the (1̄11) and (1̄1̄1̄) orientations, while the films grown from d-alanine and d-valine have an excess of (11̄1̄) and (111). Films of CuO deposited from a solution of achiral glycine consist of a racemic mixture of the (1̄11) and (11̄1̄) orientations. Chiral CuO films deposited on both single-crystal Au(001) and polycrystalline Au films were shown to exhibit chiral recognition for the electrochemical oxidation of tartaric acid.

Interference and isospin of disoriented chiral condensates.

If coherent states describe the disoriented chiral condensates (DCC's), many states of different chiral orientations should equally contribute to a given hadronic process. However, in the classical field description, we ignore the interference between the different DCC amplitudes. It results in a disregard of isospin invariance. We examine quantitatively how good this approximation is for the DCC's of a typical size.

Baryon production in a topological model

We develop and make predictions using a topological model for baryon production that we proposed in a previous paper. “Cool” partons close to mass shell are argued to be in one-to-one correspondence with independent domains which break chiral symmetry spontaneously by non-perturbatively developing randomly-oriented chiral condensates. Baryons are formed where there are topological mismatches between the chiral orientations in adjacent domains. We give an algorithm based on the random lattice approach to field theory for calculating the spatial locations of different domains and defining when they are adjacent. We show that the mean baryon multiplicity should grow faster than the number of “cool” partons, which explains the observed increase of baryon production in Ψ decays, predicts a rapid increase in baryon production at LEP, implies that baryons should not have a Poisson multiplicity distribution, and means that events with baryons should have a higher mean sphericity. A further ansatz yields a baryon energy distribution that agrees very well with TPC data.