Search Results (445)

This study addressed the issue of insufficient activity in CALB lipase during the catalytic synthesis of key chiral intermediates for moxifloxacin. A structure-guided protein engineering strategy was employed to systematically modify its functional domains. Through molecular dynamics simulations of CALB-I189K, multiple regions exhibiting high conformational flexibility were preliminarily identified. Subsequently, by integrating 3D structural alignment with active site pocket distance analysis, the functionally most critical region (143–146) was selected. A site-directed saturation mutation library was constructed specifically targeting this region. Building upon the previously reported CALB-I189K, a mutant I189K/L144R/A146K was ultimately obtained through high-throughput screening combined with chiral HPLC validation. This mutant maintains excellent stereoselectivity (E = 206.52) while enhancing catalytic efficiency (k_cat/Κ_m) to 273.73 min⁻¹·mM⁻¹, approximately 4.5-fold that of I189K. At a substrate concentration of 1 M, it achieves 50% conversion within 2.6 h, demonstrating kinetic resolution capabilities approaching industrial standards. Molecular simulation analysis indicates that the L144R and A146K mutations synergistically enhance catalytic performance primarily by optimizing spatial distances between catalytic residues. This study not only provides a high-performance catalyst for the efficient biosynthesis of moxifloxacin chiral intermediates but also offers new insights for enzyme rational design based on dynamic structural information. Full article

The size-dependent out-of-plane vibrational behavior of graphene-based nanoelectromechanical (NEMS) resonators is investigated using a molecular mechanics (MM) finite element approach. Each carbon–carbon (C–C) bond is modeled as an Euler–Bernoulli beam element, with the bending stiffness derived from the bond-angle potential, yielding an equivalent plate flexural rigidity D = (√3/6) kθ. The natural frequencies of the first four vibration modes are computed for square graphene sheets of increasing size with both zigzag (ZZ) and armchair (AC) chirality configurations under simply supported boundary conditions on all four edges. A chirality-induced frequency deviation δ(L) is defined to quantify the difference between ZZ and AC results, and a threshold size L* is identified as the sheet size at which δ falls below 1%. For mode 1, the threshold is L* = 18.5 nm; the values increase monotonically to 24.5 nm, 28.0 nm, and 31.5 nm for modes 2 through 4, indicating that higher modes require larger sheet dimensions before continuum plate theory becomes reliable. A dimensionless frequency parameter Ω = f_MM/f_CT is introduced to directly compare MM predictions with the Kirchhoff plate theory analytical solution, and the AC frequency ratio Ω = f_MM/f_CT is shown to converge toward unity with increasing sheet size. The present results provide quantitative design guidelines for graphene NEMS resonators and establish the minimum device dimensions for which isotropic continuum models yield accurate dynamic predictions. Full article

Chirality is a pervasive and functionally critical feature of biological macromolecules, yet its distributed and emergent forms remain poorly quantified in complex systems such as membrane proteins. We present Chirobiophore, a novel paradigm for capturing biochirality across scales—from atomic geometries to global structural asymmetries. Unlike traditional stereochemical metrics, Chirobiophore employs a multidimensional model-independent vector comprising Local Tetrahedral Asymmetry (LTA), Helical Path Curvature (HPC), Asymmetric Environment Score (AES), Directional Density Profile (DDP), Leaflet Asymmetry Index (LAI), and Orientation Twist Score (OTS). This framework enables coordinate-invariant comparisons of structurally diverse proteins in a continuous chirality space. We demonstrate its application to canonical, GPCR, and topologically complex membrane proteins, revealing distinct chirality signatures and functional clustering. Furthermore, we map Chirobiophore descriptors to tissue-level asymmetry indices, providing a bridge between molecular structure and morphogenetic patterning. Chirobiophore offers a unified, extensible platform for structural biology, synthetic design, and developmental modeling of chirality. Full article

Imine reductases (IREDs) have emerged as valuable biocatalysts for the asymmetric synthesis of chiral amines, key intermediates in numerous active pharmaceutical ingredients. Their ability to operate under mild reaction conditions with high chemo- and stereoselectivity provides an attractive alternative to conventional metal-catalyzed or chemical reduction processes. However, the broader industrial application of wild-type IREDs is often constrained by their limited substrate scope and moderate catalytic efficiency. Recent advances in biocatalysis have demonstrated that engineered IREDs can catalyze the reduction of a wide range of natural and non-natural imines, significantly expanding their applicability in pharmaceutical and fine chemical synthesis. In parallel, enzyme immobilization strategies have proven highly effective for improving operational stability, facilitating enzyme reuse, and enabling continuous flow biocatalytic processes. Efficient cofactor regeneration systems have further enhanced the practical implementation of IRED-based transformations. Advances in protein engineering, including structure-guided design, semi-rational mutagenesis, and directed evolution, have generated enzyme variants with improved catalytic activity, stereoselectivity, and substrate tolerance. The integration of high-throughput screening technologies and machine-learning-assisted enzyme design has further accelerated the discovery and optimization of efficient IRED biocatalysts. This review summarizes recent progress in the protein engineering and immobilization of IREDs and discusses future perspectives for their industrial application. Full article

Hollow auxetic structures enable lightweight mechanical design by reducing mass while preserving architected deformation. However, hollow auxetic studies focus on LPBF metals. This study presents a manufacturing-constrained design and validation framework for a hollow hybrid re-entrant chiral lattice produced by stereolithography. The unit cell was parameterised by chiral angle, re-entrant strut length, and hollow internal diameter, with drainage features integrated into the CAD model to preserve hollow channels during printing and post-processing. A minimum internal diameter study defined the printable design window. Within these limits, a central composite design coupled with finite element analysis mapped the response surface and identified an optimised geometry of θ = 15°, L = 3.5 mm, and d = 1.68 mm, with a predicted unit-cell negative Poisson’s ratio of about −1.17. Compression testing confirmed that the printed unit cell and 3 × 3 × 3 lattice retained the intended rotation-dominated auxetic deformation mode. At the selected comparison strain, the unit cell showed a negative Poisson’s ratio of −0.68 and the 3 × 3 × 3 lattice showed −0.29. Relative to the solid lattice, the hollow lattice reduced density by 42.4% with only a 3.0% reduction in stiffness, increasing specific stiffness by 68.9% and specific peak strength by 5.2%, but reducing specific energy absorption by 25.6% due to earlier localisation and junction driven fracture. These results provide practical design guidance for manufacturable hollow SLA auxetic lattices, especially for lightweight and stiffness-limited applications where low mass and high specific stiffness are more important than energy absorption. Full article

The on-chip detection of circularly polarized light is pivotal for advancing applications in quantum optics, information processing, and spectroscopic sensing. However, conventional chiral metasurfaces often suffer from complex multilayer fabrication, material incompatibility, or modest performance, hindering their integration with photonic circuits. Here, we introduce a monolithic all-silicon metasurface that overcomes these limitations through a singular structural innovation. By strategically truncating four corners of a conventional Z-shaped meta-atom, we induce a hybridization of optical modes that profoundly enhances chiral light–matter interaction. This deliberately engineered perturbation yields a colossal circular dichroism with an extinction ratio exceeding 66 dB, a performance that surpasses existing state-of-the-art designs by approximately three orders of magnitude. Furthermore, the proposed metasurface exhibits remarkable fabrication robustness, owing to its single-layer architecture and CMOS-compatible material. We demonstrate that this exceptional metasurface can be directly integrated with a Mercury Cadmium Telluride (MCT) photodetector to form a highly efficient, compact circular polarization detector. Our work provides a simple yet powerful paradigm for creating high-performance chiral photonic devices, paving the way for their widespread adoption in integrated optoelectronics. Full article

Chiral bound states in the continuum (BIC) metasurfaces have emerged as a promising platform for enhancing light–matter interactions, which have potential applications in advanced photonic and quantum information devices. However, simultaneously achieving near-perfect circular dichroism and highly efficient nonlinear conversion with highly symmetric structures in metasurfaces remains an open challenge. In this work, we design a $C_4$-symmetric chiral metasurface composed of eight elliptical silicon nanorods on a ${\mathrm{SiO}}_2$ substrate, where monocrystalline silicon is used as the nonlinear optical material. By combining simulations and nonlinear time-domain coupled-mode theory (TCMT), we discovered that both the optimal chirality and the nonlinear conversion efficiency can be attained simultaneously due to the critical coupling between the metasurface mode and the quasi-BIC mode. Meanwhile, a near-perfect circular dichroism (CD = 0.99) and a high nonlinear conversion efficiency of $7\times {10}^{-5}$ under a radiation intensity of $5{\mathrm{kW}/\mathrm{cm}}^2$ are numerically achieved due to the robustness of bound states in the continuum. This work offers a promising route toward high-performance chiral nonlinear photonic components, which is of great importance for the development of ultra-compact optical devices such as circular polarization detectors, chiral sensors, and nonlinear photonic chips for integrated optical and quantum information systems. Our research not only contributes to the fundamental understanding of chiral metasurfaces but also provides a practical approach for achieving high-efficiency nonlinear optical devices. Full article

This paper reports the chiral separation of menthol enantiomers using the VARICOL process to improve productivity. Amylose 3,5-dimethylphenylcarbamate coated on silica gel was employed as the chiral stationary phase, and n-hexane/2-propanol (95/5, v/v) was used as the eluent. To design and optimize the VARICOL process, a linear driving-force model was developed to predict the separation performance. Separation regions of the conventional simulated moving bed (SMB) and VARICOL processes were evaluated and compared. It was found that, under an outlet purity requirement of 95.0%, the five-column VARICOL process has a separation region comparable to that of the six-column conventional SMB process. As an illustrative example, a five-column VARICOL unit and a six-column conventional SMB unit, both operating under the same conditions, were employed to resolve the menthol racemate. Purities for both the extract and raffinate were above 95.0%, and a productivity of 0.400 g_racemate/(L_CSP∙min) and a solvent consumption of 0.355 L/g_racemate were achieved in the VARICOL process. Productivity increased by 20% while solvent consumption maintained relative to the conventional SMB process, though product purities decreased slightly. Full article

Axially chiral compounds, indispensable in asymmetric catalysis, drug discovery, and materials science, have witnessed transformative advancements in synthesis through organocatalytic kinetic resolution (OKR) over the past decade. This review systematically dissects the latest achievements (2010–2025) in OKR, focusing on catalyst design, mechanistic insights, substrate diversification, and synthetic applications across C–C biaryl, C–N heterobiaryl, and olefinic axially chiral frameworks. By harnessing non-covalent interactions, OKR has emerged as a powerful strategy to overcome the challenges of low rotational barriers and limited stereocontrol, offering sustainable and enantioselective access to privileged chiral scaffolds. Furthermore, the current challenges and future prospects in this rapidly evolving field are assessed. Full article

l-menthol is one of the most popular flavors in the world. The separation of menthol enantiomers is crucial because of the unpleasant taste of d-menthol. This work presents the chiral separation of racemic menthol by simulated moving bed chromatography for the first time. Six preparative columns packed with amylose 3,5-dimethylphenylcarbamate coated on silica gel were used for separation, and a mixture of n-hexane/isopropanol was selected as the mobile phase. The hydrodynamic properties of the SMB columns were studied to minimize the packing asymmetry in the SMB experiment. The binary adsorption isotherm of menthol enantiomers was measured by the adsorption–desorption method. Fixed-bed batch chromatography was carried out to evaluate the adsorption kinetic behavior. Mathematical models, considering the mass transfer resistance and axial dispersion, were applied to describe the dynamics of the chromatographic separation process. The SMB process for chiral separation of racemic menthol was designed by evaluating the separation region using simulations. Reasonable agreements were achieved between the predicted results and the experimental results. Purities for both the extract and raffinate were above 99.0%, and a productivity of 0.267 g_racemate/(L_CSP∙min) and a solvent consumption of 0.431 L/g_racemate were achieved. Full article

The induction of chirality to obtain enantiopure products of high synthetic value is of great importance across various scientific fields, particularly in the medical area, as it has been demonstrated that the different enantiomers of drugs interact differently with biological receptors. In this context, asymmetric catalysis focuses on the design of catalysts that are easy to synthesize, capable of efficiently and enantioselectively forming C–C bonds, and suitable for reuse in multiple catalytic processes. This work describes the application of a Pd(II) complex coordinated with the R and S forms of proline in direct Aldol, Morita–Baylis–Hillman, and Heck coupling reactions. The catalytic system efficiently promoted the aldol reaction, achieving yields of 80–95%, excellent diastereoselectivities (1:69 syn/anti), and enantiomeric excesses greater than 99%. From a mechanistic perspective, the formation of a transition state is proposed in which a proline molecule generates an enamine that, upon coordination with the metal center, is stabilized through interaction with the intermediate’s double bond. Moreover, the study of the Morita–Baylis–Hillman and Heck coupling reactions highlights the versatility of this type of catalyst. Full article

The synthesis of enantiomerically pure chiral β-nitroalcohols is a crucial objective in asymmetric catalysis. In order to efficiently obtain such chiral products, we developed a series of thermoresponsive, oxazoline–copper catalysts (Cu^II-PN_xFe_yO_z) via sequential reversible addition–fragmentation chain transfer (RAFT) polymerization. These catalysts can self-assemble in water into single-chain nanoparticles (SCNPs) with biomimetic behavior, in which intramolecular hydrophobic and metal-coordination interactions generate a confined hydrophobic cavity. Comprehensive characterization by FT-IR, TEM, DLS, CD, CA, and ICP analysis confirmed the nanostructure and composition. When applied to the aqueous-phase asymmetric Henry reaction between nitromethane and 4-nitrobenzaldehyde, the optimal catalyst (2.0 mol%) achieved a quantitative yield (96%) with excellent enantioselectivity (up to 99%) within 12 h. Furthermore, the thermosensitive poly(N-isopropylacrylamide, NIPAAm) block enabled facile catalyst recovery through temperature-induced precipitation above its lower critical solution temperature (LCST). This work presents an efficient and recyclable biomimetic catalytic system, offering a novel strategy for designing sustainable chiral catalysts for green organic synthesis. Full article

Planar chiral bisphosphine ligands based on diphenyl [2.2]paracyclophane (PhPhanePHOS) were successfully synthesized in a practical manner in four steps from commercially available 4,12-bisbromo-[2.2]paracyclophane as a new family of bisphosphine ligands. The novel PhPhanePHOS ligands provide high catalytic activity in Pd-catalyzed asymmetric allylic alkylation reactions in preliminary experiments. Full article

Chiral metasurfaces exhibit enormous potential in optical applications, and their integration with phase-change material vanadium dioxide (VO₂) provides a novel pathway for dynamic regulation. In this study, a chiral absorptive metasurface based on VO₂ is designed. By tuning the VO₂ conductivity around the operating frequency of 2.81 THz, the circular dichroism (CD) can be continuously adjusted from 0.06 to 0.95, realizing a high-contrast chiral switch. On this basis, the Pancharatnam–Berry (PB) phase is introduced to construct a chirality-dependent phase gradient: when the VO₂ conductivity is 200,000 S/m, only the left-handed circularly polarized (LCP) wave is subjected to periodic phase modulation, enabling controllable deflection of the reflected beam, while the right-handed circularly polarized (RCP) wave is selectively absorbed. This “chiral phase encoding” strategy simultaneously achieves absorptive CD tuning and reflective beam shaping on a single metasurface, significantly enhancing the flexible manipulation capability of circular polarization states in the terahertz band. It provides a compact and efficient solution for reconfigurable imaging, unidirectional communication, and integrated photonics systems. Full article

Vertical cavity surface emitting lasers (VCSELs) have shown great potential in high-speed communication, quantum information processing, and 3D sensing due to their excellent beam quality and low power consumption. However, generating high-purity and controllable circularly polarized light usually requires external optical components such as quarter-wave plates, which undoubtedly increases system complexity and volume, hindering chip-level integration. To address this issue, we propose a monolithic integration scheme that directly integrates a custom-designed double-layer asymmetric metasurface onto the upper distributed Bragg reflector of a chiral VCSEL. This metasurface consists of a rotated GaAs elliptical nanocolumn array and an anisotropic grating above it. By precisely controlling the relative orientation between the two, the in-plane symmetry of the structure is effectively broken, introducing a significant optical chirality response at a wavelength of 1550 nm. Numerical simulations show that this structure can achieve a near 100% high reflectivity for the left circularly polarized light (LCP), while suppressing the reflectivity of the right circularly polarized light (RCP) to approximately 33%, thereby obtaining an efficient in-cavity circular polarization selection function. Based on this, the proposed VCSEL can directly emit high-purity RCP without any external polarization control components. This compact circularly polarized laser source provides a key solution for achieving the next generation of highly integrated photonic chips and will have a profound impact on frontier fields such as spin optics, secure communication, and chip-level quantum light sources. Full article