Azobenzene-winged phenanthrolines(L1 and L2)were designed,synthesized,and fully characterized.Ligand L1 forms an in-situ cobalt complex,which has been effectively employed as a circular dichroism(CD)-active chiral sen...Azobenzene-winged phenanthrolines(L1 and L2)were designed,synthesized,and fully characterized.Ligand L1 forms an in-situ cobalt complex,which has been effectively employed as a circular dichroism(CD)-active chiral sensor.The resulting ternary complex(L1-Co^(2+)-amino alcohol)exhibits pronounced exciton-coupled circular dichroism(ECCD)signals at the characteristic azobenzene absorption bands.These signals arise from efficient chirality transfer from the chiral amino alcohol to the azobenzene chromophores,enabling the determination of the absolute configuration of chiral amino alcohols.Accordingly,the L1-Co^(2+)coordination system demonstrates considerably potential in chirality sensing applications.Remarkably,the induced ECCD signals are highly responsive to multiple external stimuli,including photoirradiation,solvent polarity,temperature,and redox conditions.In particular,temperature and redox changes can induce a reversible inversion of the ECCD signal,thereby establishing this system as a multifunctional,stimuli-responsive chiroptical molecular switch.展开更多
Helicene-type compounds are renowned for their unique chiral properties,however,obtaining their enantiomers usually requires laborious and costly chiral separations.Moreover,their chiroptical activity is typically lim...Helicene-type compounds are renowned for their unique chiral properties,however,obtaining their enantiomers usually requires laborious and costly chiral separations.Moreover,their chiroptical activity is typically limited to the ultraviolet spectral range,which restricts their broader applicability.To overcome these limitations,a novel and efficient strategy for synthesizing optically active compounds through the incorporation of an optically pure binaphthol(BINOL)group onto the periphery of β-isoindigo based aza dipyrrometheneboron difluoride(aza-BODIPY)analogues(BIABs)was presented.The resulting(R)/(S)-BINOL-BIABs demonstrate exceptional photostability,deep-red emission,strong Cotton effect(Δε)and high absorbance dissymmetry factor(g_(abs)).Moreover,tunable circularly polarized luminescence(CPL)with high brightness in the deep-red region was achieved.This strategy offers straightforward procedures for synthesizing optically active compounds.展开更多
Chirality,ubiquitous in living matter,plays vital roles in a series of physiological processes.The clarification of the multiple functions of chirality in bioapplications may provide innovative methodologies for engin...Chirality,ubiquitous in living matter,plays vital roles in a series of physiological processes.The clarification of the multiple functions of chirality in bioapplications may provide innovative methodologies for engineering anti-tumor agents.Nevertheless,the related research has been rarely explored.In this study,the chiral supramolecular l/d-cysteine(Cys)-Zn^(2+)-indocyanine green(ICG)nanoparticles were constructed through the coordination interaction between l/d-Cys and Zn^(2+),followed by the encapsulation of ICG.Experimental findings revealed that the d-Cys-Zn^(2+)-ICG exhibited 17.31 times higher binding affinity toward phospholipid-composed liposomes compared to l-Cys-Zn^(2+)-ICG.Furthermore,driven by chiralityspecific interaction,a 2.07 folds greater cellular internalization of d-Cys-Zn^(2+)-ICG than l-Cys-Zn^(2+)-ICG was demonstrated.Additionally,the triple-level chirality-dependent photothermal,photodynamic and Zn^(2+)releasing anti-tumor effects of l/d Cys-Zn^(2+)-ICG in vitro were verified.As a result,the d-formed nanoparticles achieved 1.93 times higher anti-tumor efficiency than the l-formed ones.The triple-level chirality-mediated anti-tumor effect highlighted in this study underscores the enormous potential of chirality in biomedicine and holds substantial significance in improving cancer therapeutic efficacy.展开更多
The optical chirality of vortex structured light has attracted more and more attention in recent years due to its fascinating properties and wide potential applications.Such an issue is typically studied in a spatial ...The optical chirality of vortex structured light has attracted more and more attention in recent years due to its fascinating properties and wide potential applications.Such an issue is typically studied in a spatial medium.This work is devoted to the study of the optical chirality of vortex structured light in the temporal medium with timevarying permittivity.A full vector theoretical model is developed to describe the optical chirality of LaguerreGaussian(LG)vortex light beams that undergo the temporal reflection and transmission.展开更多
In light of the double helix structure hypothesis for photon,we attempt to elucidate the generation mechanism underlying TF(Torsion Field)from both wave and particle perspectives and the enigma surrounding chiral life...In light of the double helix structure hypothesis for photon,we attempt to elucidate the generation mechanism underlying TF(Torsion Field)from both wave and particle perspectives and the enigma surrounding chiral life on Earth by proposing a neutrino-propagation model for TF,which will serve as a crucial key in unraveling the enigma of life’s origins and is promising to trigger a paradigm transformation in future medical and healthcare technologies.展开更多
To get large dissymmetric factor(g_(lum))of organic circularly polarized luminescence(CPL)materials is still a great challenge.Although helical chirality and planar chirality are usual efficient access to enhancement ...To get large dissymmetric factor(g_(lum))of organic circularly polarized luminescence(CPL)materials is still a great challenge.Although helical chirality and planar chirality are usual efficient access to enhancement of CPL,they are not combined together to boost CPL.Here,a new tetraphenylethylene(TPE)tetracycle acid helicate bearing both helical chirality and planar chirality was designed and synthesized.Uniquely,synergy of the helical chirality and planar chirality was used to boost CPL signals both in solution and in helical self-assemblies.In the presence of octadecylamine,the TPE helicate could form helical nanofibers that emitted strong CPL signals with an absolute g_(lum)value up to 0.237.Exceptionally,followed by addition of para-phenylenediamine,the g_(lum)value was successively increased to 0.387 due to formation of bigger helical nanofibers.Compared with that of TPE helicate itself,the CPL signal of the self-assemblies was not only magnified by 104-fold but also inversed,which was very rare result for CPL-active materials.Surprisingly,the interaction of TPE helicate with xylylenediamine even gave a gel,which was transformed into suspension by shaking.Unexpectedly,the suspension showed 40-fold stronger CPL signals than the gel with signal direction inversion each other.Using synergy of the helical chirality and planar chirality to significantly boost CPL intensity provides a new strategy in preparation of organic CPL materials having very large g_(lum)value.展开更多
The scale mismatch between nanoscale biomolecules and sub-wavelength light hinders circular dichroism(CD)spectroscopy for chiral small molecule sensing.In this study,we propose a high quality-factor(Q-factor)optical c...The scale mismatch between nanoscale biomolecules and sub-wavelength light hinders circular dichroism(CD)spectroscopy for chiral small molecule sensing.In this study,we propose a high quality-factor(Q-factor)optical cavity that offers a breakthrough solution to the intrinsic trade-off between optical chirality density and mode loss.A spin-preserving chiral metasurface utilizes bound states in the continuum(BIC)-guided mode resonance(GMR)degenerate modes to achieve a high Q-factor,while ensuring the preservation of chirality purity for circularly polarized light propagating within the cavity via spin-locking mechanism.Experimental results demonstrate that the BIC-GMR degenerate state enables near-perfect transmission CD up to 0.99,without requiring symmetry breaking.Full-wave simulations further predict that this synergistically enhanced system can achieve a Q-factor as high as 10037 and generate a localized field in the molecular interaction region with an optical chirality density enhancement of up to 400-fold,leading to 5025-fold amplification of the CD signal.This study establishes a foundation for detecting low-concentration chiral molecules,reveals high-Q enhancement,and advances chiral toward single-molecule sensitivity,opening new research avenues in chiral biosensing.展开更多
Phylogenetic relations of twining chirality of Dioscorea sp.in China were analyzed based on the genes matK,rbcL and trnL;phylogenetic character of higher-level phylogeny of twining plants was analyzed at a high taxon ...Phylogenetic relations of twining chirality of Dioscorea sp.in China were analyzed based on the genes matK,rbcL and trnL;phylogenetic character of higher-level phylogeny of twining plants was analyzed at a high taxon level based on matK gene.A significant phylogenetic framework of chirality was found:(i)based on matK analysis,right-handed Dioscorea species in China congregate completely to form a monophyly;(ii)rbcL and trnL data sets also supported Chinese right-handed Dioscorea a monophyly,although with ex...展开更多
Co-assembling chiral molecules with achiral compounds via non-covalent interactions like areneperfluoroarene(AP) interactions offers an effective approach for fabricating chiral functional materials.Herein,chiral mole...Co-assembling chiral molecules with achiral compounds via non-covalent interactions like areneperfluoroarene(AP) interactions offers an effective approach for fabricating chiral functional materials.Herein,chiral molecules L/D-PF1 and L/D-PF2 with pyrene groups were synthesized and its chiroptical properties upon co-assembly with achiral compound octafluoronaphthalene(OFN) through AP interaction were systemically studied.The co-assembly of L/D-PF1/OFN and L/D-PF2/OFN exhibited distinct chiroptical properties such as circular dichroism(CD) and circularly polarized luminescence(CPL) signals.Chirality transfer from the chirality center of L/D-PF1 and L/D-PF2 to the achiral OFN and chiral amplification were successfully achieved.Besides,no significant CPL signal was observed in the self-assembly of L/DPF1 or L/D-PF2 while co-assembly with OFN exhibited obvious CPL amplification induced by AP interaction.Notably,a reversal CD signal and CPL signal could be observed in L/D-PF2/OFN when the molar ratio changed from 1:1 to 1:2 while not found in L/D-PF1/OFN,indicating that that minor structural changes of molecules could cause large changes in assembly.In addition,a series of computational calculations were conducted to verify the AP interaction between L-PF1/L-PF2 and OFN.This work demonstrated that arene-perfluoroarene interaction could drive chiral transfer,chiral amplification and chiral inversion and provided a new method for the preparation of chiroptical materials.展开更多
Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated fo...Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated for the first time that a chiral metal-organic cage(MOC),[Zn_(6)M_(4)],as a universal chiral recognition material for both multi-mode high-performance liquid chromatography(HPLC) and capillary gas chromatography(GC) enantioseparation.Two novel HPLC CSPs with different bonding arms(CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn_(6)M_(4)] onto thiolated silica via thiol-ene click chemistry.Meanwhile,a capillary GC column statically coated with the chiral MOC [Zn_(6)M_(4)] was also fabricated.The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC(NP-HPLC) and reversed phase(RP-HPLC) but also in GC,and various racemates were well separated,including alcohols,diols,esters,ketones,ethers,amines,and epoxides.Importantly,CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation,which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns,suggesting the great potential of the two prepared CSPs in enantioseparation.This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC,and also paves the way to expand the potential applications of MOCs.展开更多
Albeit notable endeavors in the construction of organophosphorodithioates,the direct catalytic enantioselective synthesis of organophosphorodithioates still stands for a long-lasting challenge.Herein,an efficient orga...Albeit notable endeavors in the construction of organophosphorodithioates,the direct catalytic enantioselective synthesis of organophosphorodithioates still stands for a long-lasting challenge.Herein,an efficient organocatalytic enantioselective nucleophilic addition of vinylidene ortho-quinone methide with phosphinothioic thioanhydride as nucleophilic reagent has been achieved by the dual catalysis of cinchona alkaloid-derived squaramide and 4-dimethylaminopyridine.This protocol provides a straightforward approach for accessing a variety of axially chiral phosphorodithiolated styrenes in good yields(up to 98 %yield) with high stereoselectivities(up to 97 % ee and >99:1 E/Z).展开更多
Chiral amino acids(AAs)serve as essential building blocks of proteins and play vital physiological roles in living organisms.To achieve accurate,rapid,and high-throughput analysis of chiral AAs,this work proposed a me...Chiral amino acids(AAs)serve as essential building blocks of proteins and play vital physiological roles in living organisms.To achieve accurate,rapid,and high-throughput analysis of chiral AAs,this work proposed a methylbenzyl isocyanate(MBIC)derivatization strategy coupled with ultra-high performance liquid chromatography-mass spectrometry or trapped ion mobility spectrometry-mass spectrometry.The integration of a chiral carbon atom with a rigid urea-based structure can significantly enhance the separation of chiral MBIC-labeled AA enantiomers.This phenomenon can be attributed to the labeled l-AAs allow the carboxyl group to form intramolecular hydrogen bonds with the amino group in the rigid urea-based structure,whereas labeled d-AAs are unable to form such bonds.The method based on MBIC derivatization coupled with ultra-performance liquid chromatography-tandem mass spectrometry achieved simultaneous separation of 19 pairs of chiral AAs using only a C18 column within 30 min,enabling quantitatively detect twelve types of chiral AAs in the serum of healthy humans and Parkinson's patients.The distribution of twenty-four chiral AAs is observed in mouse brain using MBIC labeling-based matrix-assisted laser desorption/ionization-trapped ion mobility spectrometry-mass spectrometry imaging without prior separation.Our work elucidates the principles governing the separation of chiral AAs using derivatization methods,providing valuable guidance for the separation of chiral compounds.展开更多
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
Enantioselective C–H functionalization has emerged as an efficient and transformative tool for constructing complex chiral molecules with exceptional step-and atom-economy.While this field was historically dominated ...Enantioselective C–H functionalization has emerged as an efficient and transformative tool for constructing complex chiral molecules with exceptional step-and atom-economy.While this field was historically dominated by 4d and 5d transition metal catalysts,recent attention has shifted toward cobalt—an earthabundant,cost-effective 3d transition metal with unique reactivity.Over the past few years,remarkable progress has been achieved in cobalt-catalyzed enantioselective C–H functionalization,primarily through three catalytic systems:(1)low-valent cobalt(Ⅰ)catalysis,(2)cyclopentadienyl cobalt(Ⅲ)catalysis,and(3)in situ generated cobalt(Ⅲ)catalysis.This review provides a comprehensive survey of all reported asymmetric cobalt-catalyzed C–H activations proceeding through inner-sphere mechanisms,providing a systematic analysis of synthetic methodologies,reactivity patterns,origins of stereocontrol,mechanistic insights,and future opportunities.展开更多
The detection of amino acid enantiomers holds significant importance in biomedical,chemical,food,and other fields.Traditional chiral recognition methods using fluorescent probes primarily rely on fluorescence intensit...The detection of amino acid enantiomers holds significant importance in biomedical,chemical,food,and other fields.Traditional chiral recognition methods using fluorescent probes primarily rely on fluorescence intensity changes,which can compromise accuracy and repeatability.In this study,we report a novel fluorescent probe(R)-Z1 that achieves effective enantioselective recognition of chiral amino acids in water by altering emission wavelengths(>60 nm).This water-soluble probe(R)-Z1 exhibits cyan or yellow-green luminescence upon interaction with amino acid enantiomers,enabling reliable chiral detection of 14 natural amino acids.It also allows for the determination of enantiomeric excess through monitoring changes in luminescent color.Additionally,a logic operation with two inputs and three outputs was constructed based on these optical properties.Notably,amino acid enantiomers were successfully detected via dual-channel analysis at both the food and cellular levels.This study provides a new dynamic luminescence-based tool for the accurate sensing and detection of amino acid enantiomers.展开更多
Organic-inorganic metal halides(OIMHs)have emerged as highly promising novel multifunctional optoelectronic materials,owing to their easily adjustable properties from a variety of combinations of different components....Organic-inorganic metal halides(OIMHs)have emerged as highly promising novel multifunctional optoelectronic materials,owing to their easily adjustable properties from a variety of combinations of different components.But it is still difficult and rare to realize highly tunable multicolor luminescence within the same material.In this work,we successfully incorporated three adjustable emission centers in OIMHs to synthesize a novel OIMH(NEA)_(2)MnBr_(4),with each emission center capable of emitting one of the primary colors—red,green,and blue.The green and red emissions originate from the tetrahedron and octahedron structures in the Mn-based frame,while the blue can be attributed to the contribution of organic components.Additionally,to achieve comparable emission intensity among the three primary colors,we enhanced the blue emission performance by optimizing the ratio of organic structure components and incorporating chirality in the OIMHs.The resulting high-quality films can be obtained by spin-coating method with a photoluminescence quantum yields of up to 96%.More interestingly,by the dual manipulation of excitation wavelength and temperature,the sample can be emitted at least seven distinct colors including a standard white luminescence at(0.33,0.33),opening up promising prospects for multicolor luminescence applications such as high-end anti-counterfeiting technology,light-emitting diodes,X-ray imaging,latent fingerprints,humidity detection,and so on.Therefore,based on application scenarios and requirements,our research on this highly tunable luminescent OIMH material lays a solid foundation for further development of various functional properties of related materials.展开更多
文章使用手性大分子引发剂poly-150引发手性单体1与非手性单体2共聚得到侧基有活泼酯修饰的共聚物poly(150-150/2n),采用后修饰的方法将羟基修饰的荧光分子3a、3b、3c与poly(150-150/2n)进行酯交换反应,即可得到不同荧光基团修饰的手性...文章使用手性大分子引发剂poly-150引发手性单体1与非手性单体2共聚得到侧基有活泼酯修饰的共聚物poly(150-150/2n),采用后修饰的方法将羟基修饰的荧光分子3a、3b、3c与poly(150-150/2n)进行酯交换反应,即可得到不同荧光基团修饰的手性螺旋聚异腈poly(150-150/3n)。通过核磁共振氢谱(1 H nuclear magnetic resonance,1 H NMR)、氟核磁共振谱(19F nuclear magnetic resonance,19F NMR)等手段对聚合物的结构进行表征,使用圆二色光谱(circular dichroism,CD)、荧光光谱及圆偏振发光(circularly polarized luminescence,CPL)光谱对聚合物的光学性质进行表征,发现共聚物poly(150-150/3n)为一类具有CPL效应的高分子材料。展开更多
基金the support of this work by the National Natural Science Foundation of China(Nos.22471182,22271201,22422108,22171194)the Science&Technology Department of Sichuan Province(No.2025zNSFSC0125)+1 种基金the Fundamental Research Funds for the Central Universities(No.20826041D4117)the Comprehensive Training Platform of Specialized Laboratory,College of Chemistry,Prof.Peng Wu of the Analytical&Testing Center,Sichuan University.
文摘Azobenzene-winged phenanthrolines(L1 and L2)were designed,synthesized,and fully characterized.Ligand L1 forms an in-situ cobalt complex,which has been effectively employed as a circular dichroism(CD)-active chiral sensor.The resulting ternary complex(L1-Co^(2+)-amino alcohol)exhibits pronounced exciton-coupled circular dichroism(ECCD)signals at the characteristic azobenzene absorption bands.These signals arise from efficient chirality transfer from the chiral amino alcohol to the azobenzene chromophores,enabling the determination of the absolute configuration of chiral amino alcohols.Accordingly,the L1-Co^(2+)coordination system demonstrates considerably potential in chirality sensing applications.Remarkably,the induced ECCD signals are highly responsive to multiple external stimuli,including photoirradiation,solvent polarity,temperature,and redox conditions.In particular,temperature and redox changes can induce a reversible inversion of the ECCD signal,thereby establishing this system as a multifunctional,stimuli-responsive chiroptical molecular switch.
文摘Helicene-type compounds are renowned for their unique chiral properties,however,obtaining their enantiomers usually requires laborious and costly chiral separations.Moreover,their chiroptical activity is typically limited to the ultraviolet spectral range,which restricts their broader applicability.To overcome these limitations,a novel and efficient strategy for synthesizing optically active compounds through the incorporation of an optically pure binaphthol(BINOL)group onto the periphery of β-isoindigo based aza dipyrrometheneboron difluoride(aza-BODIPY)analogues(BIABs)was presented.The resulting(R)/(S)-BINOL-BIABs demonstrate exceptional photostability,deep-red emission,strong Cotton effect(Δε)and high absorbance dissymmetry factor(g_(abs)).Moreover,tunable circularly polarized luminescence(CPL)with high brightness in the deep-red region was achieved.This strategy offers straightforward procedures for synthesizing optically active compounds.
基金supported by the National Natural Science Foundation of China(Nos.22002138,22372144,22272146,21922202)the Chinese Postdoctoral Science Foundation(No.2021M692714)the Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘Chirality,ubiquitous in living matter,plays vital roles in a series of physiological processes.The clarification of the multiple functions of chirality in bioapplications may provide innovative methodologies for engineering anti-tumor agents.Nevertheless,the related research has been rarely explored.In this study,the chiral supramolecular l/d-cysteine(Cys)-Zn^(2+)-indocyanine green(ICG)nanoparticles were constructed through the coordination interaction between l/d-Cys and Zn^(2+),followed by the encapsulation of ICG.Experimental findings revealed that the d-Cys-Zn^(2+)-ICG exhibited 17.31 times higher binding affinity toward phospholipid-composed liposomes compared to l-Cys-Zn^(2+)-ICG.Furthermore,driven by chiralityspecific interaction,a 2.07 folds greater cellular internalization of d-Cys-Zn^(2+)-ICG than l-Cys-Zn^(2+)-ICG was demonstrated.Additionally,the triple-level chirality-dependent photothermal,photodynamic and Zn^(2+)releasing anti-tumor effects of l/d Cys-Zn^(2+)-ICG in vitro were verified.As a result,the d-formed nanoparticles achieved 1.93 times higher anti-tumor efficiency than the l-formed ones.The triple-level chirality-mediated anti-tumor effect highlighted in this study underscores the enormous potential of chirality in biomedicine and holds substantial significance in improving cancer therapeutic efficacy.
基金National Natural Science Foundation of China(12374273,12421005,92464205)Hunan Provincial Major Sci-Tech Program(2023ZJ1010)+2 种基金Key Laboratory Foundation of Complex Environment Optoelectronic Information Perception of Ministry of EducationFundamental Research Funds for the Central Universities(YJSJ25020)Innovation Fund of Xidian University。
文摘The optical chirality of vortex structured light has attracted more and more attention in recent years due to its fascinating properties and wide potential applications.Such an issue is typically studied in a spatial medium.This work is devoted to the study of the optical chirality of vortex structured light in the temporal medium with timevarying permittivity.A full vector theoretical model is developed to describe the optical chirality of LaguerreGaussian(LG)vortex light beams that undergo the temporal reflection and transmission.
文摘In light of the double helix structure hypothesis for photon,we attempt to elucidate the generation mechanism underlying TF(Torsion Field)from both wave and particle perspectives and the enigma surrounding chiral life on Earth by proposing a neutrino-propagation model for TF,which will serve as a crucial key in unraveling the enigma of life’s origins and is promising to trigger a paradigm transformation in future medical and healthcare technologies.
基金National Natural Science Foundation of China(Nos.22072050,22372066 and 22301090)the Open Research Fund(No.2024JYBKF05)of Key Laboratory of Material Chemistry for Energy Conversion and Storage(HUST)Ministry of Educationthe China Postdoctoral Science Foundation(No.2023M731189)for financial support,and thank the Analytical and Testing Centre at Huazhong University of Science and Technology for measurement.
文摘To get large dissymmetric factor(g_(lum))of organic circularly polarized luminescence(CPL)materials is still a great challenge.Although helical chirality and planar chirality are usual efficient access to enhancement of CPL,they are not combined together to boost CPL.Here,a new tetraphenylethylene(TPE)tetracycle acid helicate bearing both helical chirality and planar chirality was designed and synthesized.Uniquely,synergy of the helical chirality and planar chirality was used to boost CPL signals both in solution and in helical self-assemblies.In the presence of octadecylamine,the TPE helicate could form helical nanofibers that emitted strong CPL signals with an absolute g_(lum)value up to 0.237.Exceptionally,followed by addition of para-phenylenediamine,the g_(lum)value was successively increased to 0.387 due to formation of bigger helical nanofibers.Compared with that of TPE helicate itself,the CPL signal of the self-assemblies was not only magnified by 104-fold but also inversed,which was very rare result for CPL-active materials.Surprisingly,the interaction of TPE helicate with xylylenediamine even gave a gel,which was transformed into suspension by shaking.Unexpectedly,the suspension showed 40-fold stronger CPL signals than the gel with signal direction inversion each other.Using synergy of the helical chirality and planar chirality to significantly boost CPL intensity provides a new strategy in preparation of organic CPL materials having very large g_(lum)value.
基金financially supported by the POSCO-POSTECH-RIST Convergence Research Center program funded by POSCOthe National Research Foundation (NRF) grant (RS-2024-00462912) funded by the Ministry of Science and ICT (MSIT) of the Korean government+4 种基金partially supported by National Natural Science Foundation of China (Nos. 12274074, 12134013)Natural Science Foundation of Jiangsu Province (BK20242024)China Scholarship Council (202406090137)Postgraduate Research & Practice Innovation Program of Jiangsu Province (KYCX24_0379)the NRF Ph.D. fellowship (RS-202525437554) funded by the Ministry of Education (MOE) of the Korean government
文摘The scale mismatch between nanoscale biomolecules and sub-wavelength light hinders circular dichroism(CD)spectroscopy for chiral small molecule sensing.In this study,we propose a high quality-factor(Q-factor)optical cavity that offers a breakthrough solution to the intrinsic trade-off between optical chirality density and mode loss.A spin-preserving chiral metasurface utilizes bound states in the continuum(BIC)-guided mode resonance(GMR)degenerate modes to achieve a high Q-factor,while ensuring the preservation of chirality purity for circularly polarized light propagating within the cavity via spin-locking mechanism.Experimental results demonstrate that the BIC-GMR degenerate state enables near-perfect transmission CD up to 0.99,without requiring symmetry breaking.Full-wave simulations further predict that this synergistically enhanced system can achieve a Q-factor as high as 10037 and generate a localized field in the molecular interaction region with an optical chirality density enhancement of up to 400-fold,leading to 5025-fold amplification of the CD signal.This study establishes a foundation for detecting low-concentration chiral molecules,reveals high-Q enhancement,and advances chiral toward single-molecule sensitivity,opening new research avenues in chiral biosensing.
基金Supported by the CAS Special Grant for Postgraduate Research,Innovation and Practice~~
文摘Phylogenetic relations of twining chirality of Dioscorea sp.in China were analyzed based on the genes matK,rbcL and trnL;phylogenetic character of higher-level phylogeny of twining plants was analyzed at a high taxon level based on matK gene.A significant phylogenetic framework of chirality was found:(i)based on matK analysis,right-handed Dioscorea species in China congregate completely to form a monophyly;(ii)rbcL and trnL data sets also supported Chinese right-handed Dioscorea a monophyly,although with ex...
基金financially supported by the National Natural Science Foundation of China (Nos.22171165 and 22371170)Natural Science Foundation of Shandong Province (No.ZR2022MB080)Scientific and Technological Frontiers in Project of Henan Province(No.242102110192)。
文摘Co-assembling chiral molecules with achiral compounds via non-covalent interactions like areneperfluoroarene(AP) interactions offers an effective approach for fabricating chiral functional materials.Herein,chiral molecules L/D-PF1 and L/D-PF2 with pyrene groups were synthesized and its chiroptical properties upon co-assembly with achiral compound octafluoronaphthalene(OFN) through AP interaction were systemically studied.The co-assembly of L/D-PF1/OFN and L/D-PF2/OFN exhibited distinct chiroptical properties such as circular dichroism(CD) and circularly polarized luminescence(CPL) signals.Chirality transfer from the chirality center of L/D-PF1 and L/D-PF2 to the achiral OFN and chiral amplification were successfully achieved.Besides,no significant CPL signal was observed in the self-assembly of L/DPF1 or L/D-PF2 while co-assembly with OFN exhibited obvious CPL amplification induced by AP interaction.Notably,a reversal CD signal and CPL signal could be observed in L/D-PF2/OFN when the molar ratio changed from 1:1 to 1:2 while not found in L/D-PF1/OFN,indicating that that minor structural changes of molecules could cause large changes in assembly.In addition,a series of computational calculations were conducted to verify the AP interaction between L-PF1/L-PF2 and OFN.This work demonstrated that arene-perfluoroarene interaction could drive chiral transfer,chiral amplification and chiral inversion and provided a new method for the preparation of chiroptical materials.
基金supported by the National Natural Science Foundation of China (Nos.22064020,22364022,and 22174125)the Applied Basic Research Foundation of Yunnan Province (Nos.202101AT070101 and 202201AT070029)。
文摘Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated for the first time that a chiral metal-organic cage(MOC),[Zn_(6)M_(4)],as a universal chiral recognition material for both multi-mode high-performance liquid chromatography(HPLC) and capillary gas chromatography(GC) enantioseparation.Two novel HPLC CSPs with different bonding arms(CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn_(6)M_(4)] onto thiolated silica via thiol-ene click chemistry.Meanwhile,a capillary GC column statically coated with the chiral MOC [Zn_(6)M_(4)] was also fabricated.The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC(NP-HPLC) and reversed phase(RP-HPLC) but also in GC,and various racemates were well separated,including alcohols,diols,esters,ketones,ethers,amines,and epoxides.Importantly,CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation,which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns,suggesting the great potential of the two prepared CSPs in enantioseparation.This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC,and also paves the way to expand the potential applications of MOCs.
基金financial support from Natural Science Foundation of China (No.22161005)Guangxi Natural Science Foundation (Nos.2021GXNSFDA075005,2024GXNSFFA010001)。
文摘Albeit notable endeavors in the construction of organophosphorodithioates,the direct catalytic enantioselective synthesis of organophosphorodithioates still stands for a long-lasting challenge.Herein,an efficient organocatalytic enantioselective nucleophilic addition of vinylidene ortho-quinone methide with phosphinothioic thioanhydride as nucleophilic reagent has been achieved by the dual catalysis of cinchona alkaloid-derived squaramide and 4-dimethylaminopyridine.This protocol provides a straightforward approach for accessing a variety of axially chiral phosphorodithiolated styrenes in good yields(up to 98 %yield) with high stereoselectivities(up to 97 % ee and >99:1 E/Z).
基金supported by the National Natural Science Foundation of China(Nos.22404023,22274021,and 22036001).
文摘Chiral amino acids(AAs)serve as essential building blocks of proteins and play vital physiological roles in living organisms.To achieve accurate,rapid,and high-throughput analysis of chiral AAs,this work proposed a methylbenzyl isocyanate(MBIC)derivatization strategy coupled with ultra-high performance liquid chromatography-mass spectrometry or trapped ion mobility spectrometry-mass spectrometry.The integration of a chiral carbon atom with a rigid urea-based structure can significantly enhance the separation of chiral MBIC-labeled AA enantiomers.This phenomenon can be attributed to the labeled l-AAs allow the carboxyl group to form intramolecular hydrogen bonds with the amino group in the rigid urea-based structure,whereas labeled d-AAs are unable to form such bonds.The method based on MBIC derivatization coupled with ultra-performance liquid chromatography-tandem mass spectrometry achieved simultaneous separation of 19 pairs of chiral AAs using only a C18 column within 30 min,enabling quantitatively detect twelve types of chiral AAs in the serum of healthy humans and Parkinson's patients.The distribution of twenty-four chiral AAs is observed in mouse brain using MBIC labeling-based matrix-assisted laser desorption/ionization-trapped ion mobility spectrometry-mass spectrometry imaging without prior separation.Our work elucidates the principles governing the separation of chiral AAs using derivatization methods,providing valuable guidance for the separation of chiral compounds.
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 Natural Science Foundation of China(22271260 to Jun-Long Niu)the Natural Science Foundation of Henan Province(232301420007,242300421033 to Jun-Long Niu242301420059,252300421178 to Dandan Yang)。
文摘Enantioselective C–H functionalization has emerged as an efficient and transformative tool for constructing complex chiral molecules with exceptional step-and atom-economy.While this field was historically dominated by 4d and 5d transition metal catalysts,recent attention has shifted toward cobalt—an earthabundant,cost-effective 3d transition metal with unique reactivity.Over the past few years,remarkable progress has been achieved in cobalt-catalyzed enantioselective C–H functionalization,primarily through three catalytic systems:(1)low-valent cobalt(Ⅰ)catalysis,(2)cyclopentadienyl cobalt(Ⅲ)catalysis,and(3)in situ generated cobalt(Ⅲ)catalysis.This review provides a comprehensive survey of all reported asymmetric cobalt-catalyzed C–H activations proceeding through inner-sphere mechanisms,providing a systematic analysis of synthetic methodologies,reactivity patterns,origins of stereocontrol,mechanistic insights,and future opportunities.
基金the financial support from the National Natural Science Foundation of China(Nos.22377097,22307036,22074114)Natural Science Foundation of Hubei Province of China(Nos.2020CFB623,2021CFB556)Engineering Research Center of Phosphorus Resources Development and Utilization of Ministry of Education(No.LCX202305)。
文摘The detection of amino acid enantiomers holds significant importance in biomedical,chemical,food,and other fields.Traditional chiral recognition methods using fluorescent probes primarily rely on fluorescence intensity changes,which can compromise accuracy and repeatability.In this study,we report a novel fluorescent probe(R)-Z1 that achieves effective enantioselective recognition of chiral amino acids in water by altering emission wavelengths(>60 nm).This water-soluble probe(R)-Z1 exhibits cyan or yellow-green luminescence upon interaction with amino acid enantiomers,enabling reliable chiral detection of 14 natural amino acids.It also allows for the determination of enantiomeric excess through monitoring changes in luminescent color.Additionally,a logic operation with two inputs and three outputs was constructed based on these optical properties.Notably,amino acid enantiomers were successfully detected via dual-channel analysis at both the food and cellular levels.This study provides a new dynamic luminescence-based tool for the accurate sensing and detection of amino acid enantiomers.
基金supported by supported by the Basic Research Project of State Key Laboratory of Photovoltaic Science and Technology(No.202401020302)funding support from the National Natural Science Foundation of China(No.62274040 and No.62304046)Shanghai science and technology innovation action plan(No.24DZ3001200)。
文摘Organic-inorganic metal halides(OIMHs)have emerged as highly promising novel multifunctional optoelectronic materials,owing to their easily adjustable properties from a variety of combinations of different components.But it is still difficult and rare to realize highly tunable multicolor luminescence within the same material.In this work,we successfully incorporated three adjustable emission centers in OIMHs to synthesize a novel OIMH(NEA)_(2)MnBr_(4),with each emission center capable of emitting one of the primary colors—red,green,and blue.The green and red emissions originate from the tetrahedron and octahedron structures in the Mn-based frame,while the blue can be attributed to the contribution of organic components.Additionally,to achieve comparable emission intensity among the three primary colors,we enhanced the blue emission performance by optimizing the ratio of organic structure components and incorporating chirality in the OIMHs.The resulting high-quality films can be obtained by spin-coating method with a photoluminescence quantum yields of up to 96%.More interestingly,by the dual manipulation of excitation wavelength and temperature,the sample can be emitted at least seven distinct colors including a standard white luminescence at(0.33,0.33),opening up promising prospects for multicolor luminescence applications such as high-end anti-counterfeiting technology,light-emitting diodes,X-ray imaging,latent fingerprints,humidity detection,and so on.Therefore,based on application scenarios and requirements,our research on this highly tunable luminescent OIMH material lays a solid foundation for further development of various functional properties of related materials.
文摘文章使用手性大分子引发剂poly-150引发手性单体1与非手性单体2共聚得到侧基有活泼酯修饰的共聚物poly(150-150/2n),采用后修饰的方法将羟基修饰的荧光分子3a、3b、3c与poly(150-150/2n)进行酯交换反应,即可得到不同荧光基团修饰的手性螺旋聚异腈poly(150-150/3n)。通过核磁共振氢谱(1 H nuclear magnetic resonance,1 H NMR)、氟核磁共振谱(19F nuclear magnetic resonance,19F NMR)等手段对聚合物的结构进行表征,使用圆二色光谱(circular dichroism,CD)、荧光光谱及圆偏振发光(circularly polarized luminescence,CPL)光谱对聚合物的光学性质进行表征,发现共聚物poly(150-150/3n)为一类具有CPL效应的高分子材料。
