Tellurene,a chiral chain semiconductor with a narrow bandgap and exceptional strain sensitivity,emerges as a pivotal material for tailoring electronic and optoelectronic properties via strain engineering.This study el...Tellurene,a chiral chain semiconductor with a narrow bandgap and exceptional strain sensitivity,emerges as a pivotal material for tailoring electronic and optoelectronic properties via strain engineering.This study elucidates the fundamental mechanisms of ultrafast laser shock imprinting(LSI)in two-dimensional tellurium(Te),establishing a direct relationship between strain field orientation,mold topology,and anisotropic structural evolution.This is the first demonstration of ultrafast LSI on chiral chain Te unveiling orientation-sensitive dislocation networks.By applying controlled strain fields parallel or transverse to Te’s helical chains,we uncover two distinct deformation regimes.Strain aligned parallel to the chain’s direction induces gliding and rotation governed by weak interchain interactions,preserving covalent intrachain bonds and vibrational modes.In contrast,transverse strain drives shear-mediated multimodal deformations—tensile stretching,compression,and bending—resulting in significant lattice distortions and electronic property modulation.We discovered the critical role of mold topology on deformation:sharp-edged gratings generate localized shear forces surpassing those from homogeneous strain fields via smooth CD molds,triggering dislocation tangle formation,lattice reorientation,and inhomogeneous plastic deformation.Asymmetrical strain configurations enable localized structural transformations while retaining single-crystal integrity in adjacent regions—a balance essential for functional device integration.These insights position LSI as a precision tool for nanoscale strain engineering,capable of sculpting 2D material morphologies without compromising crystallinity.By bridging ultrafast mechanics with chiral chain material science,this work advances the design of strain-tunable devices for next-generation electronics and optoelectronics,while establishing a universal framework for manipulating anisotropic 2D systems under extreme strain rates.This work discovered crystallographic orientation-dependent deformation mechanisms in 2D Te,linking parallel strain to chain gliding and transverse strain to shear-driven multimodal distortion.It demonstrates mold geometry as a critical lever for strain localization and dislocation dynamics,with sharp-edged gratings enabling unprecedented control over lattice reorientation.Crucially,the identification of strain field conditions that reconcile severe plastic deformation with single-crystal retention offers a pathway to functional nanostructure fabrication,redefining LSI’s potential in ultrafast strain engineering of chiral chain materials.展开更多
Constructing a framework carrier to stabilize protein conformation,induce high embedding efficiency,and acquire low mass-transfer resistance is an urgent issue in the development of immobilized enzymes.Hydrogen-bonded...Constructing a framework carrier to stabilize protein conformation,induce high embedding efficiency,and acquire low mass-transfer resistance is an urgent issue in the development of immobilized enzymes.Hydrogen-bonded organic frameworks(HOFs)have promising application potential for embedding enzymes.In fact,no metal involvement is required,and HOFs exhibit superior biocompatibility,and free access to substrates in mesoporous channels.Herein,a facile in situ growth approach was proposed for the self-assembly of alcohol dehydrogenase encapsulated in HOF.The micron-scale bio-catalytic composite was rapidly synthesized under mild conditions(aqueous phase and ambient temperature)with a controllable embedding rate.The high crystallinity and periodic arrangement channels of HOF were preserved at a high enzyme encapsulation efficiency of 59%.This bio-composite improved the tolerance of the enzyme to the acid-base environment and retained 81%of its initial activity after five cycles of batch hydrogenation involving NADH coenzyme.Based on this controllably synthesized bio-catalytic material and a common lipase,we further developed a two-stage cascade microchemical system and achieved the continuous production of chiral hydroxybutyric acid(R-3-HBA).展开更多
In recent years,chiral inorganic nanomaterials have become promising candidates for applications in sensing,catalysis,biomedicine,and photonics.Plasmonic nanomaterials with an intrinsic chiral structure exhibit intrig...In recent years,chiral inorganic nanomaterials have become promising candidates for applications in sensing,catalysis,biomedicine,and photonics.Plasmonic nanomaterials with an intrinsic chiral structure exhibit intriguing geometry‑dependent optical chirality,which benefits the combination of plasmonic characteristics with chirality.Recent advances in the biomolecule‑directed geometric control of intrinsically chiral plasmonic nanomaterials have further provided great opportunities for their widespread applications in many emerging technological areas.In this review,we present the recent progress in biosensing using chiral inorganic nanomaterials,with a particular focus on electrochemical and enzyme‑mimicking catalytic approaches.This paper commences with a review of the basic tenets underlying chiral nanocatalysts,incorporating the chiral ligand‑induced mechanism and the architectures of intrinsically chiral nanostructures.Additionally,it methodically expounds upon the applications of chiral nanocatalysts in the realms of electrochemical biosensing and enzyme‑mimicking catalytic biosensing respectively.Conclusively,it proffers a prospective view of the hurdles and prospects that accompany the deployment of chiral nanoprobes for nascent biosensing applications.By rational design of the chiral nanoprobes,it is envisioned that biosensing with increasing sensitivity and resolution toward the single‑molecule level can be achieved,which will substantially promote sensing applications in many emerging interdisciplinary areas.展开更多
The catalytic enantioselective electrophilic amination reaction has emerged as a highly efficient method for synthesizing diverse nitrogen-containing chiral molecules,with the development of various asymmetric catalys...The catalytic enantioselective electrophilic amination reaction has emerged as a highly efficient method for synthesizing diverse nitrogen-containing chiral molecules,with the development of various asymmetric catalysis systems.Chiral phosphoric acids(CPA)have been widely acknowledged as versatile chiral organocatalysts since it was first discovered in 2004,finding application in catalyzing diverse asymmetric reactions.A comprehensive overview of recent advances in CPA-catalyzed asymmetric electrophilic amination reactions using different N-electrophilic reagents,including azo reagents,aryldiazonium salts,and imine derivatives,is presented.Furthermore,insights into future developments in this field are offered.展开更多
The precise manipulation of chiral crystallization for the fabrication of homochiral surfaces has emerged as a pivotal focal point within the realm of surface chemistry.In this investigation,we employed a temperature-...The precise manipulation of chiral crystallization for the fabrication of homochiral surfaces has emerged as a pivotal focal point within the realm of surface chemistry.In this investigation,we employed a temperature-regulated strategy,utilizing the conformationally chiral molecule 1,1,2,2-tetrakis(4-bromophenyl)ethene(TPEB)as a precursor to control the chiral recognition and separation process on Ag(111)surface mediated through Br···H and Br···Br interactions.At a temperature of 77 K,when TPEB was deposited onto the Ag(111)surface,it gives rise to two mirror-image racemic structures.As the temperature increases,TPEB molecules undergo a distinct transition from existing in racemic mixtures to enantiomeric excess mixtures.This transition ultimately culminates in a chiral separation process,resulting in the formation of a single-handed self-assembled structure and the acquisition of a homochiral Kagomélattice.This work meticulously monitored the chiral crystallization process of the conformationally chiral molecules on Ag(111)surface,capturing structures with diverse enantiomeric compositions.Moreover,through a combination of molecular simulations and density functional theory(DFT)calculations,we elucidated that an increase in temperature enhances the recognition between chiral molecules of the same handedness.This enhanced recognition,in turn,promotes the chiral separation process and steers the transition of the supramolecular assemblies from racemic mixtures towards single-handed structures.This study not only achieved the separation of heterochiral molecular conformations but also paved an effective avenue for the fabrication of homochiral nanostructures.展开更多
The presence of chirality,a fundamental attribute found in nature,is of great significance in the field of pharmaceutical science.Chiral drugs are unique in that their molecular structure is non-superimposable on its ...The presence of chirality,a fundamental attribute found in nature,is of great significance in the field of pharmaceutical science.Chiral drugs are unique in that their molecular structure is non-superimposable on its mirror image.This stereoisomerism significantly impacts the functionality,metabolic pathway,effectiveness,and safety of chiral medications.The enantiomers of chiral drugs can exhibit diverse pharmacological effects in the human body.As a result,it is essential to separate and purify chiral drugs effectively.Despite the abundance of reports on chiral drug separation membranes,there is a dearth of comprehensive reviews.This paper aims to fill this gap by providing a thorough review from a materials perspective,with a focus on the design and construction of chiral drug separation membranes.Furthermore,it systematically analyzes the separation mechanisms employed by these membranes.The paper also delves into the challenges and prospects related to chiral drug separation membranes,with the intention of imparting valuable insights for further research and development in this field.展开更多
The search for the chiral magnetic effect(CME) in relativistic heavy-ion collisions(HICs) is challenged by significant background contamination. We present a novel deep learning approach based on a U-Net architecture ...The search for the chiral magnetic effect(CME) in relativistic heavy-ion collisions(HICs) is challenged by significant background contamination. We present a novel deep learning approach based on a U-Net architecture to time-reversely unfold the dynamics of CME-related charge separation, enabling the reconstruction of the physics signal across the entire evolution of HICs. Trained on the events simulated by a multi-phase transport model with different cases of CME settings, our model learns to recover the charge separation based on final-state transverse momentum distributions at either the quark–gloun plasma freeze-out or hadronic freeze-out. This devises a methodological tool for the study of CME and underscores the promise of deep learning approaches in retrieving physics signals in HICs.展开更多
Chirality,a common phenomenon in nature,appears in structures ranging from galaxies and condensed matter to atomic nuclei.There is a persistent demand for new,high-precision methods to detect chiral structures,particu...Chirality,a common phenomenon in nature,appears in structures ranging from galaxies and condensed matter to atomic nuclei.There is a persistent demand for new,high-precision methods to detect chiral structures,particularly at the microscale.Here,we propose a novel method,vortex Mössbauer spectroscopy,for probing chiral structures.By leveraging the orbital angular momentum carried by vortex beams,this approach achieves high precision in detecting chiral structures at scales ranging from nanometers to hundreds of nanometers.Our simulation shows the ratio of characteristic lines in the Mössbauer spectra of ^(57)Fe under vortex beams exhibits differences of up to four orders of magnitude for atomic structures with different arrangements.Additionally,simulations reveal the response of ^(229m)Th chiral structures to vortex beams with opposite angular momenta differs by approximately 49-fold.These significant spectral variations indicate that this new vortex Mössbauer probe holds great potential for investigating the microscopic chiral structures and interactions of matter.展开更多
The simultaneous description for nuclear matter and finite nuclei has been a long-standing challenge in nuclear ab initio theory.With the success for nuclear matter,the relativistic Brueckner-Hartree-Fock(RBHF)theory ...The simultaneous description for nuclear matter and finite nuclei has been a long-standing challenge in nuclear ab initio theory.With the success for nuclear matter,the relativistic Brueckner-Hartree-Fock(RBHF)theory with covariant chiral interactions is a promising ab initio approach to describe both nuclear matter and finite nuclei.In the description of finite nuclei with the current RBHF theory,the covariant chiral interactions have to be localized to make calculations feasible.In order to examine the reliability and validity,in this letter,the RBHF theory with local and nonlocal covariant chiral interactions at leading order is applied to nuclear matter.The low-energy constants in the covariant chiral interactions determined with the local regularization are close to those with the nonlocal regularization.Moreover,the RBHF theory using covariant chiral interactions with local and nonlocal regulators provides an equally good description of the saturation properties of nuclear matter.The present work paves the way for the implementation of covariant chiral interactions in RBHF theory for finite nuclei.展开更多
Chiral metal-organic frameworks (CMOFs), a class of highly crystalline and porous materials with tailorable chiral characteristics, have currently become an interdisciplinary between chirality chemistry, coordination ...Chiral metal-organic frameworks (CMOFs), a class of highly crystalline and porous materials with tailorable chiral characteristics, have currently become an interdisciplinary between chirality chemistry, coordination chemistry, and material chemistry, which involve in many subjects including chemistry, physics, optics, medi-cine, pharmacology, biology, crystal engineering, environmental science, etc. Their special structural features such as porosity, modularity, and chirality have endowed them with a variety of unique effects in promoting enantioselective processes, particularly asymmetric catalysis. Here, we provide a brief review of the state of CMOF field from the privileged ligand design to the heterogeneous enantioselective catalysis. We hope that this review will provide researchers a better understanding of CMOF chemistry and facilitate the future research endeavors for rationally designing privileged chiral framework materials for challenging catalytic applications.展开更多
Chirality is a widespread physical phenomenon in nature,but natural materials often exhibit weak chiroptical responses.Recent advances have used chiral metasurfaces to enhance these responses,with applications in holo...Chirality is a widespread physical phenomenon in nature,but natural materials often exhibit weak chiroptical responses.Recent advances have used chiral metasurfaces to enhance these responses,with applications in holographic imaging,chiral molecule detection,and circularly polarized lasers.However,most chiral metasurfaces exhibit strong chiroptical responses only at fixed wavelengths,which limits their suitability for wavelength-tunable optical devices.We address this by designing a silicon-GST(silicon-Ge2Sb2Te5)hybrid metasurface with asymmetric cross-shaped units that support multi-wavelength resonances,achieving broadband and dynamically tunable CD(circular dichroism).In the amorphous phase,GST enables CD>0.7 in the range of 2,137 nm to 2,657 nm,with a PER(polarization extinction ratio)up to 38 dB.Upon transition to the crystalline phase,CD enhances with a redshift,and the sign of CD reverses.This enables dynamic wavelength tuning of broadband CD via the phase transition of GST.展开更多
With the rapid development of holographic technology,metasurface-based holographic communication schemes have demonstrated immense potential for electromagnetic(EM)multifunctionality.However,traditional passive metasu...With the rapid development of holographic technology,metasurface-based holographic communication schemes have demonstrated immense potential for electromagnetic(EM)multifunctionality.However,traditional passive metasurfaces are severely limited by their lack of reconfigurability,hindering the realization of versatile holographic applications.Origami,an art form that mechanically induces spatial deformations,serves as a platform for multifunctional devices and has garnered significant attention in optics,physics,and materials science.The Miura-ori folding paradigm,characterized by its continuous reconfigurability in folded states,remains unexplored in the context of holographic imaging.Herein,we integrate the principles of Rosenfeld with L-and D-metal chiral enantiomers on a Miura-ori surface to tailor the aperture distribution.Leveraging the continuously tunable nature of the Miura-ori's folded states,the chiral response of the metallic structures varies across different folding configurations,enabling distinct EM holographic imaging functionalities.In the planar state,holographic encryption is achieved.Under specific folding conditions and driven by spin circularly polarized(CP)waves at a particular frequency,multiplexed holographic images can be reconstructed on designated focal planes with CP selectivity.Notably,the fabricated origami metasurface exhibits a large negative Poisson ratio,facilitating portability and deployment and offering novel avenues for spin-selective systems,camouflage,and information encryption.展开更多
Organic ferroelastics with metal free features and intrinsically light weight are highly desirable for future applications in flexible,smart and biocompatible devices.However,organoferroelastics with plastic phase tra...Organic ferroelastics with metal free features and intrinsically light weight are highly desirable for future applications in flexible,smart and biocompatible devices.However,organoferroelastics with plastic phase transition have rarely been reported yet.Herein,we discovered ferroelasticity in a pair of organic enantiomers,(1S and/or 1R)-2,10-camphorsultam(S-and R-CPS),which undergoes a high-T_(c)plastic phase transition.Both large entropies change of∼45 J mol^(-1)K^(-1)and evidently ductile deformation process confirm the plastic phase feature.Strip-like ferroelastic domain patterns and bidirectional domain movements have been observed via polarized light microscopy and nanoindentation technique,respectively.This work highlights the discovery of organic ferroelastic combining the features of enantiomers and plastic phase transition,which contributes insights into exploration of organic multifunctional materials.展开更多
Planar chiral cyclophanes are a type of structurally intriguing organic molecules,which have found increasingly applications in the field of biologically active compounds,asymmetric catalysis,and optically pure materi...Planar chiral cyclophanes are a type of structurally intriguing organic molecules,which have found increasingly applications in the field of biologically active compounds,asymmetric catalysis,and optically pure materials.As such,significant efforts in the development of new methods to build up enantioenriched cyclophanes in a precise manner have attracted increased attention in recent years.Among the plethora of reported synthetic strategies,catalytic enantioselective method has emerged as one of the most straightforward and efficient ways to deliver optically pure planar chiral cyclophanes.In this review,the recent progress in catalytic enantioselective reactions for the synthesis of planar chiral cyclophanes will be discussed,which would stimulate the research interest of chemists for the discovery of novel asymmetric strategies for the preparation of valuable and previously difficult-to-access chiral molecules.展开更多
Symmetry breaking,a critical phenomenon in both natural and artificial systems,is pivotal in constructing chiral structures from achiral building units.This study focuses on the achiral molecule 8,8',8'',8...Symmetry breaking,a critical phenomenon in both natural and artificial systems,is pivotal in constructing chiral structures from achiral building units.This study focuses on the achiral molecule 8,8',8'',8'''-((pyrazine-2,3,5,6-tetrayltetrakis(benzene-4,1-iyl))tetrakis(oxy))tetrakis(octan-1-ol)(TPP-C8OH),an aggregation-induced emission(AIE)molecule,to explore its symmetry breaking behavior in supramolecular assembly.By analyzing TPP-C8OH in various solvents—both non-chiral and chiral—we find that chiral solvents significantly enhance the molecule's symmetry breaking and chiroptical properties.Specially,alcohol solvents,particularly dodecyl alcohol,facilitate the formation of helical structures with both left-handed(M)and right-handed(P)helices within single twisted nanoribbons.This observation contrasts with previously reported symmetry breaking phenomena in assembly systems.Chiral solvents induce assemblies with distinct helical orientations,resulting in notable circularly polarized luminescence(CPL)and circular dichroism(CD)signals.This study elucidates the impact of solvent choice on symmetry breaking and chiral assembly,offering insights into the design of advanced chiral materials with tailored self-assembly processes.展开更多
Perovskites showcased potential promise for innovative circularly polarized luminescence (CPL)-active multi-channelinformation encryption, owing to the exceptional luminescence brightness. It was still a formidablecha...Perovskites showcased potential promise for innovative circularly polarized luminescence (CPL)-active multi-channelinformation encryption, owing to the exceptional luminescence brightness. It was still a formidablechallenge to fabricate CPL-active perovskites with significant luminescent asymmetry factor (glum) and full-colour-tailorableCPL properties. Indeed, compared to isotropic perovskites, anisotropic perovskite nanowires (NWs)were conducive to carrier separation and transport for polarization enhancement. Herein, three types of CsPb(Br/I)3 NWs with green, orange, red fluorescence (FL) were respectively synthesized and assembled into chiral NWfilms. The right-handed/left-handed chiral NW films constructed by 4+4 layers and 45° inter-angles exhibitshighly symmetric and mirror-like chiral signals. The strongest chiral intensity is more than 3000 medg. CPLsignals with wide colour gamut produce ranging from 480 nm to 800 nm, and tailorable CPL wavelengths aremanipulated by the emission wavelength of perovskite NWs. A giant CPL signal with a maximum glum of up to 10^(-1) is achieved. The polarization imaging of chiral NW films produces brilliant differential circularly polarizedstructural colours, making it more widely used in multilevel anti-counterfeiting systems. A significant break-throughlies in the development of advanced chiral perovskite materials with remarkable glum and tailorable CPLproperties, which sheds new light on optical anti-counterfeiting and intelligent information encryption.展开更多
Rational tuning of chiral nanostructures of supramolecular assemblies as catalysts and investigating their chiral morphology-enantioselectivity dependence is rarely reported. Herein, we report a series of supramolecul...Rational tuning of chiral nanostructures of supramolecular assemblies as catalysts and investigating their chiral morphology-enantioselectivity dependence is rarely reported. Herein, we report a series of supramolecular M/P-helical nanoribbons(HNs) assembled from the chiral L/D-glutamate-based amphiphiles(L/D-Glu C16) and Cu(Ⅱ) ions, with their helical screw pitches adjusted from 217 nm to 104 nm through the facile regulation of their water/organic solvent assembly environment. They were then used as ideal models to reveal the chiral morphology-enantioselectivity relationship by catalyzing the asymmetric Diels-Alder reaction. Better enantioselectivity was achieved with more twist morphology. Experimental evidences of stronger chiral transfer effect from the supramolecular HNs with more twist to the aza-chalcone as reactant were obtained to understand such dependence. Our study demonstrates a new perspective for designing supramolecular catalysts with higher enantioselectivity.展开更多
Herein,we report the dynamic kinetic resolution asymmetric acylation ofγ-hydroxy-γ-perfluoroalkyl butenolides/phthalides catalyzed by amino acid-derived bifunctional organocatalysts,and a series of ketals were obtai...Herein,we report the dynamic kinetic resolution asymmetric acylation ofγ-hydroxy-γ-perfluoroalkyl butenolides/phthalides catalyzed by amino acid-derived bifunctional organocatalysts,and a series of ketals were obtained in high yields(up to 95%)and excellent enantioselectivities(up to 99%).In terms of synthetic utility,the reaction can be performed on a gram scale,and the product can be converted into potential biological nucleoside analog.展开更多
Chiral active matter exhibits a variety of collective behaviors,including phase separation,which is governed by the rule of“like chiralities attract,while opposite chiralities repel”.In this work,we investigate the ...Chiral active matter exhibits a variety of collective behaviors,including phase separation,which is governed by the rule of“like chiralities attract,while opposite chiralities repel”.In this work,we investigate the chiral demixing strategy of double-chiral partial mixture with inter-chiral frustration.We find that the inter-chiral frustration can significantly enhance the chiral demixing of active particles with different chiralities,both during the transient and in the steady state,not only accelerating the progress,but also improving the degree of phase separation.This phenomenon is reminiscent of the phase separation of binary mixtures in condensed matter physics,where the inter-chiral frustration can play a crucial role in the formation of the phase-separated states.We construct the phase diagram of the system and discuss the critical frustration for the enhancement of chiral demixing.Our work presents the first systematic investigation of inter-chiral frustration in self-propelled chiral active matter,filling a critical gap in the field.展开更多
Covalent organic cages(COCs)are three-dimensional organic molecules with permanent cavities,known for their ordered pore structures,excellent processability,and modular design.They have shown significant potential in ...Covalent organic cages(COCs)are three-dimensional organic molecules with permanent cavities,known for their ordered pore structures,excellent processability,and modular design.They have shown significant potential in applications such as gas adsorption,molecular separation,and catalysis.Introducing chiral elements into COCs results in chiral COCs with confined chiral cavities,which endows them with unique chiral functions and expands their application prospects.This review summarizes the research progress on chiral covalent organic cages,focusing on strategies for incorporating chiral elements,the structures and synthesis methods of representative chiral COCs,and advancements in their chiral functions.Additionally,we provide perspectives on future research directions.We hope this review will inspire further interest and creativity among researchers in the field of chiral molecular cages,leading to the development of materials with unique structures and functions.展开更多
基金financial support from NSF ExpandQISE program.The synthesis of tellurene was supported by NSF under grant no.CMMI-2046936supports from Purdue Research Foundation.
文摘Tellurene,a chiral chain semiconductor with a narrow bandgap and exceptional strain sensitivity,emerges as a pivotal material for tailoring electronic and optoelectronic properties via strain engineering.This study elucidates the fundamental mechanisms of ultrafast laser shock imprinting(LSI)in two-dimensional tellurium(Te),establishing a direct relationship between strain field orientation,mold topology,and anisotropic structural evolution.This is the first demonstration of ultrafast LSI on chiral chain Te unveiling orientation-sensitive dislocation networks.By applying controlled strain fields parallel or transverse to Te’s helical chains,we uncover two distinct deformation regimes.Strain aligned parallel to the chain’s direction induces gliding and rotation governed by weak interchain interactions,preserving covalent intrachain bonds and vibrational modes.In contrast,transverse strain drives shear-mediated multimodal deformations—tensile stretching,compression,and bending—resulting in significant lattice distortions and electronic property modulation.We discovered the critical role of mold topology on deformation:sharp-edged gratings generate localized shear forces surpassing those from homogeneous strain fields via smooth CD molds,triggering dislocation tangle formation,lattice reorientation,and inhomogeneous plastic deformation.Asymmetrical strain configurations enable localized structural transformations while retaining single-crystal integrity in adjacent regions—a balance essential for functional device integration.These insights position LSI as a precision tool for nanoscale strain engineering,capable of sculpting 2D material morphologies without compromising crystallinity.By bridging ultrafast mechanics with chiral chain material science,this work advances the design of strain-tunable devices for next-generation electronics and optoelectronics,while establishing a universal framework for manipulating anisotropic 2D systems under extreme strain rates.This work discovered crystallographic orientation-dependent deformation mechanisms in 2D Te,linking parallel strain to chain gliding and transverse strain to shear-driven multimodal distortion.It demonstrates mold geometry as a critical lever for strain localization and dislocation dynamics,with sharp-edged gratings enabling unprecedented control over lattice reorientation.Crucially,the identification of strain field conditions that reconcile severe plastic deformation with single-crystal retention offers a pathway to functional nanostructure fabrication,redefining LSI’s potential in ultrafast strain engineering of chiral chain materials.
基金supported by the National Key Research and Development Program of China(2019YFA0905100)the National Natural Science Foundation of China(21991102,22378227).
文摘Constructing a framework carrier to stabilize protein conformation,induce high embedding efficiency,and acquire low mass-transfer resistance is an urgent issue in the development of immobilized enzymes.Hydrogen-bonded organic frameworks(HOFs)have promising application potential for embedding enzymes.In fact,no metal involvement is required,and HOFs exhibit superior biocompatibility,and free access to substrates in mesoporous channels.Herein,a facile in situ growth approach was proposed for the self-assembly of alcohol dehydrogenase encapsulated in HOF.The micron-scale bio-catalytic composite was rapidly synthesized under mild conditions(aqueous phase and ambient temperature)with a controllable embedding rate.The high crystallinity and periodic arrangement channels of HOF were preserved at a high enzyme encapsulation efficiency of 59%.This bio-composite improved the tolerance of the enzyme to the acid-base environment and retained 81%of its initial activity after five cycles of batch hydrogenation involving NADH coenzyme.Based on this controllably synthesized bio-catalytic material and a common lipase,we further developed a two-stage cascade microchemical system and achieved the continuous production of chiral hydroxybutyric acid(R-3-HBA).
文摘In recent years,chiral inorganic nanomaterials have become promising candidates for applications in sensing,catalysis,biomedicine,and photonics.Plasmonic nanomaterials with an intrinsic chiral structure exhibit intriguing geometry‑dependent optical chirality,which benefits the combination of plasmonic characteristics with chirality.Recent advances in the biomolecule‑directed geometric control of intrinsically chiral plasmonic nanomaterials have further provided great opportunities for their widespread applications in many emerging technological areas.In this review,we present the recent progress in biosensing using chiral inorganic nanomaterials,with a particular focus on electrochemical and enzyme‑mimicking catalytic approaches.This paper commences with a review of the basic tenets underlying chiral nanocatalysts,incorporating the chiral ligand‑induced mechanism and the architectures of intrinsically chiral nanostructures.Additionally,it methodically expounds upon the applications of chiral nanocatalysts in the realms of electrochemical biosensing and enzyme‑mimicking catalytic biosensing respectively.Conclusively,it proffers a prospective view of the hurdles and prospects that accompany the deployment of chiral nanoprobes for nascent biosensing applications.By rational design of the chiral nanoprobes,it is envisioned that biosensing with increasing sensitivity and resolution toward the single‑molecule level can be achieved,which will substantially promote sensing applications in many emerging interdisciplinary areas.
文摘The catalytic enantioselective electrophilic amination reaction has emerged as a highly efficient method for synthesizing diverse nitrogen-containing chiral molecules,with the development of various asymmetric catalysis systems.Chiral phosphoric acids(CPA)have been widely acknowledged as versatile chiral organocatalysts since it was first discovered in 2004,finding application in catalyzing diverse asymmetric reactions.A comprehensive overview of recent advances in CPA-catalyzed asymmetric electrophilic amination reactions using different N-electrophilic reagents,including azo reagents,aryldiazonium salts,and imine derivatives,is presented.Furthermore,insights into future developments in this field are offered.
基金supported by the National Natural Science Foundation of China(No.22372030)the Natural Science Foundation of Jilin Province(No.YDZJ202201ZYTS328)+1 种基金the“111”project(No.B18012)the Fundamental Research Funds for the Central Universities(No.2412022ZD007).
文摘The precise manipulation of chiral crystallization for the fabrication of homochiral surfaces has emerged as a pivotal focal point within the realm of surface chemistry.In this investigation,we employed a temperature-regulated strategy,utilizing the conformationally chiral molecule 1,1,2,2-tetrakis(4-bromophenyl)ethene(TPEB)as a precursor to control the chiral recognition and separation process on Ag(111)surface mediated through Br···H and Br···Br interactions.At a temperature of 77 K,when TPEB was deposited onto the Ag(111)surface,it gives rise to two mirror-image racemic structures.As the temperature increases,TPEB molecules undergo a distinct transition from existing in racemic mixtures to enantiomeric excess mixtures.This transition ultimately culminates in a chiral separation process,resulting in the formation of a single-handed self-assembled structure and the acquisition of a homochiral Kagomélattice.This work meticulously monitored the chiral crystallization process of the conformationally chiral molecules on Ag(111)surface,capturing structures with diverse enantiomeric compositions.Moreover,through a combination of molecular simulations and density functional theory(DFT)calculations,we elucidated that an increase in temperature enhances the recognition between chiral molecules of the same handedness.This enhanced recognition,in turn,promotes the chiral separation process and steers the transition of the supramolecular assemblies from racemic mixtures towards single-handed structures.This study not only achieved the separation of heterochiral molecular conformations but also paved an effective avenue for the fabrication of homochiral nanostructures.
基金supported by the Foundation Research Project of Kaili University(No.2025ZD007)the National Key Research and Development Program of China(No.2021YFB3801503)the Joint Research Program of Shaoxing University and Shaoxing Institute,Zhejiang University(No.2023LHLG006),China.
文摘The presence of chirality,a fundamental attribute found in nature,is of great significance in the field of pharmaceutical science.Chiral drugs are unique in that their molecular structure is non-superimposable on its mirror image.This stereoisomerism significantly impacts the functionality,metabolic pathway,effectiveness,and safety of chiral medications.The enantiomers of chiral drugs can exhibit diverse pharmacological effects in the human body.As a result,it is essential to separate and purify chiral drugs effectively.Despite the abundance of reports on chiral drug separation membranes,there is a dearth of comprehensive reviews.This paper aims to fill this gap by providing a thorough review from a materials perspective,with a focus on the design and construction of chiral drug separation membranes.Furthermore,it systematically analyzes the separation mechanisms employed by these membranes.The paper also delves into the challenges and prospects related to chiral drug separation membranes,with the intention of imparting valuable insights for further research and development in this field.
基金supported by the National Natural Science Foundation of China (Grant Nos.12147101 and 12325507)the National Key Research and Development Program of China (Grant No.2022YFA1604900)+4 种基金the Guangdong Major Project of Basic and Applied Basic Research (Grant No.2020B0301030008 for S.G.and G.M.)the CUHK-Shenzhen university development fund (Grant Nos.UDF01003041 and UDF03003041)Shenzhen Peacock Fund (Grant No.2023TC0179 for K.Z.)the RIKEN TRIP initiative (RIKEN Quantum),JSPS KAKENHI (Grant No.25H01560)JST-BOOST (Grant No.JPMJBY24H9 for L.W.)。
文摘The search for the chiral magnetic effect(CME) in relativistic heavy-ion collisions(HICs) is challenged by significant background contamination. We present a novel deep learning approach based on a U-Net architecture to time-reversely unfold the dynamics of CME-related charge separation, enabling the reconstruction of the physics signal across the entire evolution of HICs. Trained on the events simulated by a multi-phase transport model with different cases of CME settings, our model learns to recover the charge separation based on final-state transverse momentum distributions at either the quark–gloun plasma freeze-out or hadronic freeze-out. This devises a methodological tool for the study of CME and underscores the promise of deep learning approaches in retrieving physics signals in HICs.
基金supported in part by the National Key R&D Program(Grant No.2023YFA1606900)the National Natural Science Foundation of China(Grant No.12235003)。
文摘Chirality,a common phenomenon in nature,appears in structures ranging from galaxies and condensed matter to atomic nuclei.There is a persistent demand for new,high-precision methods to detect chiral structures,particularly at the microscale.Here,we propose a novel method,vortex Mössbauer spectroscopy,for probing chiral structures.By leveraging the orbital angular momentum carried by vortex beams,this approach achieves high precision in detecting chiral structures at scales ranging from nanometers to hundreds of nanometers.Our simulation shows the ratio of characteristic lines in the Mössbauer spectra of ^(57)Fe under vortex beams exhibits differences of up to four orders of magnitude for atomic structures with different arrangements.Additionally,simulations reveal the response of ^(229m)Th chiral structures to vortex beams with opposite angular momenta differs by approximately 49-fold.These significant spectral variations indicate that this new vortex Mössbauer probe holds great potential for investigating the microscopic chiral structures and interactions of matter.
基金supported in part by the National Natural Science Foundation of China(Grant Nos.12435006,12435007,12475117,12141501,and 123B2080)the National Key R&D Program of China(Grant No.2024YFE0109803)the National Key Laboratory of Neutron Science and Technology(Grant No.NST202401016)。
文摘The simultaneous description for nuclear matter and finite nuclei has been a long-standing challenge in nuclear ab initio theory.With the success for nuclear matter,the relativistic Brueckner-Hartree-Fock(RBHF)theory with covariant chiral interactions is a promising ab initio approach to describe both nuclear matter and finite nuclei.In the description of finite nuclei with the current RBHF theory,the covariant chiral interactions have to be localized to make calculations feasible.In order to examine the reliability and validity,in this letter,the RBHF theory with local and nonlocal covariant chiral interactions at leading order is applied to nuclear matter.The low-energy constants in the covariant chiral interactions determined with the local regularization are close to those with the nonlocal regularization.Moreover,the RBHF theory using covariant chiral interactions with local and nonlocal regulators provides an equally good description of the saturation properties of nuclear matter.The present work paves the way for the implementation of covariant chiral interactions in RBHF theory for finite nuclei.
基金the National Key R&D Program of China(2023YFA1507601)the National Natural Science Foundation of China(22522108,52373213,22301176).
文摘Chiral metal-organic frameworks (CMOFs), a class of highly crystalline and porous materials with tailorable chiral characteristics, have currently become an interdisciplinary between chirality chemistry, coordination chemistry, and material chemistry, which involve in many subjects including chemistry, physics, optics, medi-cine, pharmacology, biology, crystal engineering, environmental science, etc. Their special structural features such as porosity, modularity, and chirality have endowed them with a variety of unique effects in promoting enantioselective processes, particularly asymmetric catalysis. Here, we provide a brief review of the state of CMOF field from the privileged ligand design to the heterogeneous enantioselective catalysis. We hope that this review will provide researchers a better understanding of CMOF chemistry and facilitate the future research endeavors for rationally designing privileged chiral framework materials for challenging catalytic applications.
文摘Chirality is a widespread physical phenomenon in nature,but natural materials often exhibit weak chiroptical responses.Recent advances have used chiral metasurfaces to enhance these responses,with applications in holographic imaging,chiral molecule detection,and circularly polarized lasers.However,most chiral metasurfaces exhibit strong chiroptical responses only at fixed wavelengths,which limits their suitability for wavelength-tunable optical devices.We address this by designing a silicon-GST(silicon-Ge2Sb2Te5)hybrid metasurface with asymmetric cross-shaped units that support multi-wavelength resonances,achieving broadband and dynamically tunable CD(circular dichroism).In the amorphous phase,GST enables CD>0.7 in the range of 2,137 nm to 2,657 nm,with a PER(polarization extinction ratio)up to 38 dB.Upon transition to the crystalline phase,CD enhances with a redshift,and the sign of CD reverses.This enables dynamic wavelength tuning of broadband CD via the phase transition of GST.
基金financial supports from National Key Research and Development Program of China(No.2022YFB3806200)。
文摘With the rapid development of holographic technology,metasurface-based holographic communication schemes have demonstrated immense potential for electromagnetic(EM)multifunctionality.However,traditional passive metasurfaces are severely limited by their lack of reconfigurability,hindering the realization of versatile holographic applications.Origami,an art form that mechanically induces spatial deformations,serves as a platform for multifunctional devices and has garnered significant attention in optics,physics,and materials science.The Miura-ori folding paradigm,characterized by its continuous reconfigurability in folded states,remains unexplored in the context of holographic imaging.Herein,we integrate the principles of Rosenfeld with L-and D-metal chiral enantiomers on a Miura-ori surface to tailor the aperture distribution.Leveraging the continuously tunable nature of the Miura-ori's folded states,the chiral response of the metallic structures varies across different folding configurations,enabling distinct EM holographic imaging functionalities.In the planar state,holographic encryption is achieved.Under specific folding conditions and driven by spin circularly polarized(CP)waves at a particular frequency,multiplexed holographic images can be reconstructed on designated focal planes with CP selectivity.Notably,the fabricated origami metasurface exhibits a large negative Poisson ratio,facilitating portability and deployment and offering novel avenues for spin-selective systems,camouflage,and information encryption.
基金supported by the National Natural Science Foundation of China(No.22271131)the Department of Science and Technology in Jiangxi Province(No.20225BCJ23029).
文摘Organic ferroelastics with metal free features and intrinsically light weight are highly desirable for future applications in flexible,smart and biocompatible devices.However,organoferroelastics with plastic phase transition have rarely been reported yet.Herein,we discovered ferroelasticity in a pair of organic enantiomers,(1S and/or 1R)-2,10-camphorsultam(S-and R-CPS),which undergoes a high-T_(c)plastic phase transition.Both large entropies change of∼45 J mol^(-1)K^(-1)and evidently ductile deformation process confirm the plastic phase feature.Strip-like ferroelastic domain patterns and bidirectional domain movements have been observed via polarized light microscopy and nanoindentation technique,respectively.This work highlights the discovery of organic ferroelastic combining the features of enantiomers and plastic phase transition,which contributes insights into exploration of organic multifunctional materials.
基金financial support provided by Huanghuai University and Hangzhou Medical College.
文摘Planar chiral cyclophanes are a type of structurally intriguing organic molecules,which have found increasingly applications in the field of biologically active compounds,asymmetric catalysis,and optically pure materials.As such,significant efforts in the development of new methods to build up enantioenriched cyclophanes in a precise manner have attracted increased attention in recent years.Among the plethora of reported synthetic strategies,catalytic enantioselective method has emerged as one of the most straightforward and efficient ways to deliver optically pure planar chiral cyclophanes.In this review,the recent progress in catalytic enantioselective reactions for the synthesis of planar chiral cyclophanes will be discussed,which would stimulate the research interest of chemists for the discovery of novel asymmetric strategies for the preparation of valuable and previously difficult-to-access chiral molecules.
基金support from the National Natural Science Foundation of China(Nos.22471198,22101208)the Fundamental Research Funds for the Central Universities.
文摘Symmetry breaking,a critical phenomenon in both natural and artificial systems,is pivotal in constructing chiral structures from achiral building units.This study focuses on the achiral molecule 8,8',8'',8'''-((pyrazine-2,3,5,6-tetrayltetrakis(benzene-4,1-iyl))tetrakis(oxy))tetrakis(octan-1-ol)(TPP-C8OH),an aggregation-induced emission(AIE)molecule,to explore its symmetry breaking behavior in supramolecular assembly.By analyzing TPP-C8OH in various solvents—both non-chiral and chiral—we find that chiral solvents significantly enhance the molecule's symmetry breaking and chiroptical properties.Specially,alcohol solvents,particularly dodecyl alcohol,facilitate the formation of helical structures with both left-handed(M)and right-handed(P)helices within single twisted nanoribbons.This observation contrasts with previously reported symmetry breaking phenomena in assembly systems.Chiral solvents induce assemblies with distinct helical orientations,resulting in notable circularly polarized luminescence(CPL)and circular dichroism(CD)signals.This study elucidates the impact of solvent choice on symmetry breaking and chiral assembly,offering insights into the design of advanced chiral materials with tailored self-assembly processes.
基金supported by the National Natural Science Foundation of China(22278184,22272065)the Natural Science Foundation of Jiangsu Province(BK20211530)+1 种基金the Fundamental Research Funds for the Central Universities(JUSRP622018,JUSRP202404022)the Key Research and Development Special Project of Yichun City,Jiangxi Province,China(2023ZDYFZX06).
文摘Perovskites showcased potential promise for innovative circularly polarized luminescence (CPL)-active multi-channelinformation encryption, owing to the exceptional luminescence brightness. It was still a formidablechallenge to fabricate CPL-active perovskites with significant luminescent asymmetry factor (glum) and full-colour-tailorableCPL properties. Indeed, compared to isotropic perovskites, anisotropic perovskite nanowires (NWs)were conducive to carrier separation and transport for polarization enhancement. Herein, three types of CsPb(Br/I)3 NWs with green, orange, red fluorescence (FL) were respectively synthesized and assembled into chiral NWfilms. The right-handed/left-handed chiral NW films constructed by 4+4 layers and 45° inter-angles exhibitshighly symmetric and mirror-like chiral signals. The strongest chiral intensity is more than 3000 medg. CPLsignals with wide colour gamut produce ranging from 480 nm to 800 nm, and tailorable CPL wavelengths aremanipulated by the emission wavelength of perovskite NWs. A giant CPL signal with a maximum glum of up to 10^(-1) is achieved. The polarization imaging of chiral NW films produces brilliant differential circularly polarizedstructural colours, making it more widely used in multilevel anti-counterfeiting systems. A significant break-throughlies in the development of advanced chiral perovskite materials with remarkable glum and tailorable CPLproperties, which sheds new light on optical anti-counterfeiting and intelligent information encryption.
基金support of this research by the National Natural Science Foundation of China(Nos.22202171,21922202,and 22272146)the Natural Science Foundation of Jiangsu Basic Research Program(No.BK20220559)+1 种基金the Natural Science Foundation of the Higher Education Institutions of Jiangsu Province(No.22KJD150009)the Jiangsu Specially-Appointed Professor Plan(Z.Xi)from the Jiangsu Education Department。
文摘Rational tuning of chiral nanostructures of supramolecular assemblies as catalysts and investigating their chiral morphology-enantioselectivity dependence is rarely reported. Herein, we report a series of supramolecular M/P-helical nanoribbons(HNs) assembled from the chiral L/D-glutamate-based amphiphiles(L/D-Glu C16) and Cu(Ⅱ) ions, with their helical screw pitches adjusted from 217 nm to 104 nm through the facile regulation of their water/organic solvent assembly environment. They were then used as ideal models to reveal the chiral morphology-enantioselectivity relationship by catalyzing the asymmetric Diels-Alder reaction. Better enantioselectivity was achieved with more twist morphology. Experimental evidences of stronger chiral transfer effect from the supramolecular HNs with more twist to the aza-chalcone as reactant were obtained to understand such dependence. Our study demonstrates a new perspective for designing supramolecular catalysts with higher enantioselectivity.
基金supported by the National Natural Science Foundation of China(Nos.82130103,82151525 and 81903465)the Central Plains Scholars and Scientists Studio Fund(2018002)+1 种基金the Natural Science Foundation of Henan Province(No.212300410051)the Science and Technology Major Project of Henan Province(No.221100310300)。
文摘Herein,we report the dynamic kinetic resolution asymmetric acylation ofγ-hydroxy-γ-perfluoroalkyl butenolides/phthalides catalyzed by amino acid-derived bifunctional organocatalysts,and a series of ketals were obtained in high yields(up to 95%)and excellent enantioselectivities(up to 99%).In terms of synthetic utility,the reaction can be performed on a gram scale,and the product can be converted into potential biological nucleoside analog.
基金supported by the National Natural Science Foun-dation of China(Grant Nos.12375031 and 11875135)China National University Student Innovation and Entrepreneurship(Grant No.202410385040)Fujian University Alliance of Physics Discipline Training Program of Innovation for Under-graduates Development Program,China.
文摘Chiral active matter exhibits a variety of collective behaviors,including phase separation,which is governed by the rule of“like chiralities attract,while opposite chiralities repel”.In this work,we investigate the chiral demixing strategy of double-chiral partial mixture with inter-chiral frustration.We find that the inter-chiral frustration can significantly enhance the chiral demixing of active particles with different chiralities,both during the transient and in the steady state,not only accelerating the progress,but also improving the degree of phase separation.This phenomenon is reminiscent of the phase separation of binary mixtures in condensed matter physics,where the inter-chiral frustration can play a crucial role in the formation of the phase-separated states.We construct the phase diagram of the system and discuss the critical frustration for the enhancement of chiral demixing.Our work presents the first systematic investigation of inter-chiral frustration in self-propelled chiral active matter,filling a critical gap in the field.
基金supported by the National Natural Science Foundation of China(Grant Nos.22271164 and U20A20259 and 22371147)the Fundamental Research Funds for the Central Universities,the NCC Fund(Grant No.NCC2020FH04)+1 种基金the Tianshan Innovation Team Plan of Xinjiang Uygur Autonomous Region(Grant No.2023D14002)Nankai University(NKU).
文摘Covalent organic cages(COCs)are three-dimensional organic molecules with permanent cavities,known for their ordered pore structures,excellent processability,and modular design.They have shown significant potential in applications such as gas adsorption,molecular separation,and catalysis.Introducing chiral elements into COCs results in chiral COCs with confined chiral cavities,which endows them with unique chiral functions and expands their application prospects.This review summarizes the research progress on chiral covalent organic cages,focusing on strategies for incorporating chiral elements,the structures and synthesis methods of representative chiral COCs,and advancements in their chiral functions.Additionally,we provide perspectives on future research directions.We hope this review will inspire further interest and creativity among researchers in the field of chiral molecular cages,leading to the development of materials with unique structures and functions.
