Two homochiral enantiomorphic 3D coordination polymers： （D-HAPA）2[Cd2Cs（D- HAPA）（m-BDC）4]＇（EtOH） （1D） and （L-HAPA）2[Cd2Cs（L-HAPA）（m-BDC）a]＇（EtOH） （1L） （APA = 2-amino-l-propanol, m-H2BDC = 1,3-b...Two homochiral enantiomorphic 3D coordination polymers： （D-HAPA）2[Cd2Cs（D- HAPA）（m-BDC）4]＇（EtOH） （1D） and （L-HAPA）2[Cd2Cs（L-HAPA）（m-BDC）a]＇（EtOH） （1L） （APA = 2-amino-l-propanol, m-H2BDC = 1,3-benzenedicarboxylate）, have been assembled solvothermally respectively with the induction of enantiomorphic organic small molecules （D,L-APA）. 1L and 1I） crystallize in chiral space group P21 with Flack parameters of-0.012（13） and -0.07（3）, respectively, and have been characterized by satisfactory elemental analysis, FT-IR spectra, CD-spectra and single-crystal X-ray diffraction. They both exhibit sqp topological net, purple fluorescence and SHG activity.展开更多
Homochiral metal-organic frameworks(MOFs)have attracted considerable attention in many fields of research,such as chiral catalysis and chiral chromatography.However,only few homochiral MOFs can be effectively used in ...Homochiral metal-organic frameworks(MOFs)have attracted considerable attention in many fields of research,such as chiral catalysis and chiral chromatography.However,only few homochiral MOFs can be effectively used in capillary electrochromatography(CEC)and their performances are far from adequate.In this study,we successfully synthesized achiral nanocrystalline MIL-53.A facile post-synthetic modification strategy was then implemented to functionalize the product,yielding a homochiral MOF:L-His-NH-MIL-53.This MOF was then employed as a chiral coating in open-tubular CEC mode(OT-CEC),and,as such,it exhibited high enantioselectivities for several racemic drugs.The homochiral MOF and the fabricated capillary coating were systematically characterized using transmission electron microscopy,scanning electron microscopy(with energy-dispersive X-ray spectrometry),Fourier-transform infrared spectroscopy,X-ray diffractometry,thermogravimetric analysis,circular dichroism spectroscopy,Brunauer-Emmett-Teller surface area measurements,and X-ray photoelectron spectroscopy.This study is expected to provide a new strategy for the design and establishment of MOF-based chiral OT-CEC systems.展开更多
Reacting homochiral （R）-2-methylpiperazine with cobalt sulfate heptahydrate by the solution method in the presence of concentrated sulfuric acid （H2SO4） yielded two coordination compounds （C5H14N2） [CO（H2O）6]...Reacting homochiral （R）-2-methylpiperazine with cobalt sulfate heptahydrate by the solution method in the presence of concentrated sulfuric acid （H2SO4） yielded two coordination compounds （C5H14N2） [CO（H2O）6]（SO4）2 （1 and 2）. They are polymorphs, but their hydrogen bonds structure differ significantly. Both 1 and 2 crystallize in chiral space group P21 which is related with point group C2, and experimental results suggest that 1 displays ferroelectric behaviors.展开更多
With the help of in-situ formed CH_3COO- anion, a pair of 3D homochiral coordination polymers with open channels were constructed by the assembly of lactic acid derivative ligands, 1.4-DIB ligands and Cd（II） ions, n...With the help of in-situ formed CH_3COO- anion, a pair of 3D homochiral coordination polymers with open channels were constructed by the assembly of lactic acid derivative ligands, 1.4-DIB ligands and Cd（II） ions, namely [Cd3（（R）-CIA）2（CH3CO2）_2（1.4-DIB）2（H2O）2]·x（vip）（1-D） and [Cd3（（S）-CIA）2（CH3CO2）2（1.4-DIB）2（H2O）2]·x（vip）（1-L）. They contain 1D interesting ladder-like Cd-（R）-CIA（3-） chains and exhibit SHG-active behavior and photoluminescent property.展开更多
Four isostructural lanthanide compounds formulated as {[Ln4（μ3-OH）4（L-asp）3- （H2O）10]（ClO4）5·10H2O}n （Ln=Nd （1）, Sm （2）, Eu （3）, Gd （4）; asp=aspartic acid） were synthe- sized by a conventional ...Four isostructural lanthanide compounds formulated as {[Ln4（μ3-OH）4（L-asp）3- （H2O）10]（ClO4）5·10H2O}n （Ln=Nd （1）, Sm （2）, Eu （3）, Gd （4）; asp=aspartic acid） were synthe- sized by a conventional solution reaction. Their structures were characterized by single-crystal X-ray diffraction, IR spectroscopy and elemental analyses （EA）. It reveals that they crystallize in the chiral P212121 space group. Their structures feature a homochiral three-dimensional （3D） lan- thanide-organic framework, which contains a cubic [Ln4（μ3-OH）4]8＋ cluster sub-building unit （SBU）. Additionally, the photoluminescence property of Eu compound was investigated in the solid-state at room temperature.展开更多
The origin of homochirality in living organisms is controversial,stands out of being particularly important and a question which is still not satisfactorily answered.A mental picture of sequence of events that is thou...The origin of homochirality in living organisms is controversial,stands out of being particularly important and a question which is still not satisfactorily answered.A mental picture of sequence of events that is thought to have preceded the existence of chirality in molecules is described.A chemical model to mimic the original abiotic conditions in an attempt to explain the preference of homochirality in living systems was tried.The effect which might have influenced this preference is presented.The surpri...展开更多
Homochiral coordination polymers(HCPs)represent a class of structurally ordered crystalline materials assembled by the coordination of metal ions or metal clusters with chiral ligands,holding great promise for applica...Homochiral coordination polymers(HCPs)represent a class of structurally ordered crystalline materials assembled by the coordination of metal ions or metal clusters with chiral ligands,holding great promise for applications in catalysis,separation,sensing,and other fields[1-9].Chiral ligands play a central role in the construction of HCPs.Proline and its derivatives have been extensively studied as homogeneous catalysts in a wide range of asymmetric organic reactions,where the pyrrolidine-NH functionality stands out as a pivotal catalytic site[10,11].展开更多
Chiral metal-organic frameworks(CMOFs),an emerging class of heterogeneous chiral catalysts,show significant potential for application in asymmetric catalysis due to their tunable pore shapes and sizes,large internal s...Chiral metal-organic frameworks(CMOFs),an emerging class of heterogeneous chiral catalysts,show significant potential for application in asymmetric catalysis due to their tunable pore shapes and sizes,large internal surface areas,and rich chiral environments[1-4].Through over 20 years of development,researchers have invested heavily in exploring new CMOFs to enhance asymmetric catalytic performance[5-10].However,the dual pursuit of a substantial specific surface area and robust stability within a single CMOF presents a considerable challenge.Additionally,efficient CMOF catalysts,frequently synthesized from privileged chiral ligands such as proline,2,2'-bis(diphenylphosphino)-1,1'-binaph thyl(BINAP),Salen,and bis(oxazoline)(Box)[11,12],tend to exhibit more complex structures compared to their corresponding privileged chiral counterparts,thereby necessitating higher production costs.Consequently,the development of novel synthetic methodologies for constructing CMOFs as effective chiral catalysts remains a challenging endeavor.展开更多
Enantiomerically pure lanthanide(Ⅲ)-based phosphonates are successfully synthesized by using(R)-or(S)-(1-phenylethylamino)-methylphosphonate acid(pempH2),namely,R-or S-[Tb3(pempH2)2(pempH)7]-Cl2·H2O(R-Tb or S-Tb...Enantiomerically pure lanthanide(Ⅲ)-based phosphonates are successfully synthesized by using(R)-or(S)-(1-phenylethylamino)-methylphosphonate acid(pempH2),namely,R-or S-[Tb3(pempH2)2(pempH)7]-Cl2·H2O(R-Tb or S-Tb),crystallizing in chiral space group P212121.Compound R-Tb shows a one-dimensional homochiral triple-stranded helical chain structure where the Tb(III)atoms are bridged by O-P-O units andμ3-O(P)bridge.The thermal analysis,photoluminescence as well as optically active properties of compounds R-Tb and S-Tb have also been investigated.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 orig...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
Homochirality in life has always been a driving force in scientific research and natural exploration. It has not been satisfactorily explained, and systematic investigations are necessary. This paper reported a homoch...Homochirality in life has always been a driving force in scientific research and natural exploration. It has not been satisfactorily explained, and systematic investigations are necessary. This paper reported a homochiral expression of proteins dependent on the stirring direction of growing media. By controlling the stirring direction clockwise (CW) and anticlockwise (ACW) of the culture medium, proteins with distinct secondary structures were obtained, and D-amino acid may be included in the protein cultured with the stirring direction of ACW. Considering the effect of force fields, which might affect the process of folding and refolding of cellular protein in this report, the control of force fields might be a good way to prepare asymmetric drugs, and the rotational direction of the earth is possibly related to the chirality in primitive life molecules.展开更多
Hierarchical chiral self-assembly is of profound significance for biomolecules for their biological functions.Atom-precise metal nanoclusters(NCs)offer better opportunities to construct hierarchical superlattices.Neve...Hierarchical chiral self-assembly is of profound significance for biomolecules for their biological functions.Atom-precise metal nanoclusters(NCs)offer better opportunities to construct hierarchical superlattices.Nevertheless,achieving hierarchical homochiral assembly of nanocrystals protected by achiral ligands has proven to be a formidable task,with existing examples primarily limited to heterochiral assembly.Here we put forward a hierarchical assembly strategy towards precisely fabricating highly ordered homochiral superstructures.First,clusterin-nanocage type copper-hydride NCs act as synthons,of which entity is featured with a hexagonal close-packed Cu_(9)kernel embedded in a C_(3)-symmetric trigonal-prismatic metallacage,leading to a chiral core-shell primary structure with either P or M conformation.Then four homochiral NCs combined with vips through synergistic noncovalent interactions spontaneously organize into a supramolecular tetrahedral secondary structure within a unit cell.Finally,these nanoscopic supramolecular motifs pack into tertiary hierarchical superlattice of chiral cubic crystalline phase.Additionally,the crystalline material shows excellent robustness,and fascinating blueexcitable near-infrared thermally activated delayed fluorescence behavior.This work not only exhibits that nanocage-type NCs can be smart as proteins to translate chiral primary structure into tertiary chiral hierarchical complexity,but also provides new insights into structure-to-superstructure,enabling bottom-up creation of higher-level hierarchical homochiral superlattice structures.展开更多
What is the most favorite and original chemistry developed in your research group?We originally proposed the design principle for molecular ferroelectrics:ferroelectrochemistry,including quasi-spherical theory,the int...What is the most favorite and original chemistry developed in your research group?We originally proposed the design principle for molecular ferroelectrics:ferroelectrochemistry,including quasi-spherical theory,the introduction of homochirality,and H/F substitution.Ferroelectrochemistry changed the blind search for molecular ferroelectrics into targeted chemical design,which will develop into a new discipline.展开更多
Three new homochiral bis-diamine-bridged bi-Mn（salen） complexes were synthesized. Their catalysis on asymmetric epoxidation of a-methylstyrene, styrene and indene was studied with NaC10 and m-CPBA as oxidants respec...Three new homochiral bis-diamine-bridged bi-Mn（salen） complexes were synthesized. Their catalysis on asymmetric epoxidation of a-methylstyrene, styrene and indene was studied with NaC10 and m-CPBA as oxidants respectively. This homogeneous catalyst exhibited comparable catalytic activity and enantioselectivity to the Jacobsen＇s catalyst in the asymmetric epoxidation of unfunctionalized olefins. Furthermore, the catalyst could be conveniently recovered and reused at least five times without significant losses of both activity and enantioselectivity. Specially, it also could be efficiently used in large-scale reactions with superior catalytic disposition being maintained at the same level, which provided the potential for the applications in industry. The effect of axial bases, temperature and solvent on activity and enantioselectivity of the catalytic system were also studied.展开更多
Helix as essential molecular chiral phenomenon at supramolecular level offers an affective method to study chiral characteristic of homochiral coordination polymers(CPs).Herein,two homochiral CPs[Cd((R)-CBA)_(2)(3,5-D...Helix as essential molecular chiral phenomenon at supramolecular level offers an affective method to study chiral characteristic of homochiral coordination polymers(CPs).Herein,two homochiral CPs[Cd((R)-CBA)_(2)(3,5-DIT)]_(n)((R)-H_(2) CBA=(R)-4-(1-carboxyethoxy)benzoic acid,3,5-DIT=3,5-di(1 H-imidazol-1-yl)toluene,1-R)and[Zn((R)-CBA)(3,5-DIT)]_(n)(2-R)were synthesized under hydrothermal conditions.In complex 1-R,only a helical chain was built by chiral ligands(R)-CBA2-,ancillary ligands 3,5-DIT and Cd(Ⅱ)ions.After Cd(Ⅱ)ions were replaced by Zn(Ⅱ)ions under similar reaction system,Zn(Ⅱ),(R)-CBA^(2-)and/or 3,5-DIT formed six types of helices,resulting in complex 2-R.So,the metal ions played a key role in the construction of helical structures.Complexes 1-R and 2-R were also characterized by elemental analysis,PXRD,TGA,CD and UV-visible absorptions.In addition,complexes 1-R and 2-R exhibited different photoluminescence behaviors in solid sate compared to free ligand(R)-H_(2)CBA.展开更多
Homochiral cis, cis-; cis,trans- and trans, trans-spiro[4.4]nonane-1,6-diols were prepared via diastereoselective reduction of enantiomerically pure spiro[4.4]nonane-1,6-dione (1) with the corresponding reducing agent...Homochiral cis, cis-; cis,trans- and trans, trans-spiro[4.4]nonane-1,6-diols were prepared via diastereoselective reduction of enantiomerically pure spiro[4.4]nonane-1,6-dione (1) with the corresponding reducing agents: lithium n-butyldiisobutylaluminium hydride for cis,cis-diol (2) with 88% yield; BH3. HF for cis,trans-diol (3) with 91% yield; LiAlH4 for trans,trans-diol (4) with 15% yield.展开更多
A chiral lanthanide metal-organic framework based on enantiopure camphoric acid （D-H2cam）, [Nd3（D-cam）8（H2O）4Cl]n （1）, has been synthesized and characterized by single-crystal X-ray structural analysis, elemen...A chiral lanthanide metal-organic framework based on enantiopure camphoric acid （D-H2cam）, [Nd3（D-cam）8（H2O）4Cl]n （1）, has been synthesized and characterized by single-crystal X-ray structural analysis, elemental analysis, IR, thermal gravimetric, and X-ray powder diffraction. Crystal data for the title compound are as follows： orthorhombic system, space group P212121 with a = 13.8287（7）, b = 14.0715（7）, c = 25.7403（12） A^°, V = 5008.8（4） A^°3, Mr = 1333.08, Z = 4, F（000） = 2644, Dc = 1.768 g/cm^3, μ（MoKα） = 3.189 mm^-1, the final R = 0.0351 and wR = 0.0814 （I 〉 2σ（I））. Compound 1 displays an 8-connected bcu topology 3D framework and hydrogen-bonding interactions stabilize the solid-state structure. The vibrational circular dichroism （VCD） spectrum and second-order nonlinear optical effect of compound 1 have been studied in the solid state.展开更多
One new chiral zeolitic rho-type metal-organic framework [Cd（L-ala）2]n（1） has been successfully synthesized based on L-alanine chiral ligand, which demonstrates the feasibility of fabricating MOF that integrates t...One new chiral zeolitic rho-type metal-organic framework [Cd（L-ala）2]n（1） has been successfully synthesized based on L-alanine chiral ligand, which demonstrates the feasibility of fabricating MOF that integrates the 4-connected zeotype topology by the employment of L-alanine. To the best of knowledge, it’s the first report that metal-organic framework based on amino acid features the chiral zeolitic rho-type structure. Compound 1 was characterized by X-ray powder diffraction, elemental analysis and single-crystal X-ray diffraction. Crystal data: C6 H9 CdN2 O4, Mr = 285.55, cubic system, space group I432, a = 24.0795（6）, V = 13961.9（10） ?3, Z = 48, Dc = 1.630 Mg/m3, F（000） = 6672, μ（Mo Kα） = 1.865 mm-1, S = 1.058, R = 0.0271 and wR = 0.0312 for 1870 observed reflections with I > 2σ（I）. The circular dichroism（CD） property of compound 1 was also investigated.展开更多
A novel and concise synthetic access to enantiopure chiral 2-aryl/alkyl substituted 4-piperidone has been demonstrated.This new route features two key steps:the highly diastereoselective conjugate addition of homochir...A novel and concise synthetic access to enantiopure chiral 2-aryl/alkyl substituted 4-piperidone has been demonstrated.This new route features two key steps:the highly diastereoselective conjugate addition of homochiral lithium amides to trans-β-substituted-α,β-unsaturated methyl esters guaranteed the enantiopurity at 2 position(de>19:1)and the intramolecular attacking of carbanions to methyl esters led to the formation of the piperidone ring.A wide range of substrates,including chiral2-aryl and 2-alkyl-4-piperidones,were successfully synthesized with modest to high yield.Moreover,some non-chiral3-substituted-4-piperidones were also synthesized with enhanced ring-formation yield,implicating the versatility of this method in construction of various piperidine rings.展开更多
基金supported by the National Basic Research Program of China(973 Program,2012CB821702)the National Natural Science Foundation of China(21233009 and 21173221)
文摘Two homochiral enantiomorphic 3D coordination polymers： （D-HAPA）2[Cd2Cs（D- HAPA）（m-BDC）4]＇（EtOH） （1D） and （L-HAPA）2[Cd2Cs（L-HAPA）（m-BDC）a]＇（EtOH） （1L） （APA = 2-amino-l-propanol, m-H2BDC = 1,3-benzenedicarboxylate）, have been assembled solvothermally respectively with the induction of enantiomorphic organic small molecules （D,L-APA）. 1L and 1I） crystallize in chiral space group P21 with Flack parameters of-0.012（13） and -0.07（3）, respectively, and have been characterized by satisfactory elemental analysis, FT-IR spectra, CD-spectra and single-crystal X-ray diffraction. They both exhibit sqp topological net, purple fluorescence and SHG activity.
基金funded by the National Natural Science Foundation of China(Grant No.:82003705).
文摘Homochiral metal-organic frameworks(MOFs)have attracted considerable attention in many fields of research,such as chiral catalysis and chiral chromatography.However,only few homochiral MOFs can be effectively used in capillary electrochromatography(CEC)and their performances are far from adequate.In this study,we successfully synthesized achiral nanocrystalline MIL-53.A facile post-synthetic modification strategy was then implemented to functionalize the product,yielding a homochiral MOF:L-His-NH-MIL-53.This MOF was then employed as a chiral coating in open-tubular CEC mode(OT-CEC),and,as such,it exhibited high enantioselectivities for several racemic drugs.The homochiral MOF and the fabricated capillary coating were systematically characterized using transmission electron microscopy,scanning electron microscopy(with energy-dispersive X-ray spectrometry),Fourier-transform infrared spectroscopy,X-ray diffractometry,thermogravimetric analysis,circular dichroism spectroscopy,Brunauer-Emmett-Teller surface area measurements,and X-ray photoelectron spectroscopy.This study is expected to provide a new strategy for the design and establishment of MOF-based chiral OT-CEC systems.
基金funded by the National Natural Science Foundation of China(No.21201087)Jiangsu Province NSF BK20131244+2 种基金the Foundation of Jiangsu Educational Committee (No.11KJB150004)sponsored by Qing Lan Project of Jiangsu provinceJiangsu Overseas Research & Training Program for University Prominent Young & Middle-aged Teacher and Presidents
文摘Reacting homochiral （R）-2-methylpiperazine with cobalt sulfate heptahydrate by the solution method in the presence of concentrated sulfuric acid （H2SO4） yielded two coordination compounds （C5H14N2） [CO（H2O）6]（SO4）2 （1 and 2）. They are polymorphs, but their hydrogen bonds structure differ significantly. Both 1 and 2 crystallize in chiral space group P21 which is related with point group C2, and experimental results suggest that 1 displays ferroelectric behaviors.
基金supported by the Natural Science Foundation of Guizhou Province(20122344)125 program of Guizhou Education Department(2012015)the Doctoral Scientific Fund of Zunyi Normal College(2012BSJJ12)
文摘With the help of in-situ formed CH_3COO- anion, a pair of 3D homochiral coordination polymers with open channels were constructed by the assembly of lactic acid derivative ligands, 1.4-DIB ligands and Cd（II） ions, namely [Cd3（（R）-CIA）2（CH3CO2）_2（1.4-DIB）2（H2O）2]·x（vip）（1-D） and [Cd3（（S）-CIA）2（CH3CO2）2（1.4-DIB）2（H2O）2]·x（vip）（1-L）. They contain 1D interesting ladder-like Cd-（R）-CIA（3-） chains and exhibit SHG-active behavior and photoluminescent property.
基金supported by the Science and Technology Department of Guizhou Province (No. J[2010]2121)Zunyi Science and Technology Bureau (No. [2010]04)
文摘Four isostructural lanthanide compounds formulated as {[Ln4（μ3-OH）4（L-asp）3- （H2O）10]（ClO4）5·10H2O}n （Ln=Nd （1）, Sm （2）, Eu （3）, Gd （4）; asp=aspartic acid） were synthe- sized by a conventional solution reaction. Their structures were characterized by single-crystal X-ray diffraction, IR spectroscopy and elemental analyses （EA）. It reveals that they crystallize in the chiral P212121 space group. Their structures feature a homochiral three-dimensional （3D） lan- thanide-organic framework, which contains a cubic [Ln4（μ3-OH）4]8＋ cluster sub-building unit （SBU）. Additionally, the photoluminescence property of Eu compound was investigated in the solid-state at room temperature.
文摘The origin of homochirality in living organisms is controversial,stands out of being particularly important and a question which is still not satisfactorily answered.A mental picture of sequence of events that is thought to have preceded the existence of chirality in molecules is described.A chemical model to mimic the original abiotic conditions in an attempt to explain the preference of homochirality in living systems was tried.The effect which might have influenced this preference is presented.The surpri...
基金supported by the National Key R&D Program of China(2022YFA1503300)the National Natural Science Foundation of China(22471273,21971241)。
文摘Homochiral coordination polymers(HCPs)represent a class of structurally ordered crystalline materials assembled by the coordination of metal ions or metal clusters with chiral ligands,holding great promise for applications in catalysis,separation,sensing,and other fields[1-9].Chiral ligands play a central role in the construction of HCPs.Proline and its derivatives have been extensively studied as homogeneous catalysts in a wide range of asymmetric organic reactions,where the pyrrolidine-NH functionality stands out as a pivotal catalytic site[10,11].
基金supported by the National Key R&D Program of China(2022YFA1503300)and the National Natural Science Foundation of China(21971241 and 21935010)。
文摘Chiral metal-organic frameworks(CMOFs),an emerging class of heterogeneous chiral catalysts,show significant potential for application in asymmetric catalysis due to their tunable pore shapes and sizes,large internal surface areas,and rich chiral environments[1-4].Through over 20 years of development,researchers have invested heavily in exploring new CMOFs to enhance asymmetric catalytic performance[5-10].However,the dual pursuit of a substantial specific surface area and robust stability within a single CMOF presents a considerable challenge.Additionally,efficient CMOF catalysts,frequently synthesized from privileged chiral ligands such as proline,2,2'-bis(diphenylphosphino)-1,1'-binaph thyl(BINAP),Salen,and bis(oxazoline)(Box)[11,12],tend to exhibit more complex structures compared to their corresponding privileged chiral counterparts,thereby necessitating higher production costs.Consequently,the development of novel synthetic methodologies for constructing CMOFs as effective chiral catalysts remains a challenging endeavor.
基金supported financially by Jiangsu Higher Education Institutions of China (18KJB150030)。
文摘Enantiomerically pure lanthanide(Ⅲ)-based phosphonates are successfully synthesized by using(R)-or(S)-(1-phenylethylamino)-methylphosphonate acid(pempH2),namely,R-or S-[Tb3(pempH2)2(pempH)7]-Cl2·H2O(R-Tb or S-Tb),crystallizing in chiral space group P212121.Compound R-Tb shows a one-dimensional homochiral triple-stranded helical chain structure where the Tb(III)atoms are bridged by O-P-O units andμ3-O(P)bridge.The thermal analysis,photoluminescence as well as optically active properties of compounds R-Tb and S-Tb have also been investigated.
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support from the Major State Basie Research Development Program (Grant No. 2006CB933100)the National Natural Science Foundation of China (Grant No. 90813019)
文摘Homochirality in life has always been a driving force in scientific research and natural exploration. It has not been satisfactorily explained, and systematic investigations are necessary. This paper reported a homochiral expression of proteins dependent on the stirring direction of growing media. By controlling the stirring direction clockwise (CW) and anticlockwise (ACW) of the culture medium, proteins with distinct secondary structures were obtained, and D-amino acid may be included in the protein cultured with the stirring direction of ACW. Considering the effect of force fields, which might affect the process of folding and refolding of cellular protein in this report, the control of force fields might be a good way to prepare asymmetric drugs, and the rotational direction of the earth is possibly related to the chirality in primitive life molecules.
基金supported by the National Natural Science Foundation of China(grant nos.22325105,92361301,52261135637,22171164,92161118,91961105,and 21641011)the Natural Science Foundation of Fujian Province(grant no.2022J01298)the Open Project Program of the State Key Laboratory of Photocatalysis on Energy and Environment(grant no.SKLPEE-KF202109).
文摘Hierarchical chiral self-assembly is of profound significance for biomolecules for their biological functions.Atom-precise metal nanoclusters(NCs)offer better opportunities to construct hierarchical superlattices.Nevertheless,achieving hierarchical homochiral assembly of nanocrystals protected by achiral ligands has proven to be a formidable task,with existing examples primarily limited to heterochiral assembly.Here we put forward a hierarchical assembly strategy towards precisely fabricating highly ordered homochiral superstructures.First,clusterin-nanocage type copper-hydride NCs act as synthons,of which entity is featured with a hexagonal close-packed Cu_(9)kernel embedded in a C_(3)-symmetric trigonal-prismatic metallacage,leading to a chiral core-shell primary structure with either P or M conformation.Then four homochiral NCs combined with vips through synergistic noncovalent interactions spontaneously organize into a supramolecular tetrahedral secondary structure within a unit cell.Finally,these nanoscopic supramolecular motifs pack into tertiary hierarchical superlattice of chiral cubic crystalline phase.Additionally,the crystalline material shows excellent robustness,and fascinating blueexcitable near-infrared thermally activated delayed fluorescence behavior.This work not only exhibits that nanocage-type NCs can be smart as proteins to translate chiral primary structure into tertiary chiral hierarchical complexity,but also provides new insights into structure-to-superstructure,enabling bottom-up creation of higher-level hierarchical homochiral superlattice structures.
基金supported by the National Natural Science Foundation of China(21991142,21831004,91856114,and 22175082)。
文摘What is the most favorite and original chemistry developed in your research group?We originally proposed the design principle for molecular ferroelectrics:ferroelectrochemistry,including quasi-spherical theory,the introduction of homochirality,and H/F substitution.Ferroelectrochemistry changed the blind search for molecular ferroelectrics into targeted chemical design,which will develop into a new discipline.
基金financially supported by National Ministry of Science and Technology Innovation Fund for High-tech Small and Medium Enterprise Technology (09C26215112399)National Ministry of Human Resources and Social Security Start-up Support Projects for Students Returned to Business, Office of Human Resources and Social Security Issued 2009 (143)
文摘Three new homochiral bis-diamine-bridged bi-Mn（salen） complexes were synthesized. Their catalysis on asymmetric epoxidation of a-methylstyrene, styrene and indene was studied with NaC10 and m-CPBA as oxidants respectively. This homogeneous catalyst exhibited comparable catalytic activity and enantioselectivity to the Jacobsen＇s catalyst in the asymmetric epoxidation of unfunctionalized olefins. Furthermore, the catalyst could be conveniently recovered and reused at least five times without significant losses of both activity and enantioselectivity. Specially, it also could be efficiently used in large-scale reactions with superior catalytic disposition being maintained at the same level, which provided the potential for the applications in industry. The effect of axial bases, temperature and solvent on activity and enantioselectivity of the catalytic system were also studied.
基金the National Natural Science Foundation of China(No.21761036)。
文摘Helix as essential molecular chiral phenomenon at supramolecular level offers an affective method to study chiral characteristic of homochiral coordination polymers(CPs).Herein,two homochiral CPs[Cd((R)-CBA)_(2)(3,5-DIT)]_(n)((R)-H_(2) CBA=(R)-4-(1-carboxyethoxy)benzoic acid,3,5-DIT=3,5-di(1 H-imidazol-1-yl)toluene,1-R)and[Zn((R)-CBA)(3,5-DIT)]_(n)(2-R)were synthesized under hydrothermal conditions.In complex 1-R,only a helical chain was built by chiral ligands(R)-CBA2-,ancillary ligands 3,5-DIT and Cd(Ⅱ)ions.After Cd(Ⅱ)ions were replaced by Zn(Ⅱ)ions under similar reaction system,Zn(Ⅱ),(R)-CBA^(2-)and/or 3,5-DIT formed six types of helices,resulting in complex 2-R.So,the metal ions played a key role in the construction of helical structures.Complexes 1-R and 2-R were also characterized by elemental analysis,PXRD,TGA,CD and UV-visible absorptions.In addition,complexes 1-R and 2-R exhibited different photoluminescence behaviors in solid sate compared to free ligand(R)-H_(2)CBA.
基金Project(29572068)supported by the National Natural Science Foundation of China.
文摘Homochiral cis, cis-; cis,trans- and trans, trans-spiro[4.4]nonane-1,6-diols were prepared via diastereoselective reduction of enantiomerically pure spiro[4.4]nonane-1,6-dione (1) with the corresponding reducing agents: lithium n-butyldiisobutylaluminium hydride for cis,cis-diol (2) with 88% yield; BH3. HF for cis,trans-diol (3) with 91% yield; LiAlH4 for trans,trans-diol (4) with 15% yield.
基金supported by National Natural Science Foundation of China(21401147)Basic Research Program of Natural Science from Shaanxi Provincial Government(2015JQ2032)+2 种基金Scientific Research Program from Education Department of Shaanxi Provincial Government(2013JK0654)Opening Foundation from State Key Laboratory of Coordination Chemistry in Nanjing University(201219)the Program for Distinguished Young Scholars of Xi’an Polytechnic University(201403)
文摘A chiral lanthanide metal-organic framework based on enantiopure camphoric acid （D-H2cam）, [Nd3（D-cam）8（H2O）4Cl]n （1）, has been synthesized and characterized by single-crystal X-ray structural analysis, elemental analysis, IR, thermal gravimetric, and X-ray powder diffraction. Crystal data for the title compound are as follows： orthorhombic system, space group P212121 with a = 13.8287（7）, b = 14.0715（7）, c = 25.7403（12） A^°, V = 5008.8（4） A^°3, Mr = 1333.08, Z = 4, F（000） = 2644, Dc = 1.768 g/cm^3, μ（MoKα） = 3.189 mm^-1, the final R = 0.0351 and wR = 0.0814 （I 〉 2σ（I））. Compound 1 displays an 8-connected bcu topology 3D framework and hydrogen-bonding interactions stabilize the solid-state structure. The vibrational circular dichroism （VCD） spectrum and second-order nonlinear optical effect of compound 1 have been studied in the solid state.
基金supported financially by National Natural Science Foundation of China(No.21601080)
文摘One new chiral zeolitic rho-type metal-organic framework [Cd（L-ala）2]n（1） has been successfully synthesized based on L-alanine chiral ligand, which demonstrates the feasibility of fabricating MOF that integrates the 4-connected zeotype topology by the employment of L-alanine. To the best of knowledge, it’s the first report that metal-organic framework based on amino acid features the chiral zeolitic rho-type structure. Compound 1 was characterized by X-ray powder diffraction, elemental analysis and single-crystal X-ray diffraction. Crystal data: C6 H9 CdN2 O4, Mr = 285.55, cubic system, space group I432, a = 24.0795（6）, V = 13961.9（10） ?3, Z = 48, Dc = 1.630 Mg/m3, F（000） = 6672, μ（Mo Kα） = 1.865 mm-1, S = 1.058, R = 0.0271 and wR = 0.0312 for 1870 observed reflections with I > 2σ（I）. The circular dichroism（CD） property of compound 1 was also investigated.
基金CAS Key Laboratory of Synthetic Chemistry of Natural Substances (2008DP173071) for analysis support
文摘A novel and concise synthetic access to enantiopure chiral 2-aryl/alkyl substituted 4-piperidone has been demonstrated.This new route features two key steps:the highly diastereoselective conjugate addition of homochiral lithium amides to trans-β-substituted-α,β-unsaturated methyl esters guaranteed the enantiopurity at 2 position(de>19:1)and the intramolecular attacking of carbanions to methyl esters led to the formation of the piperidone ring.A wide range of substrates,including chiral2-aryl and 2-alkyl-4-piperidones,were successfully synthesized with modest to high yield.Moreover,some non-chiral3-substituted-4-piperidones were also synthesized with enhanced ring-formation yield,implicating the versatility of this method in construction of various piperidine rings.
