Search Results (77)

Propylene oxide is the first and only chiral molecule to have been observed in the interstellar medium. Given the mechanisms for forming chiral species, which are important for astrobiology in understanding the origins of life, we report here an experimental and theoretical investigation into the electronic structure of propylene oxide and its evolution from the methylation and epoxidation of ethene. Here, electron momentum spectroscopy is used as an orbital-imaging technique to probe experimental orbital momentum distributions. These are directly compared with theoretical orbital momentum distributions calculated at the equilibrium geometry, and those calculated by considering the vibrational motion of the propylene oxide target. This allows us to identify which molecular orbitals are sensitive to specific vibrational normal modes, thereby facilitating understanding and controlling chemical reactivity. By extending our investigation to include intermediate species along the evolution of ethene through methylation and epoxidation, we can develop an understanding of how the orbital electronic structure evolves through this series of important chemicals. Full article

Titanium and its alloys are the most widely used metallic materials for bone contact implants. However, despite advances in implant technology, these alloys are still susceptible to post-operative clinical complications such as inflammation, which is often joined by infections and biofilm formation. A number of coatings were studied to overcome the drawbacks of these complications, but the controlled release of bioactive molecules over the first few days and the adhesion of the coating to the substrate remain recognized challenges. Carbon dots and the antibacterial potential of chiral carbon dots (CCDs) were recently reported, and their chirality was identified as a major contribution to the bactericidal effect. This study aimed to achieve a stimuli-responsive medium-term controlled release for up to one month. Two types of chiral carbon dots (CCDs) with distinct functional groups were incorporated into a stable and adherent biodegradable polymer coating, i.e., poly(lactic-co-glycolic acid) (PLGA). To enhance the coating adhesion, the titanium alloy surfaces were pre-treated and activated. The wettability, morphology, and surface composition of the coatings were characterized by contact angle, profilometry, SEM, and XPS, respectively. Coating degradation, adhesion, and CCDs release were studied at physiological pH (7.4) and at an acidic pH characteristic of an inflammatory site (pH 3.0) for up to one month. Their biological performances and blood compatibility were assessed as well. Degradation studies conducted over 28 days revealed a slow mass loss of approximately 10%, with maximum release rates for CCDs-OH and CCDs-NH₂ of 67% and 45% at pH 7.4, respectively. At pH 3.0 an inverse trend was observed with 49% and 59% maximum release after 28 days. Furthermore, the coatings did not exhibit any cytotoxic and hemolytic effects. These findings demonstrate the potential of this approach to providing titanium implants with pH-sensitive controlled release of bioactive CCDs lasting up to one month, which could address key challenges in implant-associated complications. Full article

We propose a single-phase chiral elastic metamaterial capable of simultaneously exhibiting negative effective mass density and negative bulk modulus in the ultrasonic frequency range. The unit cell consists of a regular hexagonal frame connected to a central circular mass through six obliquely oriented, slender aluminum beams. The design avoids the manufacturing complexity of multi-phase systems by relying solely on geometric topology and chirality to induce dipolar and rotational resonances. Dispersion analysis and effective parameter retrieval confirm a double-negative frequency region from 30.9 kHz to 34 kHz. Finite element simulations further demonstrate negative refraction behavior when the metamaterial is immersed in water and subjected to 32 kHz and 32.7 kHz incident plane wave. Equifrequency curves (EFCs) analysis shows excellent agreement with simulated refraction angles, validating the material’s double-negative performance. This study provides a robust, manufacturable platform for elastic wave manipulation using a single-phase metallic metamaterial design. Full article

The growing need for developing safer and more effective methods for obtaining enantiomers of chiral compounds, particularly those with pharmacological activity, highlights the potential of biocatalysis as an appropriate pharmaceutical research direction. However, low catalytic activity and stability of free enzymes are often among the substantial limitations to the wide application of biocatalysis. Therefore, to overcome these obstacles, new technological procedures are being designed. In this study, we present optimized protocols for the immobilization of Candida antarctica lipase B (CALB) on an octyl- agarose support, ensuring high enantioselectivity in an organic reaction medium. The immobilization procedures (with drying step), including buffers with different pH values and concentrations, as well as the study of the influence of temperature and immobilization time, were presented. It was found that the optimal conditions were provided by citrate buffer with a pH of 4 and a concentration of 300 mM. The immobilized CALB on the octyl-agarose support exhibited high catalytic activity in the kinetic resolution of (R,S)-1-phenylethanol via enantioselective transesterification with isopropenyl acetate in 1,2-dichloropropane (DCP), as a model reaction for lipase activity monitoring on an analytical scale. HPLC analysis demonstrated that the (R)-1-phenylethyl acetate was obtained in an enantiomeric excess of ee_p > 99% at a conversion of approximately 40%, and the enantiomeric ratio was E > 200. Thermal and storage stability studies performed on the immobilized CALB octyl-agarose support confirmed its excellent stability. After 7 days of thermal stability testing at 65 °C in a climatic chamber, the (R)-1-phenylethyl acetate was characterized by enantiomeric excess of ee_p > 99% at a conversion of around 40% (similar values of catalytic parameters to those achieved using a non-stored lipase). The documented high catalytic activity and stability of the developed CALB-octyl-agarose support allow us to consider it as a useful tool for enantioselective transesterification in organic medium. Full article

We review the in-medium modifications of effective masses (Lorentz scalar potentials or phenomenon of mass shift) of the heavy–heavy and heavy–light mesons in symmetric nuclear matter and their nuclear bound states. We use a combined approach with the quark–meson coupling (QMC) model and an effective Lagrangian. As demonstrated by the cases of pionic and kaonic atoms, studies of the meson–nucleus bound state can provide us with important information on chiral symmetry in a dense nuclear medium. In this review, we examine the mesons, $K,K^{\ast },D,D^{\ast },B,B^{\ast },\eta ,{\eta }^{\prime },\varphi ,{\eta }_c,J/\psi ,{\eta }_b,\mathsf{{\rm Y}}$, and $B_c$, where our emphasis is on the heavy mesons. In addition, we also present some new results for the $B_c$-nucleus bound states. Full article

Quasibound states in the continuum (qBICs) have aroused much attention as a feasible stage to investigate optical strong coupling due to their extremely high-quality factors (Q-factors) and extraordinary electromagnetic field enhancement. However, current demonstrations of strong coupling based on qBICs have primarily focused on the visible spectral range, while research in the near-infrared (NIR) regime remains scarce. In this work, we design a nanograting metasurface supporting Friedrich–Wintgen bound states in the continuum (FW BICs). We demonstrate that FW BIC formation stems from destructive interference between Fabry–Pérot cavity modes and metal–dielectric hybrid guided-mode resonances. To investigate the qBIC–exciton coupling system, we simulated the interaction between MoTe₂ excitons and nanograting metasurfaces. A Rabi splitting of 55.4 meV was observed, which satisfies the strong coupling criterion. Furthermore, a chiral medium layer is modeled inside the nanograting metasurface by rewriting the weak expression and boundary conditions. A mode splitting of the qBIC–chiral medium system in the circular dichroism (CD) spectrum demonstrates that the chiral response successfully transferred from the chiral medium layer to the exciton–polaritons systems through strong coupling. In comparison to the existing studies, our work demonstrates a significantly larger CD signal under the same Pascal parameters and with a thinner chiral dielectric layer. Our work provides a new ideal platform for investigating the strong coupling based on quasibound states in the continuum, which exhibits promising applications in near-infrared chiral biomedical detection. Full article

The interaction of a Gaussian vortex beam (GVB) with metamaterials during its propagation is of significant interest to the optical community. These GVBs are classified as structured light beams that possess orbital angular momentum (OAM). Understanding the behavior of structured light beams is essential for clarifying fundamental interaction mechanisms with metamaterial structures. So, this work delves into the investigation of the propagation characteristics of a GVB within a chiral material. The analytical expressions for GVB propagating through a chiral medium are obtained by using the extended Huygens–Fresnel diffraction integral formula and the optical ABCD matrix system. In a chiral medium, GVB exhibits a tendency to fragment into a left circularly polarized (LCP) beam and a right circularly polarized (RCP) beam, each following its unique propagation paths. The beam intensity and gradient force are computed and discussed for OAM mode number, beam waist radius, and chirality parameter. This research will be quite helpful for light manipulation, optical sorting, optical radiation force, the radiative transfer process, and optical guiding. Full article

The significance of the chiral symmetry restoration is studied by considering the role of the modification of the nucleon mass in nuclear medium at finite density and temperature. Using the Korea-IBS-Daegu-SKKU density functional theory, we can create models that have an identical nuclear matter equation of state but different isoscalar and isovector effective masses at zero temperature. The effect of the effective mass becomes transparent at non-zero temperatures, and it becomes more important as temperature increases. The role of the effective mass is examined thoroughly by calculating the dependence of thermodynamic variables such as free energy, internal energy, entropy, pressure and chemical potential on density, temperature and proton fraction. We find that sensitivity to the isoscalar effective mass is several times larger than that of the isovector effective mass, so the uncertainties arising from the effective mass are dominated by the isoscalar effective mass. In the analysis of the relative uncertainty, we obtain that the maximum uncertainty is less than 2% for free energy, internal energy and chemical potential, but it amounts to 20% for pressure. Entropy shows a behavior completely different from the other four variables that the uncertainty is about 40% at the saturation density and increases monotonically as density increases. The effect of the uncertainty to properties of physical systems is investigated with the proto-neutron star. It is shown that temperature depends strongly on the effective mass at a given density, and substantial swelling of the radius occurs due to the finite temperature. The equation of state is stiffer with smaller isoscalar effective mass, so the effect of the effective mass appears clearly in the mass–radius relation of the proto-neutron star, where a larger radius corresponds to a smaller effective mass. Full article

We present a theoretical framework that allows one to make an explicit connection between the phenomenology of QCD, namely the properties of the gluon correlator and Wilson loops, and a particular relativistic model for the description of nuclear matter and neutron stars: the chiral confining model. Starting with the field correlator method, which explicitly and simultaneously incorporates confinement and chiral symmetry breaking, we describe how to obtain the response of the composite nucleon to the nuclear scalar field, as well as the relative role of confinement and chiral symmetry breaking in in-medium nucleon mass evolution, thereby generating the three-body forces needed for the saturation mechanism. Full article

The range of chemical databases available has dramatically increased in recent years, but the reliability and quality of their data are often negatively affected by human-error fidelity. The size of chemical databases can make manual data curation/checking of such sets time consuming; thus, automated tools to help this process are highly desirable. Herein, we propose the use of Graph Neural Networks (GNNs) to identifying potential stereochemical misassignments in the primary asymmetric catalysis literature. Our method relies on the use of an ensemble of GNN models to predict the expected stereoselectivity of exemplars for a particular asymmetric reaction. When the majority of these models do not correlate to the reported outcome, the point is labeled as a possible stereochemical misassignment. Such identified cases are few in number and more easily investigated for their cause. We demonstrate the use of this approach to spot potential literature stereochemical misassignments in the ketone products resulting from catalytic asymmetric 1,4-addition of organoboron nucleophiles to Michael acceptors in two different databases, each one using a different family of chiral ligands (bisphosphine and diene ligands). Our results demonstrate that this methodology is useful for curation of medium-sized databases, speeding this process significantly compared to complete manual curation/checking. In the datasets investigated, human expert checking was reduced to 2.2% and 3.5% of the total data exemplars. Full article

Plasmon chirality has garnered significant interest in sensing application due to its strong electromagnetic field localization and highly tunable optical properties. Understanding the effects of mode coupling in chiral structures on chiral optical activity is particularly important for advancing this field. In this work, we numerically investigate the circular dichroism (CD) of elliptical nanodisk dimers arranged in an up-and-down configuration with a specific rotation angle. By adjusting the inter-particle distance and geometric parameters, we introduce the coupling between dipole and electric hexapole modes, forming an extended Born–Kuhn model that achieves strong CD. Our findings show that the coupling of dipole modes with electric hexapole modes in elliptical nanodisks can also show obvious Fano resonance and a strong CD effect, and the structure with the largest Fano asymmetry factor shows the highest CD. In addition, CD spectroscopy is highly sensitive to changes in the refractive index of the surrounding medium, especially in the visible and near-infrared regions, highlighting its potential for application in high-sensitivity refractive index sensors. Full article

The geometric shape, symmetry, and topology of colloidal particles often allow for controlling colloidal phase behavior and physical properties of these soft matter systems. In liquid crystalline dispersions, colloidal particles with low symmetry and nontrivial topology of surface confinement are of particular interest, including surfaces shaped as handlebodies, spirals, knots, multi-component links, and so on. These types of colloidal surfaces induce topologically nontrivial three-dimensional director field configurations and topological defects. Director switching by electric fields, laser tweezing of defects, and local photo-thermal melting of the liquid crystal host medium promote transformations among many stable and metastable particle-induced director configurations that can be revealed by means of direct label-free three-dimensional nonlinear optical imaging. The interplay between topologies of colloidal surfaces, director fields, and defects is found to show a number of unexpected features, such as knotting and linking of line defects, often uniquely arising from the nonpolar nature of the nematic director field. This review article highlights fascinating examples of new physical behavior arising from the interplay of nematic molecular order and both chiral symmetry and topology of colloidal inclusions within the nematic host. Furthermore, the article concludes with a brief discussion of how these findings may lay the groundwork for new types of topology-dictated self-assembly in soft condensed matter leading to novel mesostructured composite materials, as well as for experimental insights into the pure-math aspects of low-dimensional topology. Full article

This study aimed to optimize the kinetic resolution of building blocks for the synthesis of β-blockers using Candida rugosa lipases, which could be potentially used to synthesize enantiomerically pure β-blockers further. Reaction mixtures were incubated in a thermostated shaker. Qualitative and quantitative analyses of the reaction mixtures were performed using chiral stationary phases and the UPLC-IT-TOF system. Of the 24 catalytic systems prepared, a system containing lipase from Candida rugosa MY, [EMIM][BF₄] and toluene as a two-phase reaction medium and isopropenyl acetate as an acetylating agent was optimal. This resulted in a product with high enantiomeric purity produced via biotransformation, whose enantioselectivity was E = 67.5. Using lipases from Candida rugosa enables the enantioselective biotransformation of the β-blockers building block. The biocatalyst used, the reaction environment, and the acetylating agent significantly influence the efficiency of performer kinetic resolutions. The studies made it possible to select an optimum system, a prerequisite for obtaining a product of high enantiomeric purity. As a result of the performed biotransformation, the (S)-enantiomer of the β-blocker derivative was obtained, which can be used to further synthesize enantiomerically pure β-blockers. Full article

3,4-Methylenedioxypyrovalerone (MDPV) is an emerging, chiral, new psychoactive substance belonging to the synthetic cathinones group that has been frequently detected in wastewater effluents and aquatic environments. However, the knowledge of its enantioselective occurrence and toxicity toward aquatic organisms is scarce. The aim of this work was to develop an enantioselective liquid chromatography (LC) method to monitor the enantiomers of MDPV in environmental and ecotoxicological assays. For that, different chiral columns and mobile phases in both normal and reversed elution modes were attempted. The optimized conditions were achieved using a Daicel^® 3 μm—CHIRALPAK^® IF-3 column with 5 mM of ammonium bicarbonate (NH₄HCO₃, pH 8.8) in ultra-pure water (UPW) and acetonitrile (ACN) (10:90, v/v) as a mobile phase, at a flow rate of 0.3 mL min⁻¹. This condition was applied to monitor the racemate and the single enantiomers of MDPV in culture medium collected from ecotoxicity experiments. Racemization was observed for MDPV enantiomers (in individual exposure). The enantiomeric ratio (e.r.) of (S)-MDPV changed from an initial e.r. of 96.4/3.6 to 78.0/22.0 and for the (R)-enantiomer, the e.r changed from 15.6/84.4 to 28.3/71.7). These data highlight the importance of enantioselective monitoring of culture media in toxicity assays that involve chiral substances, since racemization can occur and lead to inaccuracy in the toxicity evaluation. Nevertheless, it is also important to stress that racemization may occur during storage conditions or sample procedures. Therefore, the enantioselective methodology is of utmost importance to warrant the quality of the results in enantioselective ecotoxicological studies. Full article

The interaction of propane-1,3-dithiol with the chiral bis-thioether, which combines two 2(5H)-furanone moieties, bridged through their carbon atoms C(4) by the propane-1,3-dithiol fragment, in DMF in the presence of potassium hydroxide or cesium carbonate resulted in the formation of an optically active fused bicyclic sulfur heterocycle, possessing 1,4-dithiepine and unsaturated γ-lactone moieties. The studied reaction follows an unexpected pathway in a basic medium with the thiolate–thiolate exchange. The structure of the novel heterocycle of the 1,4-dithiepinofuranone series is characterized by single-crystal X-ray diffraction. Full article