A supramolecular complex of Cd（II） with 1D water tapes as pillars[Cd2（dpa）2（phen）2（H2O）2]·6H2O 1 （H2dpa = diphenic acid, phen = phenanthroline）, has been synthesized and characterized by elemental analy...A supramolecular complex of Cd（II） with 1D water tapes as pillars[Cd2（dpa）2（phen）2（H2O）2]·6H2O 1 （H2dpa = diphenic acid, phen = phenanthroline）, has been synthesized and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction analysis. The crystal is of triclinic, space group P1^- with a = 9.7029（4）, b = 11.9601（5）, c = 12.1788（4） A, α = 71.6990（10）, β = 71.8740（10）, γ = 74.4680（10）°, V = 1252.39（8） A^3, C52H48Cd2N4O16, Mr = 1209.76, Z= 1, Dc = 1.604 g/cm^3,μ = 0.925 mm^-1, F（000） = 612, R = 0.0679 and wR = 0.2514 for 3870 observed reflections （I 〉 2σ（I））. Two intramolecular Cd（II） centers of this complex are encircled by two dpa^2- ligands forming an 18-membered ring, which is further assembled into a pillared three-dimensional （3D） supramolecular architecture through the synergetic effect of intermolecular face-to-face π…π stacking and weak O-H…O hydrogen-bonding interactions. Moreover, this complex exhibits photoluminescence with the main emission bands located at about 456 nm upon excitation at 355 nm in the solid state at room temperature.展开更多
The authors have prepared suprameolecular systems of chiral Schiffbase ZnAZSB （Zn（II） complexes with azo-groups） or without ZnSB （azo-groups） and colloidal AuNP （gold nanoparticles） of 10, 40 and 80 nm diamete...The authors have prepared suprameolecular systems of chiral Schiffbase ZnAZSB （Zn（II） complexes with azo-groups） or without ZnSB （azo-groups） and colloidal AuNP （gold nanoparticles） of 10, 40 and 80 nm diameters. They exhibited gradual shifts of surface plasmon bands as well as fluorescence bands. The authors observed and discussed induced CD bands on gold nanoparticles from chiral ZnAZSB or ZnSB. Absence of cis-trans photoisomerization of ZnAZSB with AuNP also supported direct contact near the surface of AuNP. Quenching and splitting of fluorescence bands of ZnSB （λex = 550 nm and λem = 400 nm） depending on concentration of ZnSB and size of AuNP also suggested intermolecular （electric） interaction on the surface of AuNE Decrease of the intensity of the CD band around 380 nm resulted from reciprocal induced CD effect due to parallel arrangement of electric transition moments of ZnAZSB or ZnSB and surface of AuNP.展开更多
Background:Pig organ xenotransplantation is a potential solution for the severe organ shortage in clinic,while immunogenic genes need to be eliminated to improve the immune compatibility between humans and pigs.Curren...Background:Pig organ xenotransplantation is a potential solution for the severe organ shortage in clinic,while immunogenic genes need to be eliminated to improve the immune compatibility between humans and pigs.Current knockout strategies are mainly aimed at the genes causing hyperacute immune rejection(HAR)that occurs in the first few hours while adaptive immune reactions orchestrated by CD4 T cell thereafter also cause graft failure,in which process the MHCⅡmolecule plays critical roles.Methods:Thus,we generate a 4-gene(GGTA1,CMAH,β4GalNT2,and CIITA)knockout pig by CRISPR/Cas9 and somatic cell nuclear transfer to compromise HAR and CD4 T cell reactions simultaneously.Results:We successfully obtained 4KO piglets with deficiency in all alleles of genes,and at cellular and tissue levels.Additionally,the safety of our animals after gene editing was verified by using whole-genome sequencing and karyotyping.Piglets have survived for more than one year in the barrier,and also survived for more than 3 months in the conventional environment,suggesting that the piglets without MHCⅡcan be raised in the barrier and then gradually mated in the conventional environment.Conclusions:4KO piglets have lower immunogenicity,are safe in genomic level,and are easier to breed than the model with both MHCⅠandⅡdeletion.展开更多
The complex containing ferroceneyl, Cd(dppf)I2(dppf=1,1 bis(diphenylphosphino) ferrocene), was synthesized and characterized by IR, Uv vis DRIS spectrum and X ray diffraction. The crystal belongs to monoclinic, space ...The complex containing ferroceneyl, Cd(dppf)I2(dppf=1,1 bis(diphenylphosphino) ferrocene), was synthesized and characterized by IR, Uv vis DRIS spectrum and X ray diffraction. The crystal belongs to monoclinic, space group C2/c, a=37.439(3)?, b=10.2472(6)?, c=18.719(1)?, β=110.4715(16)°, V=6727.8(8)?3, Z=8, Dc=1.818g·cm-3, F(000)=3536, μ=3.015mm-1, R=0.0308, wR=0.0692. dppf coordinates to Cd? as bidentate ligand, and the coordination environment of Cd? is a distorted tetrahedron. The electronic structures of Cd(dppf)I2 and Cd(dppf)Br2 are discussed by quantum chemistry calculation.展开更多
One Cd（II） complex based on dicarboxylate and N-auxiliary ligand, namely, [Cd（aip）（m-bix）]n （1, H2aip = 5-aminoisophthalic acid, m-bix = 1,3-bis（imidazol-l-yl-methyl）ben- zene）, was successfully synthesized ...One Cd（II） complex based on dicarboxylate and N-auxiliary ligand, namely, [Cd（aip）（m-bix）]n （1, H2aip = 5-aminoisophthalic acid, m-bix = 1,3-bis（imidazol-l-yl-methyl）ben- zene）, was successfully synthesized under hydrothermal conditions. Single-crystal X-ray diffraction analysis reveals that 1 belongs to the orthorhombic system, space group Pbca with a = 14.0790（11）, b = 17.0038（15）, c = 17.3191（16）, V= 4146.1（6） A3, Z = 8, D,. = 1.698 g.cm＂3, p = 1.095 mm-1, F（000） = 2128, the final R = 0.0268 and wR = 0.0623. Complex 1 is a three-dimensional architecture with fsc-3,5-Cmce-1 topology, in which the metal ions act as rare 5-connected nodes. The TGA, XRD and luminescent properties of I were studied.展开更多
The title complex [Cd（IPA）L（H2O）]n（1,H2IPA = isophthalic acid,L = 1,4-bis（pyra-zole-1-ylmethyl）benzene） has been hydrothermally synthesized,and characterized by elemental analyses,IR spectroscopy,TGA and X-ray...The title complex [Cd（IPA）L（H2O）]n（1,H2IPA = isophthalic acid,L = 1,4-bis（pyra-zole-1-ylmethyl）benzene） has been hydrothermally synthesized,and characterized by elemental analyses,IR spectroscopy,TGA and X-ray single-crystal diffraction.It crystallizes in the triclinic system,space group P1 with a = 9.3060（6）,b = 10.2374（7）,c = 11.9706（8） ？,α = 73.804（6）,β = 77.883（5）,γ = 85.942（5）°,V = 1070.7（1） ？3,Z = 2,C22H20CdN4O5,Mr = 532.82,Dc = 1.653 g/cm3,μ = 1.062 mm-1,λ（MoKα） = 0.71073 ？,F（000） = 536,R = 0.0392 and wR = 0.0640 for 3751 observed reflections with I 2σ（I）.Crystal structure analysis showed that complex 1 has a 1D double chain structure,which is assembled together through strong O-H...O hydrogen bonding interactions between coordinated water molecules and carboxylate groups of isophthalate to form a 2D supramolecular network.In addition,the solid-state fluorescent spectrum of 1 exhibits strong emission at 364 nm.展开更多
A ladder-like structure compound formed by cadmium (II) and anionic nitronyl nitroxide, [Cd2(NITpBA)4(H2O)4] (where NITpBA = 2-(4-carboxyphenyl)4,4,5,5-tetramethyl-4,5-dihydro-imidazol-1-oxyl-3-oxide), has been synthe...A ladder-like structure compound formed by cadmium (II) and anionic nitronyl nitroxide, [Cd2(NITpBA)4(H2O)4] (where NITpBA = 2-(4-carboxyphenyl)4,4,5,5-tetramethyl-4,5-dihydro-imidazol-1-oxyl-3-oxide), has been synthesized and characterized. X-ray analysis reveals that the compound 1 crystallizes in the monoclinic P21/c (No. 14) space group, and [Cd2(NITpBA)4(H2O)4] units are linked into infinite chains by radical bridging ligands.展开更多
The quantum-chemical calculations were performed to determine the nature of the equilibrium geometry of the ground and excited states of the 1,3,5-triazapentadiene complexes of platinum（Ⅱ） and theirs nature and str...The quantum-chemical calculations were performed to determine the nature of the equilibrium geometry of the ground and excited states of the 1,3,5-triazapentadiene complexes of platinum（Ⅱ） and theirs nature and structure of molecular orbitals.展开更多
Three Cd（II） metal-organic complexes, namely [Cd（phen）2Cl2]（1）, [Cd（phen）Cl2]（2） and [Cd（phen）（cam）]. H2O（3）（phen=1,10-phenanthroline, H2cam=camphoric acid）, were hydrothermally synthesized using Cd2...Three Cd（II） metal-organic complexes, namely [Cd（phen）2Cl2]（1）, [Cd（phen）Cl2]（2） and [Cd（phen）（cam）]. H2O（3）（phen=1,10-phenanthroline, H2cam=camphoric acid）, were hydrothermally synthesized using Cd2＋, phen and Hacam as raw materials under different conditions of pH values, reaction temperatures or reactant ratios. The prepared complexes were structurally characterized by means of single-crystal X-ray diffraction, and the results show that complex 1 is a 2D supramolecular complex, which consists of [Cd（phen）2Cl2] mononuclear subunits, while complex 2 shows a 1D chain structure, in which Cd（II） ions are connected by chloride（Cl ） bridges, with phen hanging on both sides of the chain. No cam anions have been observed in the structures of complexes 1 and 2. In complex 3, cam connects Cd（lI） ions to construct a 2D network, in which phen acts as terminal ligands. The adjacent 1D chains for complex 2 and the adjacent 2D layers for complex 3 are further linked by hydrogen bonding interac- tions or π-π intermolecular interactions to form 3D supramolecular networks, respectively. The effects of reaction conditions on the assembly and structures of the complexes have been discussed. The fluorescent and photocatalytic properties of complexes 1-3 and the fluorescent sensing behaviors of complexes 2 and 3 have also been investigated.展开更多
The kinetics of ternary complex formation involving Cu(5-X-1, 10-phen) and threonine (CuAL, A=5-X-1, 10-phen; L=threonine or represented by O-N; X=NO_2, Cl, H, CH_3) has been studied by temperature-jump and stopped-fl...The kinetics of ternary complex formation involving Cu(5-X-1, 10-phen) and threonine (CuAL, A=5-X-1, 10-phen; L=threonine or represented by O-N; X=NO_2, Cl, H, CH_3) has been studied by temperature-jump and stopped-flow methods. The formation rate constants, k_f(M^(-1).s^(-1)), for the complexation reaction, CuA + LCuAL, are as follows; X=NO_2, 8.68×10~8; X=Cl, 7.13×10~8; X=H, 6.12×10~8; X=CH_3, 5.42×10~8. The rate constants for zwitterion attack are nil within experimental error. It has been found that a linear free energy relationship exists between the stability(logK_(CuAL)^(CuA) of the complexes CuAL and log kf as follows: IogK_(CuAL)^(CuA)=0.13 + 0.83 logk_f, r=0.99. It suggested that the formation rate governed the stability of the ternary complexes. The rates of formation of the ternary complexes increased with decreasing electron-donating property of the substituents. A linear relationship was found to exist as expressed by the following equation: log(k_f^R/k_F^O) = 0.097σ, r=0.96. A mechanism involves a rapid equilibrium between CuA and L followed by a slow ring closure of L.展开更多
基金the State Key Basic Research and Development Plan of China (001CB108906)the Knowledge Innovation Program of the Chinese Academy of Sciences, the NSF (2006J0015)the Major Special Foundation of Fujian Province (2005HZ1027, 2005HZ01-1)
文摘A supramolecular complex of Cd（II） with 1D water tapes as pillars[Cd2（dpa）2（phen）2（H2O）2]·6H2O 1 （H2dpa = diphenic acid, phen = phenanthroline）, has been synthesized and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction analysis. The crystal is of triclinic, space group P1^- with a = 9.7029（4）, b = 11.9601（5）, c = 12.1788（4） A, α = 71.6990（10）, β = 71.8740（10）, γ = 74.4680（10）°, V = 1252.39（8） A^3, C52H48Cd2N4O16, Mr = 1209.76, Z= 1, Dc = 1.604 g/cm^3,μ = 0.925 mm^-1, F（000） = 612, R = 0.0679 and wR = 0.2514 for 3870 observed reflections （I 〉 2σ（I））. Two intramolecular Cd（II） centers of this complex are encircled by two dpa^2- ligands forming an 18-membered ring, which is further assembled into a pillared three-dimensional （3D） supramolecular architecture through the synergetic effect of intermolecular face-to-face π…π stacking and weak O-H…O hydrogen-bonding interactions. Moreover, this complex exhibits photoluminescence with the main emission bands located at about 456 nm upon excitation at 355 nm in the solid state at room temperature.
文摘The authors have prepared suprameolecular systems of chiral Schiffbase ZnAZSB （Zn（II） complexes with azo-groups） or without ZnSB （azo-groups） and colloidal AuNP （gold nanoparticles） of 10, 40 and 80 nm diameters. They exhibited gradual shifts of surface plasmon bands as well as fluorescence bands. The authors observed and discussed induced CD bands on gold nanoparticles from chiral ZnAZSB or ZnSB. Absence of cis-trans photoisomerization of ZnAZSB with AuNP also supported direct contact near the surface of AuNP. Quenching and splitting of fluorescence bands of ZnSB （λex = 550 nm and λem = 400 nm） depending on concentration of ZnSB and size of AuNP also suggested intermolecular （electric） interaction on the surface of AuNE Decrease of the intensity of the CD band around 380 nm resulted from reciprocal induced CD effect due to parallel arrangement of electric transition moments of ZnAZSB or ZnSB and surface of AuNP.
基金National Key Research and Development Program,Grant/Award Number:2019YFA0903800,2021YFA0805701,2021YFA0805905 and 2022YFA1103603CAS Project for Young Scientists in Basic Research,Grant/Award Number:YSBR-012+2 种基金STI 2030-Major Project,Grant/Award Number:2023ZD0407503National Natural Science Foundation of China,Grant/Award Number:32071456 and 82241224Strategic Priority Research Program of the Chinese Academy of Sciences,Grant/Award Number:XDA16030000。
文摘Background:Pig organ xenotransplantation is a potential solution for the severe organ shortage in clinic,while immunogenic genes need to be eliminated to improve the immune compatibility between humans and pigs.Current knockout strategies are mainly aimed at the genes causing hyperacute immune rejection(HAR)that occurs in the first few hours while adaptive immune reactions orchestrated by CD4 T cell thereafter also cause graft failure,in which process the MHCⅡmolecule plays critical roles.Methods:Thus,we generate a 4-gene(GGTA1,CMAH,β4GalNT2,and CIITA)knockout pig by CRISPR/Cas9 and somatic cell nuclear transfer to compromise HAR and CD4 T cell reactions simultaneously.Results:We successfully obtained 4KO piglets with deficiency in all alleles of genes,and at cellular and tissue levels.Additionally,the safety of our animals after gene editing was verified by using whole-genome sequencing and karyotyping.Piglets have survived for more than one year in the barrier,and also survived for more than 3 months in the conventional environment,suggesting that the piglets without MHCⅡcan be raised in the barrier and then gradually mated in the conventional environment.Conclusions:4KO piglets have lower immunogenicity,are safe in genomic level,and are easier to breed than the model with both MHCⅠandⅡdeletion.
文摘The complex containing ferroceneyl, Cd(dppf)I2(dppf=1,1 bis(diphenylphosphino) ferrocene), was synthesized and characterized by IR, Uv vis DRIS spectrum and X ray diffraction. The crystal belongs to monoclinic, space group C2/c, a=37.439(3)?, b=10.2472(6)?, c=18.719(1)?, β=110.4715(16)°, V=6727.8(8)?3, Z=8, Dc=1.818g·cm-3, F(000)=3536, μ=3.015mm-1, R=0.0308, wR=0.0692. dppf coordinates to Cd? as bidentate ligand, and the coordination environment of Cd? is a distorted tetrahedron. The electronic structures of Cd(dppf)I2 and Cd(dppf)Br2 are discussed by quantum chemistry calculation.
基金Supported by the National Natural Science Foundation of China (No. 20901004)
文摘One Cd（II） complex based on dicarboxylate and N-auxiliary ligand, namely, [Cd（aip）（m-bix）]n （1, H2aip = 5-aminoisophthalic acid, m-bix = 1,3-bis（imidazol-l-yl-methyl）ben- zene）, was successfully synthesized under hydrothermal conditions. Single-crystal X-ray diffraction analysis reveals that 1 belongs to the orthorhombic system, space group Pbca with a = 14.0790（11）, b = 17.0038（15）, c = 17.3191（16）, V= 4146.1（6） A3, Z = 8, D,. = 1.698 g.cm＂3, p = 1.095 mm-1, F（000） = 2128, the final R = 0.0268 and wR = 0.0623. Complex 1 is a three-dimensional architecture with fsc-3,5-Cmce-1 topology, in which the metal ions act as rare 5-connected nodes. The TGA, XRD and luminescent properties of I were studied.
文摘The title complex [Cd（IPA）L（H2O）]n（1,H2IPA = isophthalic acid,L = 1,4-bis（pyra-zole-1-ylmethyl）benzene） has been hydrothermally synthesized,and characterized by elemental analyses,IR spectroscopy,TGA and X-ray single-crystal diffraction.It crystallizes in the triclinic system,space group P1 with a = 9.3060（6）,b = 10.2374（7）,c = 11.9706（8） ？,α = 73.804（6）,β = 77.883（5）,γ = 85.942（5）°,V = 1070.7（1） ？3,Z = 2,C22H20CdN4O5,Mr = 532.82,Dc = 1.653 g/cm3,μ = 1.062 mm-1,λ（MoKα） = 0.71073 ？,F（000） = 536,R = 0.0392 and wR = 0.0640 for 3751 observed reflections with I 2σ（I）.Crystal structure analysis showed that complex 1 has a 1D double chain structure,which is assembled together through strong O-H...O hydrogen bonding interactions between coordinated water molecules and carboxylate groups of isophthalate to form a 2D supramolecular network.In addition,the solid-state fluorescent spectrum of 1 exhibits strong emission at 364 nm.
文摘A ladder-like structure compound formed by cadmium (II) and anionic nitronyl nitroxide, [Cd2(NITpBA)4(H2O)4] (where NITpBA = 2-(4-carboxyphenyl)4,4,5,5-tetramethyl-4,5-dihydro-imidazol-1-oxyl-3-oxide), has been synthesized and characterized. X-ray analysis reveals that the compound 1 crystallizes in the monoclinic P21/c (No. 14) space group, and [Cd2(NITpBA)4(H2O)4] units are linked into infinite chains by radical bridging ligands.
文摘The quantum-chemical calculations were performed to determine the nature of the equilibrium geometry of the ground and excited states of the 1,3,5-triazapentadiene complexes of platinum（Ⅱ） and theirs nature and structure of molecular orbitals.
文摘Three Cd（II） metal-organic complexes, namely [Cd（phen）2Cl2]（1）, [Cd（phen）Cl2]（2） and [Cd（phen）（cam）]. H2O（3）（phen=1,10-phenanthroline, H2cam=camphoric acid）, were hydrothermally synthesized using Cd2＋, phen and Hacam as raw materials under different conditions of pH values, reaction temperatures or reactant ratios. The prepared complexes were structurally characterized by means of single-crystal X-ray diffraction, and the results show that complex 1 is a 2D supramolecular complex, which consists of [Cd（phen）2Cl2] mononuclear subunits, while complex 2 shows a 1D chain structure, in which Cd（II） ions are connected by chloride（Cl ） bridges, with phen hanging on both sides of the chain. No cam anions have been observed in the structures of complexes 1 and 2. In complex 3, cam connects Cd（lI） ions to construct a 2D network, in which phen acts as terminal ligands. The adjacent 1D chains for complex 2 and the adjacent 2D layers for complex 3 are further linked by hydrogen bonding interac- tions or π-π intermolecular interactions to form 3D supramolecular networks, respectively. The effects of reaction conditions on the assembly and structures of the complexes have been discussed. The fluorescent and photocatalytic properties of complexes 1-3 and the fluorescent sensing behaviors of complexes 2 and 3 have also been investigated.
文摘The kinetics of ternary complex formation involving Cu(5-X-1, 10-phen) and threonine (CuAL, A=5-X-1, 10-phen; L=threonine or represented by O-N; X=NO_2, Cl, H, CH_3) has been studied by temperature-jump and stopped-flow methods. The formation rate constants, k_f(M^(-1).s^(-1)), for the complexation reaction, CuA + LCuAL, are as follows; X=NO_2, 8.68×10~8; X=Cl, 7.13×10~8; X=H, 6.12×10~8; X=CH_3, 5.42×10~8. The rate constants for zwitterion attack are nil within experimental error. It has been found that a linear free energy relationship exists between the stability(logK_(CuAL)^(CuA) of the complexes CuAL and log kf as follows: IogK_(CuAL)^(CuA)=0.13 + 0.83 logk_f, r=0.99. It suggested that the formation rate governed the stability of the ternary complexes. The rates of formation of the ternary complexes increased with decreasing electron-donating property of the substituents. A linear relationship was found to exist as expressed by the following equation: log(k_f^R/k_F^O) = 0.097σ, r=0.96. A mechanism involves a rapid equilibrium between CuA and L followed by a slow ring closure of L.
