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
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
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
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
A series of new chiral amide ligands were prepared from natural amino acids and applied to the copper-catalyzed asymmetric oxidative homocoupling reaction of 3-hydroxy-2-naphthoates.By optimizing the reaction conditio...A series of new chiral amide ligands were prepared from natural amino acids and applied to the copper-catalyzed asymmetric oxidative homocoupling reaction of 3-hydroxy-2-naphthoates.By optimizing the reaction conditions,it was found that when using L3(5 mol%)as the ligand,CuCl(5 mol%)as the catalyst,dichloromethane as the solvent,2,2,6,6-tetramethylpiperidine 1-oxyl(TEMPO)/O2 as the oxidant,and under the reaction condition of 40℃,this method exhibited good substrate tolerance.Under these conditions,a series of chiral 1,1'-bi-2-naphthol(BINOL)derivatives were synthesized with yields of 45%~90%and enantioselectivities ranging from 50∶50 to 97∶3.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
Optically pure chiral chemicals are important building blocks with widespread applications across mul-tiple scientific and industrial do-mains such as in pharmaceuticals,agrochemicals,and food,especially acting as pre...Optically pure chiral chemicals are important building blocks with widespread applications across mul-tiple scientific and industrial do-mains such as in pharmaceuticals,agrochemicals,and food,especially acting as precursors to synthesize biodegradable polymers.As an al-ternative to fossil resources,renew-able lignocellulosic biomass has been used to access chiral chemicals,due to the versatile inherent stere-ostructures and multiple functional groups,such as hydroxyl,carbonyl,and phenyl ether groups.Typically,as the two main units of(hemi)cel-lulose components in lignocellulosic biomass,D-xylose and D-glucose bear multiple chiral centers(e.g.,2R-3S-4R for D-xylose and 2R-3S-4R-5R for D-glucose).Lignin bearsβ-O-4 linkages,exhibiting(R,S/S,R)or(R,R/S,S)stereocenters at the side-chainαandβcarbon atoms.The valorization of biomass into optical-ly pure chiral chemicals is vital for developing a more sustainable future.This review discuss-es the production of typical chiral chemicals derived from biomass through chemocatalysis,including lactones(e.g.,R/S-valerolactone),carboxylic acids(e.g.,D/L-glyceric acid,D/L-lactic acid),polyols(e.g.,tetrose),furans,oligosaccharides,and others.Two strategies are generally employed.One approach involves first producing achiral platform chemicals from biomass,followed by the introduction of asymmetric catalysts to reconstruct stereocenters.The second relates to selectively preserving one or more inherent stereocenters in the natural biomass structure during complex cascade reactions in which biomass feedstock acts as a“chi-ral pool",thus eliminating the establishment of stereocenter.The feedstock,methods em-ployed,and enantioselectivity and applications of the target chiral chemicals are discussed.Despite these advances,the synthesis of optically pure chemicals from biomass is still in its in-fancy.The coming decade presents both extraordinary challenges and opportunities in biomass-derived chiral chemistry.Future research should be focused on:(1)integrating well-established asymmetric catalysis techniques and methods with biomass’s inherent chiral pools,presenting an unprecedented opportunity to expand the chemical space of sustainable chiral compounds;(2)mastering polyfunctional complexity of chiral chemicals through holis-tic utilization of biomass’multichiral centers;(3)unlocking lignin’s stereochemical treasury that represents the next frontier in biomass valorization.展开更多
Circularly polarized luminescence perovskite nanocrystals(NCs)hold great potential in the field of information encryption,3D display and spintronics.However,the synthesis of the chiral perovskites is still confronted ...Circularly polarized luminescence perovskite nanocrystals(NCs)hold great potential in the field of information encryption,3D display and spintronics.However,the synthesis of the chiral perovskites is still confronted with various problems,such as cumbersome synthesis process,poor compatibility and limited processability,which impede their further implementation.In this study,a one-step wet-ball-milling method is proposed for the scale-up synthesis(up to 500 mL)of chiral perovskite ink,where the chiral molecule R-/S-1,2-diphenylethylenediamine(R-/S-DPEM)are introduced as chiral initiator.Chiral R-/S-DPEM molecules can endow the chirality to perovskite NCs through the strong coupling with perovskite surface.Specifically,ethyl cellulose is incorporated as passivating agents and structural supporting molecules,which can not only passivate the perovskite NCs and improve their stability,but also enable the chiral ink to possess better processability.The obtained ink is compatible with multiple substrates,which can be directly processed into various luminescent patterns by means of screen printing,writing,impregnation,laser engraving,etc.These patterns demonstrate high storage stability,flexibility and water resistance,fulfilling the requirements of a wide range of occasions in the future.This work provides a feasible solution for scalable synthesis of chiral perovskite inks,which offer promising prospects in optical anti-counterfeiting,information encryption and wearable optoelectronic devices.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.
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(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.
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...
文摘A series of new chiral amide ligands were prepared from natural amino acids and applied to the copper-catalyzed asymmetric oxidative homocoupling reaction of 3-hydroxy-2-naphthoates.By optimizing the reaction conditions,it was found that when using L3(5 mol%)as the ligand,CuCl(5 mol%)as the catalyst,dichloromethane as the solvent,2,2,6,6-tetramethylpiperidine 1-oxyl(TEMPO)/O2 as the oxidant,and under the reaction condition of 40℃,this method exhibited good substrate tolerance.Under these conditions,a series of chiral 1,1'-bi-2-naphthol(BINOL)derivatives were synthesized with yields of 45%~90%and enantioselectivities ranging from 50∶50 to 97∶3.
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 Sci-ence Foundation of China(Nos.22478263,22308230)Natural Science Foundation of Sichuan(No.2024NSF-SC1134)+2 种基金China Postdoctoral Science Foundation(No.2024T170612)111 center(B17030)the Fun-damental Research Funds for the Central Universities.
文摘Optically pure chiral chemicals are important building blocks with widespread applications across mul-tiple scientific and industrial do-mains such as in pharmaceuticals,agrochemicals,and food,especially acting as precursors to synthesize biodegradable polymers.As an al-ternative to fossil resources,renew-able lignocellulosic biomass has been used to access chiral chemicals,due to the versatile inherent stere-ostructures and multiple functional groups,such as hydroxyl,carbonyl,and phenyl ether groups.Typically,as the two main units of(hemi)cel-lulose components in lignocellulosic biomass,D-xylose and D-glucose bear multiple chiral centers(e.g.,2R-3S-4R for D-xylose and 2R-3S-4R-5R for D-glucose).Lignin bearsβ-O-4 linkages,exhibiting(R,S/S,R)or(R,R/S,S)stereocenters at the side-chainαandβcarbon atoms.The valorization of biomass into optical-ly pure chiral chemicals is vital for developing a more sustainable future.This review discuss-es the production of typical chiral chemicals derived from biomass through chemocatalysis,including lactones(e.g.,R/S-valerolactone),carboxylic acids(e.g.,D/L-glyceric acid,D/L-lactic acid),polyols(e.g.,tetrose),furans,oligosaccharides,and others.Two strategies are generally employed.One approach involves first producing achiral platform chemicals from biomass,followed by the introduction of asymmetric catalysts to reconstruct stereocenters.The second relates to selectively preserving one or more inherent stereocenters in the natural biomass structure during complex cascade reactions in which biomass feedstock acts as a“chi-ral pool",thus eliminating the establishment of stereocenter.The feedstock,methods em-ployed,and enantioselectivity and applications of the target chiral chemicals are discussed.Despite these advances,the synthesis of optically pure chemicals from biomass is still in its in-fancy.The coming decade presents both extraordinary challenges and opportunities in biomass-derived chiral chemistry.Future research should be focused on:(1)integrating well-established asymmetric catalysis techniques and methods with biomass’s inherent chiral pools,presenting an unprecedented opportunity to expand the chemical space of sustainable chiral compounds;(2)mastering polyfunctional complexity of chiral chemicals through holis-tic utilization of biomass’multichiral centers;(3)unlocking lignin’s stereochemical treasury that represents the next frontier in biomass valorization.
基金supported by National Natural Science Foundation of China(Grant Nos.52572185,12204427 and 52272166)Natural Science Foundation of Henan Province of China(Grant Nos.242300421217,and 222300420299).
文摘Circularly polarized luminescence perovskite nanocrystals(NCs)hold great potential in the field of information encryption,3D display and spintronics.However,the synthesis of the chiral perovskites is still confronted with various problems,such as cumbersome synthesis process,poor compatibility and limited processability,which impede their further implementation.In this study,a one-step wet-ball-milling method is proposed for the scale-up synthesis(up to 500 mL)of chiral perovskite ink,where the chiral molecule R-/S-1,2-diphenylethylenediamine(R-/S-DPEM)are introduced as chiral initiator.Chiral R-/S-DPEM molecules can endow the chirality to perovskite NCs through the strong coupling with perovskite surface.Specifically,ethyl cellulose is incorporated as passivating agents and structural supporting molecules,which can not only passivate the perovskite NCs and improve their stability,but also enable the chiral ink to possess better processability.The obtained ink is compatible with multiple substrates,which can be directly processed into various luminescent patterns by means of screen printing,writing,impregnation,laser engraving,etc.These patterns demonstrate high storage stability,flexibility and water resistance,fulfilling the requirements of a wide range of occasions in the future.This work provides a feasible solution for scalable synthesis of chiral perovskite inks,which offer promising prospects in optical anti-counterfeiting,information encryption and wearable optoelectronic devices.
