Chirality is a fundamental geometric property that manifests across molecular and nanoscale systems,profoundly influencing physical,chemical,and biological processes.At the intersection of chiral chemistry and nanosci...Chirality is a fundamental geometric property that manifests across molecular and nanoscale systems,profoundly influencing physical,chemical,and biological processes.At the intersection of chiral chemistry and nanoscience,chiral nanomaterials have emerged as a transformative class of materials,exhibiting unique spin-dependent properties governed by the chiral-induced spin selectivity(CISS)effect.This quantum phenomenon,rooted in spin-orbit coupling and spin filtering mechanisms,enables precise modulation of electron spin polarization,unlocking new opportunities in catalysis,spintronics,and energy conversion.This review provides a comprehensive overview of the CISS effect in chiral nanomaterials,elucidating its underlying mechanisms—including spin-orbit interactions,spin filtering,and spin blockade—and surveying advanced techniques for characterizing both structural chirality and spin polarization.We further highlight emerging applications in electrocatalysis,photocatalysis,and spintronic device engineering.Despite significant progress,key challenges remain in unraveling the fundamental physics,achieving accurate spin characterization,and translating these phenomena into robust,scalable technologies.Continued interdisciplinary research into the rational design and functionalization of chiral nanomaterials is poised to drive breakthroughs in sustainable energy,next-generation catalysis,and quantum information technologies.展开更多
Life on Earth uses a common set of L-amino acids(L-aa)to construct proteins and D-nucleosides(D-Nu)to form nucleic acids,which serve as the carrier of genetic information.Herein,we reveal the in-trinsic mechanism of c...Life on Earth uses a common set of L-amino acids(L-aa)to construct proteins and D-nucleosides(D-Nu)to form nucleic acids,which serve as the carrier of genetic information.Herein,we reveal the in-trinsic mechanism of chiral selection of L-aa and D-Nu from the perspective of chemical origin of life.This work employed^(15)N-labeled L-aa and performed one-pot synthesis of nucleotide amidate of amino acid(N-aa-NMP)using equal amounts of L-^(15)N-aa and D-^(14)N-aa with D-/L-Nu in the aqueous solution of trimetaphosphate,generating L-^(15)N-aa-NMP and D-^(14)N-aa-NMP,respectively.The ^(31)P-NMR data indicated that L-aa was preferentially selected during the formation of N-aa-NMP in the presence of D-Nu.Surpris-ingly,D-aa was preferred over L-aa in the presence of L-Nu.Further analysis revealed that L-^(15)N-aa-D-NMP vs.D-^(14)N-aa-L-NMP and D-^(14)N-aa-D-NMP vs.L-^(15)N-aa-L-NMP were mirror isomers of each other,respec-tively.These data suggest that there could be a set of chiral systems opposite to that on Earth,which infers there might be a world of life that is a mirror image of the Earth.展开更多
In the present work,two Troger's base-based macrocycles(TBBMs)with different bridging ethylene glycol chains(T1,n=1;T3,n=3)were successfully synthesized and studied via the crystal analysis.These two TBBMs possess...In the present work,two Troger's base-based macrocycles(TBBMs)with different bridging ethylene glycol chains(T1,n=1;T3,n=3)were successfully synthesized and studied via the crystal analysis.These two TBBMs possess rare rectangular-like cavities and show chiral selection during the crystallization.T1with short glycol chain(n=1)crystallized as racemates,while T3 with long glycol chain(n=3)was found as meso isomer.In contrast to T1 and T3,for T2(n=2)both rac-T2 and meso isomer R2NS2N-T2has been observed in our previous report.Thus,the synthesis of new TBBMs T1 and T3 with different bridging ethylene glycol chains not only makes the study of TBBMs more systematically,but also helps to understand the relationship between the size of the rectangular cavity and the chiral selection of Troger's base-based macrocycles during their crystallization.展开更多
Single-walled carbon nanotubes(SWNTs)with enriched(n,m)species are in high demand for various advanced applications.Since the SWNT structure is largely influenced by the chemistry of the active catalyst during growth ...Single-walled carbon nanotubes(SWNTs)with enriched(n,m)species are in high demand for various advanced applications.Since the SWNT structure is largely influenced by the chemistry of the active catalyst during growth process,exploiting novel catalyst with bias towards specific SWNT chiralities has been challenging.In this work,we introduce a vanadium catalyst supported by mesoporous magnesia(V-MgO)for the selective growth of SWNTs using CO chemical vapor deposition(CVD).At a reaction temperature of 650℃,the(6,5)SWNT content reaches an impressive 67.9%among all semiconducting species,exceeding the selectivity of many commercial SWNT products.Post-CVD analysis reveals that the catalyst transforms into vanadium carbide(VC),which acts as a nucleation site for SWNT growth.Molecular dynamics simulations indicate that the energy at the SWNT-VC interface and the growth kinetics of SWNTs contribute to the chirality selectivity.This research opens up possibilities for the selective synthesis of SWNTs using cost-effective early transition metals,illuminating their future applications in fields such as bioimaging.展开更多
Semiconducting single-walled carbon nanotubes(s-SWCNTs)are fascinating materials for future electronic and optical applications.Conjugated polymer wrapping is one of the most promising methods for mass production of h...Semiconducting single-walled carbon nanotubes(s-SWCNTs)are fascinating materials for future electronic and optical applications.Conjugated polymer wrapping is one of the most promising methods for mass production of high purity s-SWCNTs.However,its chiral selectivity is relatively inferior to other s-SWCNT production methods.In this paper,the chiral selectivity of two polymers,poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(6,6′-{2,2′-bipyridine})](PFO-BPy)and poly[9-(1-octylonoyl)-9H-carbazole-2,7-diyl](PCz),which are representatives of widely used polyfluorene and polycarbazole families,respectively,were comparatively studied.Both polymers exhibited high selectivity for a subset of existing chiral species in each of the commercially available raw SWCNT materials(CoMoCAT,HiPco,and arc-discharge)which cover a diameter range of 0.6–1.8 nm.Less chiral species were selected by PFO-BPy from small diameter(<1 nm)raw SWCNT materials,while more from large diameter(>1.2 nm)raw materials.High chiral purity(6,5)(>99%)and(7,5)(>75%)solutions were extracted by PFO-BPy and PCz from CoMoCAT materials,respectively.The different chiral angle and diameter selections for different raw materials by both polymers were ascribed to their different geometrical structures and related polymer-tube interactions.Our work provides indispensable information for better understanding the mechanism of polymer wrapping method and improving extraction of single chirality sSWCNTs.展开更多
Amino acid homochirality,as a unique behavior of life,could have originated synchronously with the genetic code.In this paper,phosphoryl amino-acid-5′-nucleosides with P-N bond are postulated to be a chiral origin mo...Amino acid homochirality,as a unique behavior of life,could have originated synchronously with the genetic code.In this paper,phosphoryl amino-acid-5′-nucleosides with P-N bond are postulated to be a chiral origin model in prebiotic molecular evolution.The enthalpy change in the intramolecular interaction between the nucleotide base and the amino-acid side-chain determines the sta-bility of the particular complex,resulting in a preferred conformation associated with the chirality of amino acids.Based on the theoretical model,our experiments and calculations show that the chiral selection of the earliest amino acids for L-enantiomers seems to be a strict stereochemi-cal/physicochemical determinism.As other amino acids developed biosynthetically from the earliest amino acids,we infer that the chirality of the later amino acids was inherited from the precursor amino acids.This idea probably goes far back in history,but it is hoped that it will be a guide for further ex-periments in this area.展开更多
Chiral perovskites(CPs)have attracted enormous attentions since they have combined chirality and optoelectrical properties well which is promising in circularly polarized luminescence(CPL)application and of great impo...Chiral perovskites(CPs)have attracted enormous attentions since they have combined chirality and optoelectrical properties well which is promising in circularly polarized luminescence(CPL)application and of great importance for future spin-optoelectronics.However,there is a key contradiction that in chiral perovskites chirality distorts the crystal structure,leading to poor photoluminescence(PL)properties.Achieving the balance between chirality and PL is a major challenge for strong CPL from chiral perovskites.Differently,two-dimensional(2D)chiral perovskite has shown fascinating chiral induced spin selectivity(CISS)effect which can act as spin injector under ambient conditions.Here,we propose an effective strategy to achieve high CPL activity generated from quantum dots(QDs)by introducing 2D chiral perovskite as a chiral source,providing spin polarized carriers through the CISS effect.The as-synthesized QDs/CP composites exhibit dissymmetry factors(glum)up to 9.06×10^(−3).For the first time,we performed grazing incident wide angle X-ray scattering(GIWAXS)measurements,showing the chirality originates from the distorted lattices caused by the large chiral organic cations.Besides,time-resolved PL(TR-PL)measurements verify the enhanced CPL activity should be attributed to the charge transport between two components.These findings provide a useful method to achieve CPL in QDs/2D chiral perovskite heterojunctions which could be promising in spinoptoelectronics application.展开更多
CONSPECTUS:Chirality has been relevant to numerous core scientific topics over the past century.Recently,the value of chirality in artificial functional materials has been recognized and investigated intensively.Funct...CONSPECTUS:Chirality has been relevant to numerous core scientific topics over the past century.Recently,the value of chirality in artificial functional materials has been recognized and investigated intensively.Functional materials with chirality demonstrate some characteristic properties lacking in their achiral counterparts.Specifically,in chiral materials,optical rotatory dispersion,circular dichroism(CD),circularly polarized luminescence,nonlinear optical effect,and chiral-induced spin selectivity have been observed.展开更多
基金supported by the Shanghai Pilot Program for Basic Research-Shanghai Jiao Tong University(21TQ1400211)the National Key Research and Development Program of China(2023YFB4004900)the Natural Science Foundation of Chongqing,China(CSTB2024NSCQ-MSX1115)。
文摘Chirality is a fundamental geometric property that manifests across molecular and nanoscale systems,profoundly influencing physical,chemical,and biological processes.At the intersection of chiral chemistry and nanoscience,chiral nanomaterials have emerged as a transformative class of materials,exhibiting unique spin-dependent properties governed by the chiral-induced spin selectivity(CISS)effect.This quantum phenomenon,rooted in spin-orbit coupling and spin filtering mechanisms,enables precise modulation of electron spin polarization,unlocking new opportunities in catalysis,spintronics,and energy conversion.This review provides a comprehensive overview of the CISS effect in chiral nanomaterials,elucidating its underlying mechanisms—including spin-orbit interactions,spin filtering,and spin blockade—and surveying advanced techniques for characterizing both structural chirality and spin polarization.We further highlight emerging applications in electrocatalysis,photocatalysis,and spintronic device engineering.Despite significant progress,key challenges remain in unraveling the fundamental physics,achieving accurate spin characterization,and translating these phenomena into robust,scalable technologies.Continued interdisciplinary research into the rational design and functionalization of chiral nanomaterials is poised to drive breakthroughs in sustainable energy,next-generation catalysis,and quantum information technologies.
基金supported by the National Natural Science Foundation of China (Nos.91856126,42003062,21778042 and 41876072)Scientific Research Grant of Ningbo University (No.215432000282)Ningbo Top Talent Project (No.215-432094250)。
文摘Life on Earth uses a common set of L-amino acids(L-aa)to construct proteins and D-nucleosides(D-Nu)to form nucleic acids,which serve as the carrier of genetic information.Herein,we reveal the in-trinsic mechanism of chiral selection of L-aa and D-Nu from the perspective of chemical origin of life.This work employed^(15)N-labeled L-aa and performed one-pot synthesis of nucleotide amidate of amino acid(N-aa-NMP)using equal amounts of L-^(15)N-aa and D-^(14)N-aa with D-/L-Nu in the aqueous solution of trimetaphosphate,generating L-^(15)N-aa-NMP and D-^(14)N-aa-NMP,respectively.The ^(31)P-NMR data indicated that L-aa was preferentially selected during the formation of N-aa-NMP in the presence of D-Nu.Surpris-ingly,D-aa was preferred over L-aa in the presence of L-Nu.Further analysis revealed that L-^(15)N-aa-D-NMP vs.D-^(14)N-aa-L-NMP and D-^(14)N-aa-D-NMP vs.L-^(15)N-aa-L-NMP were mirror isomers of each other,respec-tively.These data suggest that there could be a set of chiral systems opposite to that on Earth,which infers there might be a world of life that is a mirror image of the Earth.
基金the financial support from the National Natural Science Foundation of China(Nos.21901113,21871135)the Natural Science Foundation of Jiangsu Province(No.BK20190287)financially supported by the Starry Night Science Foundation of Zhejiang University Shanghai Institute for Advanced Study(No.SN-ZJU-SIAS-006)。
文摘In the present work,two Troger's base-based macrocycles(TBBMs)with different bridging ethylene glycol chains(T1,n=1;T3,n=3)were successfully synthesized and studied via the crystal analysis.These two TBBMs possess rare rectangular-like cavities and show chiral selection during the crystallization.T1with short glycol chain(n=1)crystallized as racemates,while T3 with long glycol chain(n=3)was found as meso isomer.In contrast to T1 and T3,for T2(n=2)both rac-T2 and meso isomer R2NS2N-T2has been observed in our previous report.Thus,the synthesis of new TBBMs T1 and T3 with different bridging ethylene glycol chains not only makes the study of TBBMs more systematically,but also helps to understand the relationship between the size of the rectangular cavity and the chiral selection of Troger's base-based macrocycles during their crystallization.
基金financially supported by the Key Basic Research Project of Shandong Province(No.ZR2019ZD49)Taishan Scholar Foundation of Shandong Province(No.tstp20230627)Open Research Fund of State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences。
文摘Single-walled carbon nanotubes(SWNTs)with enriched(n,m)species are in high demand for various advanced applications.Since the SWNT structure is largely influenced by the chemistry of the active catalyst during growth process,exploiting novel catalyst with bias towards specific SWNT chiralities has been challenging.In this work,we introduce a vanadium catalyst supported by mesoporous magnesia(V-MgO)for the selective growth of SWNTs using CO chemical vapor deposition(CVD).At a reaction temperature of 650℃,the(6,5)SWNT content reaches an impressive 67.9%among all semiconducting species,exceeding the selectivity of many commercial SWNT products.Post-CVD analysis reveals that the catalyst transforms into vanadium carbide(VC),which acts as a nucleation site for SWNT growth.Molecular dynamics simulations indicate that the energy at the SWNT-VC interface and the growth kinetics of SWNTs contribute to the chirality selectivity.This research opens up possibilities for the selective synthesis of SWNTs using cost-effective early transition metals,illuminating their future applications in fields such as bioimaging.
基金the National Natural Science Foundation of China(Nos.U21A6004 and 51991341)Science and Technology Major Project of Shanxi(No.202101030201022)Young Talents Program of Beijing(No.2018000020028G349)。
文摘Semiconducting single-walled carbon nanotubes(s-SWCNTs)are fascinating materials for future electronic and optical applications.Conjugated polymer wrapping is one of the most promising methods for mass production of high purity s-SWCNTs.However,its chiral selectivity is relatively inferior to other s-SWCNT production methods.In this paper,the chiral selectivity of two polymers,poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(6,6′-{2,2′-bipyridine})](PFO-BPy)and poly[9-(1-octylonoyl)-9H-carbazole-2,7-diyl](PCz),which are representatives of widely used polyfluorene and polycarbazole families,respectively,were comparatively studied.Both polymers exhibited high selectivity for a subset of existing chiral species in each of the commercially available raw SWCNT materials(CoMoCAT,HiPco,and arc-discharge)which cover a diameter range of 0.6–1.8 nm.Less chiral species were selected by PFO-BPy from small diameter(<1 nm)raw SWCNT materials,while more from large diameter(>1.2 nm)raw materials.High chiral purity(6,5)(>99%)and(7,5)(>75%)solutions were extracted by PFO-BPy and PCz from CoMoCAT materials,respectively.The different chiral angle and diameter selections for different raw materials by both polymers were ascribed to their different geometrical structures and related polymer-tube interactions.Our work provides indispensable information for better understanding the mechanism of polymer wrapping method and improving extraction of single chirality sSWCNTs.
基金Supported by the National Natural Science Foundation of China(Grant No.20572061)the Science Foundation of Xiamen University(Grant No.Z03120)
文摘Amino acid homochirality,as a unique behavior of life,could have originated synchronously with the genetic code.In this paper,phosphoryl amino-acid-5′-nucleosides with P-N bond are postulated to be a chiral origin model in prebiotic molecular evolution.The enthalpy change in the intramolecular interaction between the nucleotide base and the amino-acid side-chain determines the sta-bility of the particular complex,resulting in a preferred conformation associated with the chirality of amino acids.Based on the theoretical model,our experiments and calculations show that the chiral selection of the earliest amino acids for L-enantiomers seems to be a strict stereochemi-cal/physicochemical determinism.As other amino acids developed biosynthetically from the earliest amino acids,we infer that the chirality of the later amino acids was inherited from the precursor amino acids.This idea probably goes far back in history,but it is hoped that it will be a guide for further ex-periments in this area.
基金Guangdong Basic and Applied Basic Research Foundation(Nos.2022A1515011071,2019A1515111093,and 2022A1515011614)the National Natural Science Foundation of China(Nos.62122034,61875082,61905107,62204107,and 62205138)+2 种基金Innovation Project of Department of Education of Guangdong Province(No.2019KTSCX157)Shenzhen Innovation Project(Nos.JCYJ20210324104413036 and JCYJ20190809152411655)Q.Q.W.and H.M.Z.acknowledge the support from China Postdoctoral Science Foundation(Nos.2021M691397 and 2021M691411).
文摘Chiral perovskites(CPs)have attracted enormous attentions since they have combined chirality and optoelectrical properties well which is promising in circularly polarized luminescence(CPL)application and of great importance for future spin-optoelectronics.However,there is a key contradiction that in chiral perovskites chirality distorts the crystal structure,leading to poor photoluminescence(PL)properties.Achieving the balance between chirality and PL is a major challenge for strong CPL from chiral perovskites.Differently,two-dimensional(2D)chiral perovskite has shown fascinating chiral induced spin selectivity(CISS)effect which can act as spin injector under ambient conditions.Here,we propose an effective strategy to achieve high CPL activity generated from quantum dots(QDs)by introducing 2D chiral perovskite as a chiral source,providing spin polarized carriers through the CISS effect.The as-synthesized QDs/CP composites exhibit dissymmetry factors(glum)up to 9.06×10^(−3).For the first time,we performed grazing incident wide angle X-ray scattering(GIWAXS)measurements,showing the chirality originates from the distorted lattices caused by the large chiral organic cations.Besides,time-resolved PL(TR-PL)measurements verify the enhanced CPL activity should be attributed to the charge transport between two components.These findings provide a useful method to achieve CPL in QDs/2D chiral perovskite heterojunctions which could be promising in spinoptoelectronics application.
基金supported by the Ministry of Science and Technology of China(Grant no.2021YFA1200303)the National Natural Science Foundation of China(Grant nos.21721002,52003065)+3 种基金the Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB36000000)China Postdoctoral Science Foundation(Grant no.2019M660584)the China Scholarship Council(202104910462,202004910155)the Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2023RC102).
文摘CONSPECTUS:Chirality has been relevant to numerous core scientific topics over the past century.Recently,the value of chirality in artificial functional materials has been recognized and investigated intensively.Functional materials with chirality demonstrate some characteristic properties lacking in their achiral counterparts.Specifically,in chiral materials,optical rotatory dispersion,circular dichroism(CD),circularly polarized luminescence,nonlinear optical effect,and chiral-induced spin selectivity have been observed.
