Nonsuperimposable Mirror Images Research Articles

Structural Chirality and Electronic Chirality in Quantum Materials

In chemistry and biochemistry, chirality represents the structural asymmetry characterized by nonsuperimposable mirror images for a material such as DNA. In physics, however, chirality commonly refers to the spin–momentum locking of a particle or quasiparticle in the momentum space. While seemingly disconnected, structural chirality in molecules and crystals can drive electronic chirality through orbital–momentum locking; that is, chirality can be transferred from the atomic geometry to electronic orbitals. Electronic chirality provides an insightful understanding of chirality-induced spin selectivity, in which electrons exhibit salient spin polarization after going through a chiral material, and electrical magnetochiral anisotropy, which is characterized by diode-like transport. It further gives rise to new phenomena, such as anomalous circularly polarized light emission, in which the light handedness relies on the emission direction. These chirality-driven effects will generate broad impacts for fundamental science and technology applications in spintronics, optoelectronics, and biochemistry.

Capturing electron-driven chiral dynamics in UV-excited molecules

Chiral molecules, used in applications such as enantioselective photocatalysis1, circularly polarized light detection2 and emission3 and molecular switches4,5, exist in two geometrical configurations that are non-superimposable mirror images of each other. These so-called (R) and (S) enantiomers exhibit different physical and chemical properties when interacting with other chiral entities. Attosecond technology might enable influence over such interactions, given that it can probe and even direct electron motion within molecules on the intrinsic electronic timescale6 and thereby control reactivity7–9. Electron currents in photoexcited chiral molecules have indeed been predicted to enable enantiosensitive molecular orientation10, but electron-driven chiral dynamics in neutral molecules have not yet been demonstrated owing to the lack of ultrashort, non-ionizing and perturbative light pulses. Here we use time-resolved photoelectron circular dichroism (TR-PECD)11–15 with an unprecedented temporal resolution of 2.9 fs to map the coherent electronic motion initiated by ultraviolet (UV) excitation of neutral chiral molecules. We find that electronic beatings between Rydberg states lead to periodic modulations of the chiroptical response on the few-femtosecond timescale, showing a sign inversion in less than 10 fs. Calculations validate this and also confirm that the combination of the photoinduced chiral current with a circularly polarized probe pulse realizes an enantioselective filter of molecular orientations following photoionization. We anticipate that our approach will enable further investigations of ultrafast electron dynamics in chiral systems and reveal a route towards enantiosensitive charge-directed reactivity.

Linear stability analysis of chemical mechanism, Listanalchem: A tool for the search of spontaneous mirror symmetry breaking

Homochirality, the phenomenon by which one of two virtually identical (non-superimposable mirror images) compounds is favored over the other in the chemistry of life, has been regarded as a requisite for the emergence of all living things on earth. Spontaneous mirror symmetry breaking has been proposed to produce the imbalance. Under this framework, Frank presented, in his foundational article “On spontaneous asymmetric synthesis”, a simple chemical reaction network that displays spontaneous symmetry breaking for a specific set of reaction rates. Research has since focused on finding more complex and plausible models, each one with its advantages and disadvantages. Nevertheless, finding reaction rate values that make a model exhibit spontaneous symmetry breaking is a complex task, even for specially crafted models. LInear STability ANALysis of CHEmical Mechanism, Listanalchem, is a method and software for the search for appropriate reaction rates. It includes four different algorithms inspired by the analysis of Frank's network. Two classical algorithms are also included in Listanalchem: the Trace-Determinant plane and the Stoichiometric Network Analysis by Bruce Clarke. Listanalchem reads a chemical reaction network from plain text and runs one or more of the available algorithms according to the user selection. Listanalchem is tested and verified by studying classical, modified, and recent models proposed to explain the origin of biological homochirality.•Listanalchem allows a fast and reliable search for instability behavior in chemical mechanisms that pretend to explain spontaneous mirror symmetry breaking.•Listanalchem contains several model examples, including the most cited in the related literature.•Listanalchem is a tool that tests models that pretend to explain the origin of biological homochirality, helps find errors, and aids in designing new models.

The Whole Theory of This Universe—A Step Forward to Einstein, Part-3<sup>rd</sup>: “The Universal Theory of Visible and Invisible Universe”

We believe that the universe is of two types: visible and invisible. Nothing is at rest between the invisible and visible universes. All microscopic bodies as well as all macroscopic bodies are in motion along curved paths (i.e. in circles). The universe inside an atom is as vast as the visible universe. An atom consists of millions of particles or particle galaxies which contain central energy pools or central energy cores. Energy pools present in the centre of the invisible universe inside atomic or subatomic particles from which particles and energy are continuously interconverting. In a dense central energy pool, two opposite charges are created due to the swirling motion of microscopic energy droplets. Small microscopic energy droplets may swirl either clockwise or anti-clockwise to produce microscopic tornadoes which are non-superimposable mirror images of each other and gain the property of positive and negative charges. Hence, the electrostatic force is originated between these two opposite charges, which are then changed into a pair of particles, i.e. catitron, which carries a positive charge, and anitron which carries a negative charge. All the other millions of subatomic particles or particle galaxies are produced in the same way. So, the electrostatic force is the basic force, and all other forces originate from this basic electrostatic force of attraction. When charged particles move, they produce an oscillating electric field, and the spinning of these particles produces oscillating magnetic fields. These oscillating electric and magnetic fields are perpendicular to each other and, by their interaction, an oscillating gravitational field is produced which is also perpendicular to both the oscillating electric field and the oscillating magnetic field. The Earth’s axial tilt, which causes the Earth’s precessional motion, is caused by the parallel alignment of the Earth’s magnetic field with the magnetic field of the Sun. Gravity is not a cause of space-time curvature, but gravity causes space-time curvature. Space-time curvature is nothing but a curved path around a heavy object. The Universal Theory of Visible and Invisible Universe—The Whole Theory of This Universe—A Step Forward to Einstein, opens new windows in the challenging fields of science and research, i.e. visible and invisible universe, universe inside an atom, what is the stuff of the entire universe? What will happen at the end of this whole universe?

Population effects of chiral snail shell development relate handedness to health and disease

The spiral patterns of snail shells exhibit chirality, or “handedness.” These patterns often heavily favor the dextral (right-handed, or clockwise) over the sinistral (left-handed, clockwise) phenotype. While the developmental pathways resulting in each enantiomorph (non-superimposable mirror image form) have been studied extensively, there has been limited investigation into how the emphasis on one spiral direction over the other may confer survival benefit. This perspective essay proposes that developmental events determining cell cleavage robustness, mating compatibility, and predator evasion can influence the distribution of dextral and sinistral snails. The connection between chirality and survivability has broader implications for exploring the role of handedness in diseases and their treatments.

Nonlinear helical dichroism in chiral and achiral molecules

Chiral interactions are prevalent in nature, driving a variety of biochemical processes. Discerning the two non-superimposable mirror images of a chiral molecule, known as enantiomers, requires interaction with a chiral reagent with known handedness. Circularly polarized light beams are often used as a chiral reagent. Here we demonstrate efficient chiral sensitivity with linearly polarized helical light beams carrying an orbital angular momentum of ±lħ, in which the handedness is defined by the twisted wavefront structure tracing a left- or right-handed corkscrew pattern as it propagates in space. By probing the nonlinear optical response, we show that helicity-dependent nonlinear absorption occurs even in achiral molecules and can be controlled. We model this effect by considering induced multipole moments in light–matter interactions. Design and control of light–matter interactions with helical light may open new opportunities in chiroptical spectroscopy, light-driven molecular machines, optical switching and in situ ultrafast probing of chiral systems and magnetic materials.

Identifying Chirality in Line Drawings of Molecules Using Imbalanced Dataset Sampler for a Multilabel Classification Task.

Chirality, the ability of some molecules to exist as two non-superimposable mirror images, profoundly influences both chemistry and biology. Advances in deep learning enable the automatic recognition of chemical structure diagrams, however, studies on discovering the molecule chirality are scarce and the machine-readable molecular representations are not always sufficient to fully support the encoding of this important property. Here, we pretrained networks on a ChEMBL+ dataset (79641 molecules) and fine-tuned them for the binary classification of chirality (achiral/chiral) or multilabel chirality type classifications (none/centre/axial/planar). To address the label combination imbalanced problem in the multilabel task, the study proposed a Formulated Imbalanced Dataset Sampler (FIDS) to sample a formulated amount of minority label combinations on top of the training set. On a 10-fold cross validation experiment using our CHIRAL dataset (1142 manually curated molecules), our models achieved up to an accuracy of 90 % in the binary task. In the multilabel task incorporated with FIDS, the overall performance increases from 87 % to 89 % and the accuracy per label combination can attained up to a 50 % increase. Through the study of heatmaps, our work also exemplified the potential of deep neural network to make predictions based on the actual location of chirality elements.

Enantioselective Topological Frequency Conversion.

Two molecules are enantiomers if they are nonsuperimposable mirror images of each other. Electric dipole-allowed cyclic transitions |1⟩ → |2⟩ → |3⟩ → |1⟩ obey the symmetry relation , where = (μ21R,SE21)(μ13R,SE13)(μ32R,SE32) and R and S label the two enantiomers. Herein, we generalize the concept of topological frequency conversion to an ensemble of enantiomers. We show that, within a rotating-frame, the pumping power between fields of frequency ω1 and ω2 is sensitive to enantiomeric excess, = ℏ[ω1ω2CLR/(2π)](NR - NS), where Ni is the number of enantiomers i and CLR is an enantiomer-dependent Chern number. Connections with chiroptical microwave spectroscopy are made. Our work provides an underexplored and fertile connection between topological physics and molecular chirality.

Engineering of inorganic nanostructures with hierarchy of chiral geometries at multiple scales

Engineering of inorganic nanostructures with hierarchy of chiral geometries at multiple scales

Computational Activity to Visualize Stereoisomers in Molecules with an Axis of Chirality

The topic of chirality is often a difficult concept to grasp for the typical undergraduate chemistry student. Often, the chirality of molecules is taught by using the concept of an asymmetric carbon center that generates molecules with nonsuperimposable mirror images. When students encounter a chiral molecule lacking a stereogenic center such as an asymmetric carbon, the confusion is amplified. In order to study this distinction, this computational study was designed to help students visualize molecules containing an axis of chirality but no stereogenic center. The molecules chosen for this activity are allenes, binaphthyls, and spiranes. Students first perform a visual inspection by drawing the possible enantiomers side-by-side in a 3D structure drawing program. They then compute vibrational circular dichroism (VCD) spectra for the enantiomers. Chiral molecules uniquely interact with circularly polarized light due to the dissymmetry in their molecular orbitals. Therefore, determining if a molecule is chiral may be achieved by computing its VCD spectrum: where chiral molecules produce a peaked spectrum and achiral molecules feature a zero-intensity flat-lined spectrum. For a given enantiomer, the VCD spectrum shows both positive and negative peaks. Just as enantiomers are mirror images, VCD spectra are mirror images of each other, meaning a positive peak from one enantiomer will be a negative peak from the other enantiomer.

Elucidating Peptidoglycan Structure: An Analytical Toolset.

Peptidoglycan (PG) is a ubiquitous structural polysaccharide of the bacterial cell wall, essential in preserving cell integrity by withstanding turgor pressure. Any change that affects its biosynthesis or degradation will disturb cell viability, therefore PG is one of the main targets of antimicrobial drugs. Considering its major role in cell structure and integrity, the study of PG is of utmost relevance, with prospective ramifications to several disciplines such as microbiology, pharmacology, agriculture, and pathogenesis. Traditionally, high-performance liquid chromatography (HPLC) has been the workhorse of PG analysis. In recent years, technological and bioinformatic developments have upgraded this seminal technique, making analysis more sensitive and efficient than ever before. Here we describe a set of analytical tools for the study of PG structure (from composition to 3D architecture), identify the most recent trends, and discuss future challenges in the field.

Chirality Effect on Cholesterol Modulation of Protein Function.

Cholesterol is a key steroidal, lipid biomolecule found abundantly in plasma membranes of eukaryotic cells. It is an important structural component of cellular membranes and regulates membrane fluidity and permeability. Cholesterol is also essential for normal functioning of key proteins including ion-channels, G protein-coupled receptors (GPCRs), membrane bound steroid receptors, and receptor kinases. It is thought that cholesterol exerts its actions via specific binding to chiral proteins and lipids as well as through non-specific physiochemical interactions. Distinguishing between the specific and the non-specific interactions can be difficult. Although much remains unclear, progress has been made in recent years by utilizing ent-cholesterol, the enantiomer of natural cholesterol (nat-cholesterol) as a probe. Ent-Cholesterol is the non-superimposable mirror image of nat-cholesterol and exhibits identical physiochemical properties as nat-cholesterol. Hence, if the biological effects of cholesterol result solely due to membrane effects, it is expected that there will be no difference between ent-cholesterol and nat-cholesterol. However, when direct binding with chiral proteins and lipids is involved, the enantiomer is expected to potentially elicit significantly different, measurable effects due to formation of diastereomeric complexes. In this chapter, we have reviewed the literature related to ent-cholesterol and its use as a probe for various biophysical and biological interactions of cholesterol.

Catalytic deracemization of chiral allenes by sensitized excitation with visible light.

Chiral compounds exist asenantiomers that are non-superimposable mirror images of each other. Owing to the importance of enantiomerically pure chiral compounds1-for example, as active pharmaceutical ingredients-separation of racemates (1:1 mixtures of enantiomers) is extensively performed2. Frequently, however, only a single enantiomeric form of a chiral compound is required, which raises the question of how a racemate can be selectively converted into a single enantiomer. Such a deracemization3 process is entropically disfavoured and cannot be performed by a conventional catalyst in solution. Here we show that it is possible to photochemically deracemize chiral compounds with high enantioselectivity using irradiation with visible light (wavelength of 420 nanometres) in the presence of catalytic quantities (2.5 mole per cent) of a chiral sensitizer. We converted an array of 17 chiral racemic allenes into the respective single enantiomers with 89 to 97 per cent enantiomeric excess. The sensitizer is postulated to operate by triplet energy transfer to the allene, with different energy-transfer efficiencies for the two enantiomers. It thus serves as a unidirectional catalyst that converts one enantiomer but not the other, and the decrease in entropy is compensated by light energy. Photochemical deracemization enables the direct formation of enantiopure materials from a racemic mixture of the same compound, providing a novel approach to the challenge of creating asymmetry.

Epitaxial Electrodeposition of Chiral Metal Surfaces on Silicon(643).

Surfaces of achiral materials exhibit two-dimensional chirality if they lack mirror symmetry. An example is the (643) surface of face-centered-cubic metals such as Au. The (643) and (6̅4̅3̅) surfaces are non-superimposable mirror images of each other. Chiral surfaces offer the possibility of serving as heterogeneous catalysts for chiral synthesis or providing a platform for chiral separation or crystallization. Here, we show the symmetry requirements for surface chirality, and we demonstrate that chiral surfaces can be produced by electrochemically depositing epitaxial films of Au onto commercially available Si(643) wafers. Au(643) is deposited onto one side of the wafer, and its enantiomer Au(6̅4̅3̅) is deposited on the other side of the wafer. In addition to the (643) orientation, the (8 14 17) orientation of Au is produced on the Si(643) wafers. The (8 14 17) orientation has a similar kinked surface to the (643) surface, but it has staggered kinks. Other metal films including Pt, Ni, Cu, and Ag that are electrodeposited onto the Au films exhibit strong in-plane and out-of-plane order. Hence, the method provides a pathway for producing chiral surfaces of a wide range of materials, and it obviates the need to work with expensive single crystals. The Ag/Au/Si(643) surface showed a preference for the electrochemical oxidation of d-glucose, whereas the Ag/Au/Si(6̅4̅3̅) surface showed preference for the oxidation of l-glucose.

Determination of Enantiomeric Excess in Pharmaceutical Active Agents: The Role of High Performance Liquid Chromatography

Chiral drugs are composed of molecules with the same chemical structure, but different 3-dimensional molecular arrangements. Chirality is defined as non-super imposable mirror images.A pair of stereoisomer’s that is non-super imposable mirror images of one another is an enantiomer and therefore has different 3-dimensional configuration. Several drugs of clinical importance are enantiomers. However, there is an increasing trend for the pharmaceutical industries to develop and market drug products

Human Liver Microsomes Atropselectively Metabolize 2,2',3,4',6-Pentachlorobiphenyl (PCB 91) to a 1,2-Shift Product as the Major Metabolite.

Polychlorinated biphenlys (PCBs) and their hydroxylated metabolites (OH-PCBs) have been implicated in neurodevelopmental disorders. Several neurotoxic PCBs, such as PCB 91, are chiral because they form stable rotational isomers, or atropisomers, that are nonsuperimposable mirror images of each other. Because only limited information about the metabolism of these PCBs by human cytochrome P450 (P450) enzymes is available, we investigated the biotransformation of PCB 91 to OH-PCBs by human liver microsomes (HLMs). Racemic PCB 91 was incubated with pooled or individual donor HLMs at 37 °C, and levels and chiral signatures of PCB 91 and its metabolites were determined. Several OH-PCBs were formed in the order 2,2',4,4',6-pentachlorobiphenyl-3-ol (3-100; 1,2 shift product) > 2,2',3,4',6-pentachlorobiphenyl-5-ol (5-91) ≫ 2,2',3,4',6-pentachlorobiphenyl-4-ol (4-91) ≫ 4,5-dihydroxy-2,2',3,4',6-pentachlorobiphenyl (4,5-91). Metabolite formation rates displayed interindividual variability. The first eluting atropisomers of PCB 91, 3-100 and 4-91, and the second eluting atropisomer of 5-91 were enriched in most metabolism studies. The unexpected, preferential formation of a 1,2-shift product and the variability of the OH-PCBs profiles in experiments with individual donor HLMs underline the need for further systematic studies of the atropselective metabolism of PCBs in humans.

Enantiomer-specific measurements of current-use pesticides in aquatic systems.

Some current-use pesticides are chiral and have nonsuperimposable mirror images called enantiomers that exhibit identical physical-chemical properties but can behave differently when in contact with other chiral molecules (e.g., regarding degradation and uptake). These differences can result in variations in enantiomer presence in the environment and potentially change the toxicity of pesticide residues. Several current-use chiral pesticides are applied in urban and agricultural areas, with increased potential to enter watersheds and adversely affect aquatic organisms. The present study describes a stereoselective analytical method for the current-use pesticides fipronil, cis-bifenthrin, cis-permethrin, cypermethrin, and cyfluthrin. We show use of the method by characterizing enantiomer fractions in environmental sample extracts (sediment and water), and laboratory-dosed fish and concrete extracts previously collected by California organizations. Enantiomer fractions for most environmental samples are the same as racemic standards (equal amounts of enantiomers, enantiomer fraction = 0.5) and therefore are not expected to differ in toxicity from racemic mixtures typically tested. In laboratory-derived samples, enantiomer fractions are more frequently nonracemic and favor the less toxic enantiomer; permethrin enantiomer fractions range from 0.094 to 0.391 in one type of concrete runoff and enantiomer fractions of bifenthrin in dosed fish range from 0.378 to 0.499. We use enantiomer fractions as a screening tool to understand environmental exposure and explore ways this uncommon measurement could be used to better understand toxicity and risk. Environ Toxicol Chem 2018;37:99-106. Published 2017 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

Emergent Properties of an Organic Semiconductor Driven by its Molecular Chirality.

Chiral molecules exist as pairs of nonsuperimposable mirror images; a fundamental symmetry property vastly underexplored in organic electronic devices. Here, we show that organic field-effect transistors (OFETs) made from the helically chiral molecule 1-aza[6]helicene can display up to an 80-fold difference in hole mobility, together with differences in thin-film photophysics and morphology, solely depending on whether a single handedness or a 1:1 mixture of left- and right-handed molecules is employed under analogous fabrication conditions. As the molecular properties of either mirror image isomer are identical, these changes must be a result of the different bulk packing induced by chiral composition. Such underlying structures are investigated using crystal structure prediction, a computational methodology rarely applied to molecular materials, and linked to the difference in charge transport. These results illustrate that chirality may be used as a key tuning parameter in future device applications.

The added value of small-molecule chirality in technological applications

Chirality is a fundamental symmetry property; chiral objects, such as chiral small molecules, exist as a pair of non-superimposable mirror images. Although small-molecule chirality is routinely considered in biologically focused application areas (such as drug discovery and chemical biology), other areas of scientific development have not considered small-molecule chirality to be central to their approach. In this Review, we highlight recent research in which chirality has enabled advancement in technological applications. We showcase examples in which the presence of small-molecule chirality is exploited in ways beyond the simple interaction of two different chiral molecules; this can enable the detection and emission of chiral light, help to control molecular motion, or provide a means to control electron spin and bulk charge transport. Thus, we demonstrate that small-molecule chirality is a highly promising avenue for a wide range of technologically oriented scientific endeavours. Although it is a fundamental property of many small molecules, chirality is not widely exploited in materials applications as its benefits are not widely recognized — indeed, the need for stereoselective synthesis may be seen as a disadvantage. In this Review, we highlight recent research in which chirality has had an enabling impact in technological applications.

Absolute configuration of 2,2',3,3',6-pentachlorinatedbiphenyl (PCB 84) atropisomers.

Nineteen polychlorinated biphenyl (PCB) congeners, such as 2,2',3,3',6-pentachlorobiphenyl (PCB 84), display axial chirality because they form stable rotational isomers, or atropisomers, that are non-superimposable mirror images of each other. Although chiral PCBs undergo atropselective biotransformation and atropselectively alter biological processes, the absolute structure of only a few PCB atropisomers has been determined experimentally. To help close this knowledge gap, pure PCB 84 atropisomers were obtained by semi-preparative liquid chromatography with two serially connected Nucleodex β-PM columns. The absolute configuration of both atropisomers was determined by X-ray single-crystal diffraction. The PCB 84 atropisomer eluting first and second on the Nucleodex β-PM column correspond to (aR)-(-)-PCB 84 and (aS)-(+)-PCB 84, respectively. Enantioselective gas chromatographic analysis with the β-cyclodextrin-based CP-Chirasil-Dex CB gas chromatography column showed the same elution order as the Nucleodex β-PM column. Based on earlier reports, the atropisomers eluting first and second on the BGB-172 gas chromatography column are (aR)-(-)-PCB 84 and (aS)-(+)-PCB 84, respectively. An inversion of the elution order is observed on the Cyclosil-B gas chromatography and Cellulose-3 liquid chromatography columns. These results advance the interpretation of environmental and human biomonitoring as well as toxicological studies.