Due to the lack of inversion,mirror or other roto-inversion symmetries,chiral crystals possess a well-defined handedness which,when combined with time-reversal symmetry breaking from the application of magnetic fields...Due to the lack of inversion,mirror or other roto-inversion symmetries,chiral crystals possess a well-defined handedness which,when combined with time-reversal symmetry breaking from the application of magnetic fields,can give rise to directional dichroism of the electrical transport phenomena via the magnetochiral anisotropy.In this study,we investigate the nonreciprocal magneto-transport in microdevices of NbGe_(2),a superconductor with structural chirality.A giant nonreciprocal signal from vortex motions is observed during the superconducting transition,with the ratio of nonreciprocal resistance to the normal resistanceγreaching 6×10^(5)T^(-1)·A^(-1).Interestingly,the intensity can be adjusted and even sign-reversed by varying the current,the temperature,and the crystalline orientation.Our findings illustrate intricate vortex dynamics and offer ways of manipulation on the rectification effect in superconductors with structural chirality.展开更多
We consider the inverse electromagnetic scattering problem of determining the shape of a perfectly conducting core inside a penetrable chiral body. We prove the well-posedness of the corresponding direct scattering pr...We consider the inverse electromagnetic scattering problem of determining the shape of a perfectly conducting core inside a penetrable chiral body. We prove the well-posedness of the corresponding direct scattering problem by the variational method. We focus on a uniqueness result for the inverse scattering problem that is under what conditions an obstacle can be identified by the knowledge of the electric far-field pattern corresponding to all time-harmonic incident planes waves with a fixed wave number. To this end, we establish a chiral mixed reciprocity relation that connects the electric far-field pattern of a spherical wave with the scattered field of a plane wave.展开更多
Helical hierarchy found in biomolecules like cellulose,chitin,and collagen underpins the remarkable mechanical strength and vibrant colors observed in living organisms.This study advances the integration of helical/ch...Helical hierarchy found in biomolecules like cellulose,chitin,and collagen underpins the remarkable mechanical strength and vibrant colors observed in living organisms.This study advances the integration of helical/chiral assembly and 3D printing technology,providing precise spatial control over chiral nano/microstructures of rod-shaped colloidal nanoparticles in intricate geometries.We designed reactive chiral inks based on cellulose nanocrystal(CNC)suspensions and acrylamide monomers,enabling the chiral assembly at nano/microscale,beyond the resolution seen in printed materials.We employed a range of complementary techniques including Orthogonal Superposition rheometry and in situ rheo-optic measurements under steady shear rate conditions.These techniques help us to understand the nature of the nonlinear flow behavior of the chiral inks,and directly probe the flow-induced microstructural dynamics and phase transitions at constant shear rates,as well as their post-flow relaxation.Furthermore,we analyzed the photo-curing process to identify key parameters affecting gelation kinetics and structural integrity of the printed object within the supporting bath.These insights into the interplay between the chiral inks self-assembly dynamics,3D printing flow kinematics and photopolymerization kinetics provide a roadmap to direct the out-of-equilibrium arrangement of CNC particles in the 3D printed filaments,ranging from uniform nematic to 3D concentric chiral structures with controlled pitch length,as well as random orientation of chiral domains.Our biomimetic approach can pave the way for the creation of materials with superior mechanical properties or programable photonic responses that arise from 3D nano/microstructure and can be translated into larger scale 3D printed designs.展开更多
Flurbiprofen(FB),a nonsteroidal anti-inflammatory drug,is widely employed in treating ocular inflammation owing to its remarkable anti-inflammatory effects.However,the racemic nature of its commercially available form...Flurbiprofen(FB),a nonsteroidal anti-inflammatory drug,is widely employed in treating ocular inflammation owing to its remarkable anti-inflammatory effects.However,the racemic nature of its commercially available formulation(Ocufen^(R))limits the full potential of its therapeutic activity,as the(S)-enantiomer is responsible for the desired antiinflammatory effects.Additionally,the limited corneal permeability of FB significantly restricts its bioavailability.In this study,we successfully separated the chiral isomers of FB to obtain the highly active(S)-FB.Subsequently,utilizing ion-pairing technology,we coupled(S)-FB with various counter-ions,such as sodium,diethylamine,trimethamine(TMA),and l-arginine,to enhance its ocular bioavailability.A comprehensive evaluation encompassed balanced solubility,octanol-water partition coefficient,corneal permeability,ocular pharmacokinetics,tissue distribution,and in vivo ocular anti-inflammatory activity of each chiral isomer salt.Among the various formulations,S-FBTMA exhibited superior water solubility(about 1–12 mg/ml),lipid solubility(1<lgP_(ow)<3)and corneal permeability.In comparison to Ocufen^(R),S-FBTMA demonstrated significantly higher in vivo antiinflammatory activity and lower ocular irritability(such as conjunctival congestion and tingling).The findings from this research highlight the potential of chiral separation and ion-pair enhanced permeation techniques in providing pharmaceutical enterprises focused on drug development with a valuable avenue for improving therapeutic outcomes.展开更多
Chirality(Greek“handiness”)is a property of many com-plex molecules.Chiral molecules exist in two forms,one being the mirror image of the other.Like for our hands,it is impossible to make the images identical by a s...Chirality(Greek“handiness”)is a property of many com-plex molecules.Chiral molecules exist in two forms,one being the mirror image of the other.Like for our hands,it is impossible to make the images identical by a suitable rota-tion.The two forms are called left-handed and right-handed.They have the same binding energy,because the electro-magnetic interaction,which holds the molecule together,does not change under a reflection.Other properties that are insensitive to the geometry are also the same.The different geometry is the reason why the left-handed form turns the polarization plane of transmitted light in one direction by some angle while the right-handed form turns it in the oppo-site direction by the same angle.However,the geometrical differences between the two species may have other conse-quences.The two species of the carvon molecule shown in Fig.1 taste quite differently.展开更多
We study the chiral bound states in a coupled-resonator array with staggered hopping strengths,which interacts with a two-level small atom through a single coupling point or two adjacent ones.In addition to the two ty...We study the chiral bound states in a coupled-resonator array with staggered hopping strengths,which interacts with a two-level small atom through a single coupling point or two adjacent ones.In addition to the two typical bound states found above and below the energy bands,this system presents an extraordinary chiral bound state located within the energy gap.We use the chirality to quantify the breaking of the mirror symmetry.We find that the chirality value undergoes continuous changes by tuning the coupling strengths.The preferred direction of the chirality is controlled not only by the competition between the intracell and the intercell hoppings in the coupled-resonator array,but also by the coherence between the two coupling points.In the case with one coupling point,the chirality values varies monotonously with difference between the intracell hopping and the intercell hoppings.While in the case with two coupling points,due to the coherence between the two coupling points the perfect chiral states can be obtained.展开更多
The chiral 2×2 charge order has been reported and confirmed in the kagome superconductor RbV_(3)Sb_(5),while its interplay with superconductivity remains elusive owing to its lowest superconducting transition tem...The chiral 2×2 charge order has been reported and confirmed in the kagome superconductor RbV_(3)Sb_(5),while its interplay with superconductivity remains elusive owing to its lowest superconducting transition temperature Tc of about 0.85K in the AV_(3)Sb_(5) family(A=K,Rb,Cs)that severely challenges electronic spectroscopic probes.Here,utilizing dilution-refrigerator-based scanning tunneling microscopy down to 30 mK,we observe chiral 2×2 pair density waves with residual Fermi arcs in RbV_(3)Sb_(5).We find a superconducting gap of 150 μeV with substantial residual in-gap states.The spatial distribution of this gap exhibits chiral 2×2 modulations,signaling a chiral pair density wave(PDW).Our quasi-particle interference imaging of the zero-energy residual states further reveals arc-like patterns.We discuss the relation of the gap modulations with the residual Fermi arcs under the space-momentum correspondence between PDW and Bogoliubov Fermi states.展开更多
Two-dimensional covalent organic frameworks(2D COFs)feature extendedπ-conjugation and ordered stacking sequence,showing great promise for high-performance photocatalysis.Periodic atomic frameworks of 2D COFs facilita...Two-dimensional covalent organic frameworks(2D COFs)feature extendedπ-conjugation and ordered stacking sequence,showing great promise for high-performance photocatalysis.Periodic atomic frameworks of 2D COFs facilitate the in-plane photogenerated charge transfer,but the precise ordered alignment is limited due to the non-covalentπ-stacking of COF layers,accordingly hindering out-of-plane transfer kinetics.Herein,we address a chiral induction method to construct a parallelly superimposed stacking chiral COF ultrathin shell on the support of SiO_(2) microsphere.Compared to the achiral COF analogues,the chiral COF shell with the parallel AA-stacking structure is more conducive to enhance the built-in electric field and accumulates photogenerated electrons for the rapid migration,thereby affording superior photocatalytic performance in hydrogen evolution from water splitting.Taking the simplest ketoenamine-linked chiral COF as a shell of SiO_(2) particle,the resulting composite exhibits an impressive hydrogen evolution rate of 107.1 mmol g^(-1)h^(-1)along with the apparent quantum efficiency of 14.31% at 475 nm.Furthermore,the composite photocatalysts could be fabricated into a film device,displaying a remarkable photocatalytic performance of 178.0 mmol m^(-2)h^(-1)for hydrogen evolution.Our work underpins the surface engineering of organic photocatalysts and illustrates the significance of COF stacking structures in regulating electronic properties.展开更多
In this paper,a multifunctional chiral metasurface is presented to achieve asymmetric transmission(AT)and linear-polarization conversion(LPC).The designed metasurface consists of a cross swords-like shape and two hole...In this paper,a multifunctional chiral metasurface is presented to achieve asymmetric transmission(AT)and linear-polarization conversion(LPC).The designed metasurface consists of a cross swords-like shape and two holes in the lower side of the unit cell.In the frequency band from 8.3 GHz to 10.4 GHz,AT is realized with more than 90%efficiency and the same chiral metasurface transforms linear polarized wave into its orthogonal counterpart with high efficiency.For LPC,the polarization conversion ratio(PCR)is greater than 95%.The proposed metasurface is stable against the incident angles of striking electromagnetic(EM)waves up to 60°for both operations of AT and LPC.展开更多
Chiral metamaterials have been proven to possess many appealing mechanical phenomena,such as negative Poisson's ratio,high-impact resistance,and energy absorption.This work extends the applications of chiral metam...Chiral metamaterials have been proven to possess many appealing mechanical phenomena,such as negative Poisson's ratio,high-impact resistance,and energy absorption.This work extends the applications of chiral metamaterials to underwater sound insulation.Various chiral metamaterials with low acoustic impedance and proper stiffness are inversely designed using the topology optimization scheme.Low acoustic impedance enables the metamaterials to have a high and broadband sound transmission loss(STL),while proper stiffness guarantees its robust acoustic performance under a hydrostatic pressure.As proof-of-concept demonstrations,two specimens are fabricated and tested in a water-filled impedance tube.Experimental results show that,on average,over 95%incident sound energy can be isolated by the specimens in a broad frequency range from 1 k Hz to 5 k Hz,while the sound insulation performance keeps stable under a certain hydrostatic pressure.This work may provide new insights for chiral metamaterials into the underwater applications with sound insulation.展开更多
We study theoretically the electrical shot noise properties of tunnel junctions between a normal metal and a superconductor with the mixture of singlet s-wave and chiral triplet p-wave pairing due to broken inversion ...We study theoretically the electrical shot noise properties of tunnel junctions between a normal metal and a superconductor with the mixture of singlet s-wave and chiral triplet p-wave pairing due to broken inversion symmetry. We investigate how the shot noise properties vary as the relative amplitude between the two parity components in the pairing potential is changed. It is demonstrated that some characteristics of the electrical shot noise properties of such tunnel junctions may depend sensitively on the relative amplitude between the two parity components in the pairing potential, and some significant changes may occur in the electrical shot noise properties when the relative amplitude between the two parity components is varied from the singlet s-wave pairing dominated regime to the chiral triplet p-wave pairing dominated regime. In the chiral triplet p-wave pairing dominated regime, the ratio of noise power to electric current is close to 2e both in the in-gap and in the out-gap region. In the singlet s-wave pairing dominated regime, the value of this ratio is close to 4e in the inner gap region but may reduce to about 2e in the outer gap region as the relative amplitude of the chiral triplet pairing component is increased. The variations of the differential shot noise with the bias voltage also exhibit some significantly different features in different regimes. Such different features can serve as useful diagnostic tools for the determination of the relative magnitude of the two parity components in the pairing potential.展开更多
Owing to the good adjustability and the strong near-field enhancement,surface plasmons are widely used in optical force trap,thus the optical force trap can achieve excellent performance.Here,we use the Laguerre–Gaus...Owing to the good adjustability and the strong near-field enhancement,surface plasmons are widely used in optical force trap,thus the optical force trap can achieve excellent performance.Here,we use the Laguerre–Gaussian beam and a plasmonic gold ring to separate enantiomers by the chiral optical force.Along with the radial optical force that traps the particles,there is also a chirality-sign-sensitive lateral force arising from the optical spin angular momentum,which is caused by the interaction between optical orbit angular momentum and gold ring structure.By selecting a specific incident wavelength,the strong angular scattering and non-chiral related azimuthal optical force can be suppressed.Thus the chiral related azimuthal optical force can induce an opposite orbital rotation of the trapped particles with chirality of different sign near the gold ring.This work proposes an effective approach for catchingand separating chiral enantiomers.展开更多
Aroma(volatile)compounds play important ecological functions in plants,and also contribute to the quality of plant-derived foods.Moreover,chiral aroma compounds affect their functions in plants and lead to different f...Aroma(volatile)compounds play important ecological functions in plants,and also contribute to the quality of plant-derived foods.Moreover,chiral aroma compounds affect their functions in plants and lead to different flavor quality properties.Formations of chiral aroma compounds are due to the presence of enzymes producing these compounds in plants,which are generally involved in the final biosynthetic step of the aroma compounds.Here,we review recent progress in research on the plant-derived enzymes producing chiral aroma compounds,and their changes in response to environmental factors.The chiral aroma enzymes that have been reported produce(R)-linalool,(S)-linalool,(R)-limonene,and(S)-limonene,etc.,and these enzymes are found in various plant species.We also discuss the origins of enantioselectivity in the plant-derived enzymes producing chiral aroma compounds and summarize the potential use of plants containing enzymes producing chiral aroma compounds for producing chiral flavors/fragrances.展开更多
For decades,chiral nanomaterials have been extensively studied because of their extraordinary properties.Chiral nanostructures have attracted a lot of interest because of their potential applications including biosens...For decades,chiral nanomaterials have been extensively studied because of their extraordinary properties.Chiral nanostructures have attracted a lot of interest because of their potential applications including biosensing,asymmetric catalysis,optical devices,and negative index materials.Circularly polarized light(CPL)is the most attractive source for chirality owing to its high availability,and now it has been used as a chiral source for the preparation of chiral matter.In this review,the recent progress in the field of CPL-enabled chiral nanomaterials is summarized.Firstly,the recent advancements in the fabrication of chiral materials using circularly polarized light are described,focusing on the unique strategies.Secondly,an overview of the potential applications of chiral nanomaterials driven by CPL is provided,with a particular emphasis on biosensing,catalysis,and phototherapy.Finally,a perspective on the challenges in the field of CPL-enabled chiral nanomaterials is given.展开更多
Capillary electrochromatography(CEC)plays a significant role in chiral separation via the double separation principle,partition coefficient difference between the two phases,and electroosmotic flow-driven separation.G...Capillary electrochromatography(CEC)plays a significant role in chiral separation via the double separation principle,partition coefficient difference between the two phases,and electroosmotic flow-driven separation.Given the distinct properties of the inner wall stationary phase(SP),the separation ability of each SP differs from one another.Particularly,it provides large room for promising applications of open tubular capillary electrochromatography(OT-CEC).We divided the OT-CEC SPs developed over the past four years into six types:ionic liquids,nanoparticle materials,microporous materials,biomaterials,non-nanopolymers,and others,to mainly introduce their characteristics in chiral drug separation.There also added a few classic SPs that occurred within ten years as supplements to enrich the features of each SP.Additionally,we discuss their applications in metabolomics,food,cosmetics,environment,and biology as analytes in addition to chiral drugs.OT-CEC plays an increasingly significant role in chiral separation and may promote the development of capillary electrophoresis(CE)combined with other instruments in recent years,such as CE with mass spectrometry(CE/MS)and CE with ultraviolet light detector(CE/UV).展开更多
Chirality plays an important role in biological processes,and enantiomers often possess similar physical properties and different physiologic functions.In recent years,chiral detection of enantiomers become a popular ...Chirality plays an important role in biological processes,and enantiomers often possess similar physical properties and different physiologic functions.In recent years,chiral detection of enantiomers become a popular topic.Plasmonic metasurfaces enhance weak inherent chiral effects of biomolecules,so they are used in chiral detection.Artificial intelligence algorithm makes a lot of contribution to many aspects of nanophotonics.Here,we propose a nanostructure design method based on reinforcement learning and devise chiral nanostructures to distinguish enantiomers.The algorithm finds out the metallic nanostructures with a sharp peak in circular dichroism spectra and emphasizes the frequency shifts caused by nearfield interaction of nanostructures and biomolecules.Our work inspires universal and efficient machine-learning methods for nanophotonic design.展开更多
Chirality is ubiquitous in natural world.Although with similar physical and chemical properties,chiral enantiomers could play different roles in biochemical processes.Discrimination of chiral enantiomers is extremely ...Chirality is ubiquitous in natural world.Although with similar physical and chemical properties,chiral enantiomers could play different roles in biochemical processes.Discrimination of chiral enantiomers is extremely important in biochemical,analytical chemistry,and pharmaceutical industries.Conventional chiroptical spectroscopic methods are disadvantageous at a limited detection sensitivity because of the weak signals of natural chiral molecules.Recently,superchiral fields were proposed to effectively enhance the interaction between light and molecules,allowing for ultrasensitive chiral detection.Intensive theoretical and experimental works have been devoted to generation of superchiral fields based on artificial nanostructures and their application in ultrasensitive chiral sensing.In this review,we present a survey on these works.We begin with the introduction of chiral properties of electromagnetic fields.Then,the optical chirality enhancement and ultrasensitive chiral detection based on chiral and achiral nanostructures are discussed respectively.Finally,we give a short summary and a perspective for the future ultrasensitive chiral sensing.展开更多
Chirality,as the symmetric breaking of molecules,plays an essential role in physical,chemical and especially biological processes,which highlights the accurate distinction among heterochiralities as well as the precis...Chirality,as the symmetric breaking of molecules,plays an essential role in physical,chemical and especially biological processes,which highlights the accurate distinction among heterochiralities as well as the precise preparation for homochirality.To this end,the well-designed structure-specific recognizer and catalysis reactor are necessitated,respectively.However,each kind of target molecules requires a custom-made chiral partner and the dynamic disorder of spatial-orientation distribution of molecules at the ensemble level leads to an inefficient protocol.In this perspective article,we developed a universal strategy capable of realizing the chirality detection and control by the external symmetry breaking based on the alignment of the molecular frame to external stimuli.Specifically,in combination with the discussion about the relationship among the chirality(molecule),spin(electron)and polarization(photon),i.e.,the three natural symmetry breaking,single-molecule junctions were proposed to achieve a single-molecule/event-resolved detection and synthesis.The fixation of the molecular orientation and the CMOS-compatibility provide an efficient interface to achieve the external input of symmetry breaking.This perspective is believed to offer more efficient applications in accurate chirality detection and precise asymmetric synthesis via the close collaboration of chemists,physicists,materials scientists,and engineers.展开更多
We investigate asymmetric spin wave scattering behaviors caused by vortex chirality in a cross-shaped ferromagnetic system by using the micromagnetic simulations.In the system,four scattering behaviors are found:(i)as...We investigate asymmetric spin wave scattering behaviors caused by vortex chirality in a cross-shaped ferromagnetic system by using the micromagnetic simulations.In the system,four scattering behaviors are found:(i)asymmetric skew scattering,depending on the polarity of vortex core,(ii)back scattering(reflection),depending on the vortex core stiffness,(iii)side deflection scattering,depending on structural symmetry of the vortex circulation,and(iv)geometrical scattering,depending on waveguide structure.The first and second scattering behaviors are attributed to nonlinear topological magnon spin Hall effect related to magnon spin-transfer torque effect,which has value for magnonic exploration and application.展开更多
Overlook of chiral consideration in transdermal drug delivery increases administrated dose and risk of side effects,decreasing therapeutical effects.To improve the transdermal delivery efficiency of eutomer,this work ...Overlook of chiral consideration in transdermal drug delivery increases administrated dose and risk of side effects,decreasing therapeutical effects.To improve the transdermal delivery efficiency of eutomer,this work focused on investigating the law and mechanism of enantioselective enhancing effects of chiral permeation enhancers on drug enantiomers.Chiral nonsteroidal anti-inflammatory drugs and terpene permeation enhancers were selected as model drug and enhancers.The results indicated that the L-isomer of permeation enhancers increased the skin absorption of S-enantiomer of drug and D-isomer improve the permeation of R-enantiomer,in which the enhancement effect(ER)of Lmenthol on S-enantiomer(ER=3.23)was higher than that on R-enantiomer(ER=1.49).According to the pharmacokinetics results,L-menthol tended to enhance the permeation of S-enantiomer better than R-enantiomer(2.56 fold),and showed excellent in vitro/in vivo correlations.The mechanism study showed that L-isomer of permeation enhancers improved the permeation of S-enantiomer by increasing the retention,but the D-isomer by improving partition for better permeation.Enantioselective mechanism indicated that the weaker chiral H-bond interaction between drug-chiral enhancers was caused by the enantiomeric conformation.Additionally,stronger chiral enhancers-skin interaction between L-isomer and S-conformation of ceramide produced better enhancing effects.In conclusion,enantioselective interaction of chiral drug-chiral enhancers and chiral enhancers-chiral skin played a critical role in transdermal drug delivery,rational utilization of which contributed to improving the uptake of eutomer and inhibiting distomers to decrease a half of dose and side effects,increasing transdermal therapeutical efficiency.展开更多
基金Project supported by the National Key R&D Program of China(Grant No.2022YFA1403603)the National Natural Science Foundation of China(Grant Nos.U2032213,12104461,12374129,and 12304156)+1 种基金Chinese Academy of Sciences(Grant Nos.YSBR-084,and JZHKYPT-2021-08)A portion of this work was supported by the High Magnetic Field Laboratory of Anhui Province.
文摘Due to the lack of inversion,mirror or other roto-inversion symmetries,chiral crystals possess a well-defined handedness which,when combined with time-reversal symmetry breaking from the application of magnetic fields,can give rise to directional dichroism of the electrical transport phenomena via the magnetochiral anisotropy.In this study,we investigate the nonreciprocal magneto-transport in microdevices of NbGe_(2),a superconductor with structural chirality.A giant nonreciprocal signal from vortex motions is observed during the superconducting transition,with the ratio of nonreciprocal resistance to the normal resistanceγreaching 6×10^(5)T^(-1)·A^(-1).Interestingly,the intensity can be adjusted and even sign-reversed by varying the current,the temperature,and the crystalline orientation.Our findings illustrate intricate vortex dynamics and offer ways of manipulation on the rectification effect in superconductors with structural chirality.
文摘We consider the inverse electromagnetic scattering problem of determining the shape of a perfectly conducting core inside a penetrable chiral body. We prove the well-posedness of the corresponding direct scattering problem by the variational method. We focus on a uniqueness result for the inverse scattering problem that is under what conditions an obstacle can be identified by the knowledge of the electric far-field pattern corresponding to all time-harmonic incident planes waves with a fixed wave number. To this end, we establish a chiral mixed reciprocity relation that connects the electric far-field pattern of a spherical wave with the scattered field of a plane wave.
基金the support from the University of South Carolina
文摘Helical hierarchy found in biomolecules like cellulose,chitin,and collagen underpins the remarkable mechanical strength and vibrant colors observed in living organisms.This study advances the integration of helical/chiral assembly and 3D printing technology,providing precise spatial control over chiral nano/microstructures of rod-shaped colloidal nanoparticles in intricate geometries.We designed reactive chiral inks based on cellulose nanocrystal(CNC)suspensions and acrylamide monomers,enabling the chiral assembly at nano/microscale,beyond the resolution seen in printed materials.We employed a range of complementary techniques including Orthogonal Superposition rheometry and in situ rheo-optic measurements under steady shear rate conditions.These techniques help us to understand the nature of the nonlinear flow behavior of the chiral inks,and directly probe the flow-induced microstructural dynamics and phase transitions at constant shear rates,as well as their post-flow relaxation.Furthermore,we analyzed the photo-curing process to identify key parameters affecting gelation kinetics and structural integrity of the printed object within the supporting bath.These insights into the interplay between the chiral inks self-assembly dynamics,3D printing flow kinematics and photopolymerization kinetics provide a roadmap to direct the out-of-equilibrium arrangement of CNC particles in the 3D printed filaments,ranging from uniform nematic to 3D concentric chiral structures with controlled pitch length,as well as random orientation of chiral domains.Our biomimetic approach can pave the way for the creation of materials with superior mechanical properties or programable photonic responses that arise from 3D nano/microstructure and can be translated into larger scale 3D printed designs.
基金financially supported by the National Postdoctoral Foundation of China(No.2023M730375)Liaoning Province Department of Education Project(No.LJKMZ20221365)the State Key Laboratory of Natural and Biomimetic Drugs(No.K202215)。
文摘Flurbiprofen(FB),a nonsteroidal anti-inflammatory drug,is widely employed in treating ocular inflammation owing to its remarkable anti-inflammatory effects.However,the racemic nature of its commercially available formulation(Ocufen^(R))limits the full potential of its therapeutic activity,as the(S)-enantiomer is responsible for the desired antiinflammatory effects.Additionally,the limited corneal permeability of FB significantly restricts its bioavailability.In this study,we successfully separated the chiral isomers of FB to obtain the highly active(S)-FB.Subsequently,utilizing ion-pairing technology,we coupled(S)-FB with various counter-ions,such as sodium,diethylamine,trimethamine(TMA),and l-arginine,to enhance its ocular bioavailability.A comprehensive evaluation encompassed balanced solubility,octanol-water partition coefficient,corneal permeability,ocular pharmacokinetics,tissue distribution,and in vivo ocular anti-inflammatory activity of each chiral isomer salt.Among the various formulations,S-FBTMA exhibited superior water solubility(about 1–12 mg/ml),lipid solubility(1<lgP_(ow)<3)and corneal permeability.In comparison to Ocufen^(R),S-FBTMA demonstrated significantly higher in vivo antiinflammatory activity and lower ocular irritability(such as conjunctival congestion and tingling).The findings from this research highlight the potential of chiral separation and ion-pair enhanced permeation techniques in providing pharmaceutical enterprises focused on drug development with a valuable avenue for improving therapeutic outcomes.
文摘Chirality(Greek“handiness”)is a property of many com-plex molecules.Chiral molecules exist in two forms,one being the mirror image of the other.Like for our hands,it is impossible to make the images identical by a suitable rota-tion.The two forms are called left-handed and right-handed.They have the same binding energy,because the electro-magnetic interaction,which holds the molecule together,does not change under a reflection.Other properties that are insensitive to the geometry are also the same.The different geometry is the reason why the left-handed form turns the polarization plane of transmitted light in one direction by some angle while the right-handed form turns it in the oppo-site direction by the same angle.However,the geometrical differences between the two species may have other conse-quences.The two species of the carvon molecule shown in Fig.1 taste quite differently.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11975095,12075082,11935006,and 12247105)the Major Sci-Tech Program of Hunan Province,China(Grant No.2023ZJ1010)the Natural Science Foundation of Guangdong Province,China(Grant Nos.2019A1515011400 and 2023A151501223).
文摘We study the chiral bound states in a coupled-resonator array with staggered hopping strengths,which interacts with a two-level small atom through a single coupling point or two adjacent ones.In addition to the two typical bound states found above and below the energy bands,this system presents an extraordinary chiral bound state located within the energy gap.We use the chirality to quantify the breaking of the mirror symmetry.We find that the chirality value undergoes continuous changes by tuning the coupling strengths.The preferred direction of the chirality is controlled not only by the competition between the intracell and the intercell hoppings in the coupled-resonator array,but also by the coherence between the two coupling points.In the case with one coupling point,the chirality values varies monotonously with difference between the intracell hopping and the intercell hoppings.While in the case with two coupling points,due to the coherence between the two coupling points the perfect chiral states can be obtained.
基金supported by the National Key R&D Program of China(Grant Nos.2023YFA1407300,2023YFA1406500,2022YFA1403800,and 2023YFF0718403)the National Natural Science Foundation of China(Grant Nos.12374060,12274459,and 12074162)+2 种基金Guangdong Provincial Quantum Science Strategic Initiative(Grant No.GDZX2201001)the Beijing Natural Science Foundation(Grant No.Z200005)Guangdong Basic and Applied Basic Research Foundation(Grant No.2022B1515130005)。
文摘The chiral 2×2 charge order has been reported and confirmed in the kagome superconductor RbV_(3)Sb_(5),while its interplay with superconductivity remains elusive owing to its lowest superconducting transition temperature Tc of about 0.85K in the AV_(3)Sb_(5) family(A=K,Rb,Cs)that severely challenges electronic spectroscopic probes.Here,utilizing dilution-refrigerator-based scanning tunneling microscopy down to 30 mK,we observe chiral 2×2 pair density waves with residual Fermi arcs in RbV_(3)Sb_(5).We find a superconducting gap of 150 μeV with substantial residual in-gap states.The spatial distribution of this gap exhibits chiral 2×2 modulations,signaling a chiral pair density wave(PDW).Our quasi-particle interference imaging of the zero-energy residual states further reveals arc-like patterns.We discuss the relation of the gap modulations with the residual Fermi arcs under the space-momentum correspondence between PDW and Bogoliubov Fermi states.
文摘Two-dimensional covalent organic frameworks(2D COFs)feature extendedπ-conjugation and ordered stacking sequence,showing great promise for high-performance photocatalysis.Periodic atomic frameworks of 2D COFs facilitate the in-plane photogenerated charge transfer,but the precise ordered alignment is limited due to the non-covalentπ-stacking of COF layers,accordingly hindering out-of-plane transfer kinetics.Herein,we address a chiral induction method to construct a parallelly superimposed stacking chiral COF ultrathin shell on the support of SiO_(2) microsphere.Compared to the achiral COF analogues,the chiral COF shell with the parallel AA-stacking structure is more conducive to enhance the built-in electric field and accumulates photogenerated electrons for the rapid migration,thereby affording superior photocatalytic performance in hydrogen evolution from water splitting.Taking the simplest ketoenamine-linked chiral COF as a shell of SiO_(2) particle,the resulting composite exhibits an impressive hydrogen evolution rate of 107.1 mmol g^(-1)h^(-1)along with the apparent quantum efficiency of 14.31% at 475 nm.Furthermore,the composite photocatalysts could be fabricated into a film device,displaying a remarkable photocatalytic performance of 178.0 mmol m^(-2)h^(-1)for hydrogen evolution.Our work underpins the surface engineering of organic photocatalysts and illustrates the significance of COF stacking structures in regulating electronic properties.
文摘In this paper,a multifunctional chiral metasurface is presented to achieve asymmetric transmission(AT)and linear-polarization conversion(LPC).The designed metasurface consists of a cross swords-like shape and two holes in the lower side of the unit cell.In the frequency band from 8.3 GHz to 10.4 GHz,AT is realized with more than 90%efficiency and the same chiral metasurface transforms linear polarized wave into its orthogonal counterpart with high efficiency.For LPC,the polarization conversion ratio(PCR)is greater than 95%.The proposed metasurface is stable against the incident angles of striking electromagnetic(EM)waves up to 60°for both operations of AT and LPC.
基金supported by the National Natural Science Foundation of China(Nos.52171327,11991032,52201386,and 51805537)。
文摘Chiral metamaterials have been proven to possess many appealing mechanical phenomena,such as negative Poisson's ratio,high-impact resistance,and energy absorption.This work extends the applications of chiral metamaterials to underwater sound insulation.Various chiral metamaterials with low acoustic impedance and proper stiffness are inversely designed using the topology optimization scheme.Low acoustic impedance enables the metamaterials to have a high and broadband sound transmission loss(STL),while proper stiffness guarantees its robust acoustic performance under a hydrostatic pressure.As proof-of-concept demonstrations,two specimens are fabricated and tested in a water-filled impedance tube.Experimental results show that,on average,over 95%incident sound energy can be isolated by the specimens in a broad frequency range from 1 k Hz to 5 k Hz,while the sound insulation performance keeps stable under a certain hydrostatic pressure.This work may provide new insights for chiral metamaterials into the underwater applications with sound insulation.
文摘We study theoretically the electrical shot noise properties of tunnel junctions between a normal metal and a superconductor with the mixture of singlet s-wave and chiral triplet p-wave pairing due to broken inversion symmetry. We investigate how the shot noise properties vary as the relative amplitude between the two parity components in the pairing potential is changed. It is demonstrated that some characteristics of the electrical shot noise properties of such tunnel junctions may depend sensitively on the relative amplitude between the two parity components in the pairing potential, and some significant changes may occur in the electrical shot noise properties when the relative amplitude between the two parity components is varied from the singlet s-wave pairing dominated regime to the chiral triplet p-wave pairing dominated regime. In the chiral triplet p-wave pairing dominated regime, the ratio of noise power to electric current is close to 2e both in the in-gap and in the out-gap region. In the singlet s-wave pairing dominated regime, the value of this ratio is close to 4e in the inner gap region but may reduce to about 2e in the outer gap region as the relative amplitude of the chiral triplet pairing component is increased. The variations of the differential shot noise with the bias voltage also exhibit some significantly different features in different regimes. Such different features can serve as useful diagnostic tools for the determination of the relative magnitude of the two parity components in the pairing potential.
基金Project supported by the National Natural Science Foundation of China (Grant No.12074054)the Fundamental Research Funds for the Central Universities,China (Grant No.DUT21LK06)。
文摘Owing to the good adjustability and the strong near-field enhancement,surface plasmons are widely used in optical force trap,thus the optical force trap can achieve excellent performance.Here,we use the Laguerre–Gaussian beam and a plasmonic gold ring to separate enantiomers by the chiral optical force.Along with the radial optical force that traps the particles,there is also a chirality-sign-sensitive lateral force arising from the optical spin angular momentum,which is caused by the interaction between optical orbit angular momentum and gold ring structure.By selecting a specific incident wavelength,the strong angular scattering and non-chiral related azimuthal optical force can be suppressed.Thus the chiral related azimuthal optical force can induce an opposite orbital rotation of the trapped particles with chirality of different sign near the gold ring.This work proposes an effective approach for catchingand separating chiral enantiomers.
基金supported by the financial supports from the Guangdong Basic and Applied Basic Research Foundation(2020A1515010539)the Medical Science and Technology Research Foundation of Guangdong Province,China(A2019046)+1 种基金Guangdong Province Higher Vocational Colleges&Schools Pearl River Scholar(50117G25002)the Key Project of Universities in Guangdong Province(2021ZDZX4066).
文摘Aroma(volatile)compounds play important ecological functions in plants,and also contribute to the quality of plant-derived foods.Moreover,chiral aroma compounds affect their functions in plants and lead to different flavor quality properties.Formations of chiral aroma compounds are due to the presence of enzymes producing these compounds in plants,which are generally involved in the final biosynthetic step of the aroma compounds.Here,we review recent progress in research on the plant-derived enzymes producing chiral aroma compounds,and their changes in response to environmental factors.The chiral aroma enzymes that have been reported produce(R)-linalool,(S)-linalool,(R)-limonene,and(S)-limonene,etc.,and these enzymes are found in various plant species.We also discuss the origins of enantioselectivity in the plant-derived enzymes producing chiral aroma compounds and summarize the potential use of plants containing enzymes producing chiral aroma compounds for producing chiral flavors/fragrances.
基金financially the National Natural Science Foundation of China(51902136)the Fundamental Research Funds for the Central Universities(JUSRP12003,JUSRP622026)Natural Science Foundation of Jiangsu Province(BK20211236)。
文摘For decades,chiral nanomaterials have been extensively studied because of their extraordinary properties.Chiral nanostructures have attracted a lot of interest because of their potential applications including biosensing,asymmetric catalysis,optical devices,and negative index materials.Circularly polarized light(CPL)is the most attractive source for chirality owing to its high availability,and now it has been used as a chiral source for the preparation of chiral matter.In this review,the recent progress in the field of CPL-enabled chiral nanomaterials is summarized.Firstly,the recent advancements in the fabrication of chiral materials using circularly polarized light are described,focusing on the unique strategies.Secondly,an overview of the potential applications of chiral nanomaterials driven by CPL is provided,with a particular emphasis on biosensing,catalysis,and phototherapy.Finally,a perspective on the challenges in the field of CPL-enabled chiral nanomaterials is given.
基金This study was funded by the Project of National Natural Science Foundation of China(Grant No.:82003705)the Shanghai Science and Technology Innovation Foundation(Grant Nos.:23010500200 and 23ZR1422700).
文摘Capillary electrochromatography(CEC)plays a significant role in chiral separation via the double separation principle,partition coefficient difference between the two phases,and electroosmotic flow-driven separation.Given the distinct properties of the inner wall stationary phase(SP),the separation ability of each SP differs from one another.Particularly,it provides large room for promising applications of open tubular capillary electrochromatography(OT-CEC).We divided the OT-CEC SPs developed over the past four years into six types:ionic liquids,nanoparticle materials,microporous materials,biomaterials,non-nanopolymers,and others,to mainly introduce their characteristics in chiral drug separation.There also added a few classic SPs that occurred within ten years as supplements to enrich the features of each SP.Additionally,we discuss their applications in metabolomics,food,cosmetics,environment,and biology as analytes in addition to chiral drugs.OT-CEC plays an increasingly significant role in chiral separation and may promote the development of capillary electrophoresis(CE)combined with other instruments in recent years,such as CE with mass spectrometry(CE/MS)and CE with ultraviolet light detector(CE/UV).
基金This work is supported by the National Science Foundation of China(Grant Nos.12027807,62225501,and 11974002)National Key Research and Development Program of China(Grant No.2020YFA0211300,2020YFA0906900,and 2021YFF1200500)PKU-Baidu Fund Project(Grant No.2020BD023),and High-performance Computing Platform of Peking University.
文摘Chirality plays an important role in biological processes,and enantiomers often possess similar physical properties and different physiologic functions.In recent years,chiral detection of enantiomers become a popular topic.Plasmonic metasurfaces enhance weak inherent chiral effects of biomolecules,so they are used in chiral detection.Artificial intelligence algorithm makes a lot of contribution to many aspects of nanophotonics.Here,we propose a nanostructure design method based on reinforcement learning and devise chiral nanostructures to distinguish enantiomers.The algorithm finds out the metallic nanostructures with a sharp peak in circular dichroism spectra and emphasizes the frequency shifts caused by nearfield interaction of nanostructures and biomolecules.Our work inspires universal and efficient machine-learning methods for nanophotonic design.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.91850205 and 11904021).
文摘Chirality is ubiquitous in natural world.Although with similar physical and chemical properties,chiral enantiomers could play different roles in biochemical processes.Discrimination of chiral enantiomers is extremely important in biochemical,analytical chemistry,and pharmaceutical industries.Conventional chiroptical spectroscopic methods are disadvantageous at a limited detection sensitivity because of the weak signals of natural chiral molecules.Recently,superchiral fields were proposed to effectively enhance the interaction between light and molecules,allowing for ultrasensitive chiral detection.Intensive theoretical and experimental works have been devoted to generation of superchiral fields based on artificial nanostructures and their application in ultrasensitive chiral sensing.In this review,we present a survey on these works.We begin with the introduction of chiral properties of electromagnetic fields.Then,the optical chirality enhancement and ultrasensitive chiral detection based on chiral and achiral nanostructures are discussed respectively.Finally,we give a short summary and a perspective for the future ultrasensitive chiral sensing.
基金supports from the National Key R&D Program of China(2021YFA1200101 and 2022YFE0128700)the National Natural Science Foundation of China(22150013 and 21933001)+2 种基金the New Cornerstone Science Foundation through the XPLORER PRIZEthe Natural Science Foundation of Beijing(2222009)“Frontiers Science Centre for New Organic Matter”at Nankai University(63181206).
文摘Chirality,as the symmetric breaking of molecules,plays an essential role in physical,chemical and especially biological processes,which highlights the accurate distinction among heterochiralities as well as the precise preparation for homochirality.To this end,the well-designed structure-specific recognizer and catalysis reactor are necessitated,respectively.However,each kind of target molecules requires a custom-made chiral partner and the dynamic disorder of spatial-orientation distribution of molecules at the ensemble level leads to an inefficient protocol.In this perspective article,we developed a universal strategy capable of realizing the chirality detection and control by the external symmetry breaking based on the alignment of the molecular frame to external stimuli.Specifically,in combination with the discussion about the relationship among the chirality(molecule),spin(electron)and polarization(photon),i.e.,the three natural symmetry breaking,single-molecule junctions were proposed to achieve a single-molecule/event-resolved detection and synthesis.The fixation of the molecular orientation and the CMOS-compatibility provide an efficient interface to achieve the external input of symmetry breaking.This perspective is believed to offer more efficient applications in accurate chirality detection and precise asymmetric synthesis via the close collaboration of chemists,physicists,materials scientists,and engineers.
基金Project supported by the Basic Science Research Program of the National Research Foundation of Korea(Grant No.2021R1F1A1050539)the Yanbian University Research Project(Grant No.482022104)the Yichang Natural Science Research Project(Grant No.A22-3-010)。
文摘We investigate asymmetric spin wave scattering behaviors caused by vortex chirality in a cross-shaped ferromagnetic system by using the micromagnetic simulations.In the system,four scattering behaviors are found:(i)asymmetric skew scattering,depending on the polarity of vortex core,(ii)back scattering(reflection),depending on the vortex core stiffness,(iii)side deflection scattering,depending on structural symmetry of the vortex circulation,and(iv)geometrical scattering,depending on waveguide structure.The first and second scattering behaviors are attributed to nonlinear topological magnon spin Hall effect related to magnon spin-transfer torque effect,which has value for magnonic exploration and application.
基金supported by the National Natural Science Foundation of China(Grant No.82273879)
文摘Overlook of chiral consideration in transdermal drug delivery increases administrated dose and risk of side effects,decreasing therapeutical effects.To improve the transdermal delivery efficiency of eutomer,this work focused on investigating the law and mechanism of enantioselective enhancing effects of chiral permeation enhancers on drug enantiomers.Chiral nonsteroidal anti-inflammatory drugs and terpene permeation enhancers were selected as model drug and enhancers.The results indicated that the L-isomer of permeation enhancers increased the skin absorption of S-enantiomer of drug and D-isomer improve the permeation of R-enantiomer,in which the enhancement effect(ER)of Lmenthol on S-enantiomer(ER=3.23)was higher than that on R-enantiomer(ER=1.49).According to the pharmacokinetics results,L-menthol tended to enhance the permeation of S-enantiomer better than R-enantiomer(2.56 fold),and showed excellent in vitro/in vivo correlations.The mechanism study showed that L-isomer of permeation enhancers improved the permeation of S-enantiomer by increasing the retention,but the D-isomer by improving partition for better permeation.Enantioselective mechanism indicated that the weaker chiral H-bond interaction between drug-chiral enhancers was caused by the enantiomeric conformation.Additionally,stronger chiral enhancers-skin interaction between L-isomer and S-conformation of ceramide produced better enhancing effects.In conclusion,enantioselective interaction of chiral drug-chiral enhancers and chiral enhancers-chiral skin played a critical role in transdermal drug delivery,rational utilization of which contributed to improving the uptake of eutomer and inhibiting distomers to decrease a half of dose and side effects,increasing transdermal therapeutical efficiency.