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2014 Volume 30 Issue 5
2014, 30(5): 969-976
doi: 10.11862/CJIC.2014.146
Abstract:
Using pyridine-derived cyclometalated ligands and tetraphenylimidodiphosphinate (Htpip) ancillary ligand, three iridium complexes of Ir(ppy)2tpip (Hppy=2-phenylpyridine), Ir(npy)2tpip (Hnpy=2-(naphthalene-1-yl)pyridine) and Ir(pnpy)2tpip (Hpnpy=2-(phenathren-9-yl)pyridine) were synthesized. Their structures were deter-mined by 1H NMR, MS(MALDI-TOF), and the complex Ir(ppy)2tpip was also characterized by crystal structure analysis. Extended π conjugation in cyclometalated ligands leads to narrower bandgap resulting in the red shift emission from 516 nm to 600, 633 nm (from green to red). Consequently, when the cyclometalated ligands change from ppy to npy and pnpy, the quantum efficiencies of the complexes are also improved to 0.36, 0.51 and 0.53, respectively. The conjugative effect of the aromatic rings affects the electron density of heterocycle pyridine and thus increases the energy of LUM Oas evidenced by the spectroscopic data and the computational calculation results. The regular patterns between the ligand structure and the emission can be applied for designing novel iridium complexes with various colors.
Using pyridine-derived cyclometalated ligands and tetraphenylimidodiphosphinate (Htpip) ancillary ligand, three iridium complexes of Ir(ppy)2tpip (Hppy=2-phenylpyridine), Ir(npy)2tpip (Hnpy=2-(naphthalene-1-yl)pyridine) and Ir(pnpy)2tpip (Hpnpy=2-(phenathren-9-yl)pyridine) were synthesized. Their structures were deter-mined by 1H NMR, MS(MALDI-TOF), and the complex Ir(ppy)2tpip was also characterized by crystal structure analysis. Extended π conjugation in cyclometalated ligands leads to narrower bandgap resulting in the red shift emission from 516 nm to 600, 633 nm (from green to red). Consequently, when the cyclometalated ligands change from ppy to npy and pnpy, the quantum efficiencies of the complexes are also improved to 0.36, 0.51 and 0.53, respectively. The conjugative effect of the aromatic rings affects the electron density of heterocycle pyridine and thus increases the energy of LUM Oas evidenced by the spectroscopic data and the computational calculation results. The regular patterns between the ligand structure and the emission can be applied for designing novel iridium complexes with various colors.
2014, 30(5): 977-983
doi: 10.11862/CJIC.2014.144
Abstract:
The surface modification of magnesium-aluminum hydrotalcites was made by sodium dodecyl benzene sulfonate (SDBS), Tween-80 and anionic-nonionic surfactant. Inverse gas chromatography (IGC) was used to investigate the surface properties of the MgAl-LDHs, SDBS-LDHs, Tween-LDHs and SDBS/Tween-LDHs. The surface free energy (ΔG0) and the dispersive component of the surface energy (γsd) were estimated. The results show that the ΔG0 and γsd of the modified LDHs are lower than that of MgAl-LDHs, ΔG0 and γsd of the SDBS/Tween-LDHs are the lowest. This indicates that the chemical stability of SDBS/Tween-LDHs is better than that of other modified LDHs. In addition, the value of γsd decreases with the increasing of temperature, so the compatibility with polymer can be improved by increasing the temperature in the preparation of polymer/hydrotalcite materials.
The surface modification of magnesium-aluminum hydrotalcites was made by sodium dodecyl benzene sulfonate (SDBS), Tween-80 and anionic-nonionic surfactant. Inverse gas chromatography (IGC) was used to investigate the surface properties of the MgAl-LDHs, SDBS-LDHs, Tween-LDHs and SDBS/Tween-LDHs. The surface free energy (ΔG0) and the dispersive component of the surface energy (γsd) were estimated. The results show that the ΔG0 and γsd of the modified LDHs are lower than that of MgAl-LDHs, ΔG0 and γsd of the SDBS/Tween-LDHs are the lowest. This indicates that the chemical stability of SDBS/Tween-LDHs is better than that of other modified LDHs. In addition, the value of γsd decreases with the increasing of temperature, so the compatibility with polymer can be improved by increasing the temperature in the preparation of polymer/hydrotalcite materials.
2014, 30(5): 984-992
doi: 10.11862/CJIC.2014.158
Abstract:
A Schiff base derivate from isonicotinohydrazide and p-N,N-di(2-hydroxyethyl)amino benzaldehyde, together with its organotin complex, have been synthesized and characterized by 1H NMR spectroscopy, elemental analyses and X-ray crystallography. The planar Schiff base compound coordinated to the tin center in a bidentate mode, with the trans-C=N-conformation changed to be cis in the complex. The crystal data of the complex and the large red shift in the fluorescence spectra demonstrated an extension of the π-conjunction due to the coordination. In vitro cytotoxicity data showed that both compounds were more cytotoxic than cisplatin against A-549, MCF-7 and Hela tumor cell lines. The interactions of both compounds with CT-DNA were preliminarily studied by UV-Vis and fluorescence spectroscopy, which suggested that the organotin complex likely induces the distortion of DNA double helix through covalent bonding, while the hydrogen bonds and the large planar structure of the molecule hindered the Schiff base compound from intercalating into the DNA double helix.
A Schiff base derivate from isonicotinohydrazide and p-N,N-di(2-hydroxyethyl)amino benzaldehyde, together with its organotin complex, have been synthesized and characterized by 1H NMR spectroscopy, elemental analyses and X-ray crystallography. The planar Schiff base compound coordinated to the tin center in a bidentate mode, with the trans-C=N-conformation changed to be cis in the complex. The crystal data of the complex and the large red shift in the fluorescence spectra demonstrated an extension of the π-conjunction due to the coordination. In vitro cytotoxicity data showed that both compounds were more cytotoxic than cisplatin against A-549, MCF-7 and Hela tumor cell lines. The interactions of both compounds with CT-DNA were preliminarily studied by UV-Vis and fluorescence spectroscopy, which suggested that the organotin complex likely induces the distortion of DNA double helix through covalent bonding, while the hydrogen bonds and the large planar structure of the molecule hindered the Schiff base compound from intercalating into the DNA double helix.
2014, 30(5): 993-1000
doi: 10.11862/CJIC.2014.175
Abstract:
Via hydrothermal method, MIL-101 was loaded on to the pretreated P25 to obtain MIL-101/P25 composites that were structurally characterized using X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), N2 adsorption-desorption (BET), thermogravimetry (TG), field emission transmission electron microscopy (FETEM) and photoluminescence (PL), meanwhile, the stability of MIL-101 and the composites was investigated, and the synergistic effect induced by compounding was quantitatively evaluated by the proposed synergistic factor. The results show that MIL-101 has sheet-like morphology, and a portion of it combined with P25. After compounding, the stability of MIL-101 is promoted. Compounding can bring the synergistic effect at the appropriate ratio, and when the molar ratio of Cr(NO3)3·9H2O to P25 is 1:1, the composite exhibits the highest activity for the visible light photocatalytic degradation of rhodamine B, and the synergistic factor is 1.64. The composite also exhibits high photocatalytic activity for the degradation of colorless organic pollutant salicylic acid.
Via hydrothermal method, MIL-101 was loaded on to the pretreated P25 to obtain MIL-101/P25 composites that were structurally characterized using X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), N2 adsorption-desorption (BET), thermogravimetry (TG), field emission transmission electron microscopy (FETEM) and photoluminescence (PL), meanwhile, the stability of MIL-101 and the composites was investigated, and the synergistic effect induced by compounding was quantitatively evaluated by the proposed synergistic factor. The results show that MIL-101 has sheet-like morphology, and a portion of it combined with P25. After compounding, the stability of MIL-101 is promoted. Compounding can bring the synergistic effect at the appropriate ratio, and when the molar ratio of Cr(NO3)3·9H2O to P25 is 1:1, the composite exhibits the highest activity for the visible light photocatalytic degradation of rhodamine B, and the synergistic factor is 1.64. The composite also exhibits high photocatalytic activity for the degradation of colorless organic pollutant salicylic acid.
2014, 30(5): 1001-1008
doi: 10.11862/CJIC.2014.186
Abstract:
Aseries of transition metal coordination compounds based on the ligand, triethylenediamine(dabco), [CdCl3H(dabco)2] (1), [CoCl3Hdabco] (2), [NiCl2(H2O)3Hdabco]Cl (3), [CuCl3H(dabco)2]Cl·H2O (4) have been prepared and characterized by elemental analyses, IRspectra, thermogravimety and single crystal X-Ray diffraction structure analyses. Compound 1 displays an one-dimensional straight chain via the hydrogen bonding interactions. Compound 2 possesses the left helix molecular structure. Compound 3 possesses the right helix molecular structure and compound 4 exhibits a two-dimensional molecular sheet with grids. Compounds 1 to 4 show intensive photoluminescence.
Aseries of transition metal coordination compounds based on the ligand, triethylenediamine(dabco), [CdCl3H(dabco)2] (1), [CoCl3Hdabco] (2), [NiCl2(H2O)3Hdabco]Cl (3), [CuCl3H(dabco)2]Cl·H2O (4) have been prepared and characterized by elemental analyses, IRspectra, thermogravimety and single crystal X-Ray diffraction structure analyses. Compound 1 displays an one-dimensional straight chain via the hydrogen bonding interactions. Compound 2 possesses the left helix molecular structure. Compound 3 possesses the right helix molecular structure and compound 4 exhibits a two-dimensional molecular sheet with grids. Compounds 1 to 4 show intensive photoluminescence.
2014, 30(5): 1009-1016
doi: 10.11862/CJIC.2014.023
Abstract:
The adsorption thermodynamics and mechanism of acid red 88(AR88), acid orange 3(AO3) and acid violet 90(AV90) on MgAl Layered double hydroxides with 3:1 Mg/Al molar ratio were investigated. The adsorption isotherms were measured at different temperatures, and the functions of thermodynamics were also calculated. The results indicated that the adsorption process on MgAl-LDO were well consistent with the Langmuir equation and were also spontaneous and exothermic. Three kinetics models were used to describe the kinetics experimental data, and it was found that the pseudo-second order kinetics model was best fitted. The Gibbs free energy was calculated to be 7 to 15 kJ·mol-1 because of Hydrogen bonds between the layers and dye molecular. According to the calculation of Materials Studio5.5, the mechanism of adsorption process was that most dye anions were adsorbed on the surface of MgAl-LDO accompanied with intercalated into the layer.
The adsorption thermodynamics and mechanism of acid red 88(AR88), acid orange 3(AO3) and acid violet 90(AV90) on MgAl Layered double hydroxides with 3:1 Mg/Al molar ratio were investigated. The adsorption isotherms were measured at different temperatures, and the functions of thermodynamics were also calculated. The results indicated that the adsorption process on MgAl-LDO were well consistent with the Langmuir equation and were also spontaneous and exothermic. Three kinetics models were used to describe the kinetics experimental data, and it was found that the pseudo-second order kinetics model was best fitted. The Gibbs free energy was calculated to be 7 to 15 kJ·mol-1 because of Hydrogen bonds between the layers and dye molecular. According to the calculation of Materials Studio5.5, the mechanism of adsorption process was that most dye anions were adsorbed on the surface of MgAl-LDO accompanied with intercalated into the layer.
2014, 30(5): 1017-1024
doi: 10.11862/CJIC.2014.177
Abstract:
Acopper(Ⅱ) complex: [Cu(H2O)(PyTA)2](ClO4)2[PyTA=2,4-diamino-6-(2'-pyridyl)-1,3,5-triazine], was synthesized and characterized by elemental analysis, molar conductivity, IR, UV-Vis and single crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c, with the crystal cell parameters: a=0.98024(6) nm, b=1.24831(7) nm, c=2.15727(11) nm; β=108.657(3)°; Z=4, V=2.5010(2) nm3, R1=0.0543, wR2=0.1506. The complex was assayed against gram-positive (S.aureus, B. subtilis, B. thuringiensis) and gram-negative (X. oryzae, Salmonella, E. coil)bacteria by doubling dilutions method, and the interaction of the complex to DNA was investigated by electronic absorption, fluorescence, viscosity measurement and agarose gel electrophoresis assay. The results showed that the complex has good antibacterial activities, and could bind to CT-DNA by an intercalative mode, and cleave pBR322 DNAby hydroxyl radicals as the active species in the presence of Vit C.
Acopper(Ⅱ) complex: [Cu(H2O)(PyTA)2](ClO4)2[PyTA=2,4-diamino-6-(2'-pyridyl)-1,3,5-triazine], was synthesized and characterized by elemental analysis, molar conductivity, IR, UV-Vis and single crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c, with the crystal cell parameters: a=0.98024(6) nm, b=1.24831(7) nm, c=2.15727(11) nm; β=108.657(3)°; Z=4, V=2.5010(2) nm3, R1=0.0543, wR2=0.1506. The complex was assayed against gram-positive (S.aureus, B. subtilis, B. thuringiensis) and gram-negative (X. oryzae, Salmonella, E. coil)bacteria by doubling dilutions method, and the interaction of the complex to DNA was investigated by electronic absorption, fluorescence, viscosity measurement and agarose gel electrophoresis assay. The results showed that the complex has good antibacterial activities, and could bind to CT-DNA by an intercalative mode, and cleave pBR322 DNAby hydroxyl radicals as the active species in the presence of Vit C.
2014, 30(5): 1025-1030
doi: 10.11862/CJIC.2014.130
Abstract:
The two nickel (Ⅱ) complexes [Ni(L)(Himdz)](1)、[Ni(L)(Mimdz)](2) were synthesized from the reaction of tridentate Schiff base (1-phenyl-3-[(2-hydroxyphenyl)imino]-1-butanone) (H2L) and monodentate N-heterocycles [imidazole (Himdz), 2-methylimidazole (Mimdz)] with Ni(OAc)2·4H2O and characterized by elemental analysis, IR, 1H NMR spectroscopy. An X-ray structure determination of the complexes has been completed. In the solid state, both [Ni(L)(Himdz)] (1), [Ni(L)(Mimdz)] (2) crystallize in P21/c space groups, and exist as dimers due to intermolecular C-H…π interactions. Each of the dimeric molecules forms a one-dimensional zigzag chain via intermolecular N-H…O hydrogen bonds involving the heterocycle N-H group, respectively. The antibacterial activities of the ligand and complexes were tested against seven kinds of bacteria. The results show that the complexes 1 and 2 possess inhibiting effects.
The two nickel (Ⅱ) complexes [Ni(L)(Himdz)](1)、[Ni(L)(Mimdz)](2) were synthesized from the reaction of tridentate Schiff base (1-phenyl-3-[(2-hydroxyphenyl)imino]-1-butanone) (H2L) and monodentate N-heterocycles [imidazole (Himdz), 2-methylimidazole (Mimdz)] with Ni(OAc)2·4H2O and characterized by elemental analysis, IR, 1H NMR spectroscopy. An X-ray structure determination of the complexes has been completed. In the solid state, both [Ni(L)(Himdz)] (1), [Ni(L)(Mimdz)] (2) crystallize in P21/c space groups, and exist as dimers due to intermolecular C-H…π interactions. Each of the dimeric molecules forms a one-dimensional zigzag chain via intermolecular N-H…O hydrogen bonds involving the heterocycle N-H group, respectively. The antibacterial activities of the ligand and complexes were tested against seven kinds of bacteria. The results show that the complexes 1 and 2 possess inhibiting effects.
2014, 30(5): 1031-1037
doi: 10.11862/CJIC.2014.178
Abstract:
Two novel complexes [Sb(Ⅲ)(MeBnNCS2)3] (1) and [Bi(Ⅲ)(MeBnNCS2)3] (2) were synthesized and characterized by elemental analysis, IR, 1H NMR, TG-DTG and X-ray single-crystal diffraction. Both complexes belong to monoclinic system, P21/c space group, for 1: a=0.9551(7) nm, b=1.3575(10) nm, c=2.4681(17) nm, β=104.01(2)°, Z=4, V=3.105 (4) nm3, Dc=1.520 g·cm-3, F(000)=1440, μ=1.314 mm-1, the final R1=0.0339, wR2=0.0832, S=1.010, for 2: a=1.3390(6) nm, b=0.9975(5) nm, c=2.4261(5) nm, β=98.433(7)°, Z=4, V=3.205(2) nm3, Dc=1.653 g·cm-3, F(000)=1568, μ=5.912 mm-1, the final R1=0.0398, wR2=0.0864, S=1.089. The central M(Ⅲ) are coordinated by six sulfur atoms from three legends, completing distorted octahedral coordination environment in 1 and pentagonal pyramid configuration in 2. For 2, the adjacent molecules are formed the dimmer structure by the weak interactions of Bi…S. The complexes were valued for their antimicrobial activities by agar diffusion method. The results indicate that the complex 1 to be active against the four test bacterial organisms.
Two novel complexes [Sb(Ⅲ)(MeBnNCS2)3] (1) and [Bi(Ⅲ)(MeBnNCS2)3] (2) were synthesized and characterized by elemental analysis, IR, 1H NMR, TG-DTG and X-ray single-crystal diffraction. Both complexes belong to monoclinic system, P21/c space group, for 1: a=0.9551(7) nm, b=1.3575(10) nm, c=2.4681(17) nm, β=104.01(2)°, Z=4, V=3.105 (4) nm3, Dc=1.520 g·cm-3, F(000)=1440, μ=1.314 mm-1, the final R1=0.0339, wR2=0.0832, S=1.010, for 2: a=1.3390(6) nm, b=0.9975(5) nm, c=2.4261(5) nm, β=98.433(7)°, Z=4, V=3.205(2) nm3, Dc=1.653 g·cm-3, F(000)=1568, μ=5.912 mm-1, the final R1=0.0398, wR2=0.0864, S=1.089. The central M(Ⅲ) are coordinated by six sulfur atoms from three legends, completing distorted octahedral coordination environment in 1 and pentagonal pyramid configuration in 2. For 2, the adjacent molecules are formed the dimmer structure by the weak interactions of Bi…S. The complexes were valued for their antimicrobial activities by agar diffusion method. The results indicate that the complex 1 to be active against the four test bacterial organisms.
2014, 30(5): 1038-1044
doi: 10.11862/CJIC.2014.115
Abstract:
Four polymers ([Mn(H2O)(PTZDA)(BDC)]n(1), [Co(H2O)(PTZDA)(BDC)]n(2), [Zn(H2O)(PTZDA)(BDC)]n(3), [Cd(H2O)(PTZDA)(BDC)]n(4) (PTZDA=6-(pyridyl-2-yl)-1,3,5-triazine-2,4-diamine, BDC=terephthalate) have been synthesized by hydrothermal reactions and structurally charecaterized by single crystal X-ray diffraction, elemental analysis, IR, TG and PXRD. Structural analysis reveals that the metal ions of compounds 1~4 are bridged by two carboxyl group from, terephthalate acid and are chelated by two nitrogen atoms from PTZD Aligand to form a one dimensional chain. These chains are further extended to 3D supramolecular structure by hydrogen bonds. The magnetic properties of compound 1~2 have been studied, indicating that they exist weak anti-ferromagnetism. Luminescent properties of compounds 3~4 indicates complex 3 and 4 possessing quality of photo-luminescent, which is assigned to the ligands.
Four polymers ([Mn(H2O)(PTZDA)(BDC)]n(1), [Co(H2O)(PTZDA)(BDC)]n(2), [Zn(H2O)(PTZDA)(BDC)]n(3), [Cd(H2O)(PTZDA)(BDC)]n(4) (PTZDA=6-(pyridyl-2-yl)-1,3,5-triazine-2,4-diamine, BDC=terephthalate) have been synthesized by hydrothermal reactions and structurally charecaterized by single crystal X-ray diffraction, elemental analysis, IR, TG and PXRD. Structural analysis reveals that the metal ions of compounds 1~4 are bridged by two carboxyl group from, terephthalate acid and are chelated by two nitrogen atoms from PTZD Aligand to form a one dimensional chain. These chains are further extended to 3D supramolecular structure by hydrogen bonds. The magnetic properties of compound 1~2 have been studied, indicating that they exist weak anti-ferromagnetism. Luminescent properties of compounds 3~4 indicates complex 3 and 4 possessing quality of photo-luminescent, which is assigned to the ligands.
2014, 30(5): 1045-1050
doi: 10.11862/CJIC.2014.049
Abstract:
La1.6Sr0.4NiO4-Ag hollow nanofibers are successfully prepared by electro-spinning technology. The phase and morphology of the materials are characterized by XRD and SEM. The results show that La1.6Sr0.4NiO4-Ag hollow nanofibers with an average diameter in 400 nm are obtained after sintering at 800 ℃ for 2 h. The La1.6Sr0.4NiO4-Ag nanofiber forms mesh-like morphology and good contact with the electrolyte after sintering at 850 ℃ for 1 h. The Electrochemical Impedance Spectroscopy (EIS) measurements show that the area specific resistance (ASR) of La1.6Sr0.4NiO4-Ag nanofiber cathode is 0.32 cm2 at 700 ℃ in air. The oxygen partial pressure measurement indicates that the rate limiting step of the nanofiber cathode is charge transfer process from 600 to 700 ℃.
La1.6Sr0.4NiO4-Ag hollow nanofibers are successfully prepared by electro-spinning technology. The phase and morphology of the materials are characterized by XRD and SEM. The results show that La1.6Sr0.4NiO4-Ag hollow nanofibers with an average diameter in 400 nm are obtained after sintering at 800 ℃ for 2 h. The La1.6Sr0.4NiO4-Ag nanofiber forms mesh-like morphology and good contact with the electrolyte after sintering at 850 ℃ for 1 h. The Electrochemical Impedance Spectroscopy (EIS) measurements show that the area specific resistance (ASR) of La1.6Sr0.4NiO4-Ag nanofiber cathode is 0.32 cm2 at 700 ℃ in air. The oxygen partial pressure measurement indicates that the rate limiting step of the nanofiber cathode is charge transfer process from 600 to 700 ℃.
2014, 30(5): 1051-1055
doi: 10.11862/CJIC.2014.113
Abstract:
Based on a series of chemical reaction, the bulk substituent group tBu and the formyl group are introduced to the pyridine ring, which reacts with 2,6-diisopropylaniline to form the 2-(N-2,6-diisopropylphenylimino) methylene-6-tert-butylpyridine (g) ligand, and then the corresponding [NiBr2(g)] (h) complex is synthesized. From the single-crystal X-ray diffraction analysis, the structure of complex h is the single ligand for the single metal. The h complex crystallizes in orthorhombic with a=1.52776(14) nm, b=1.60846(15) nm, c=1.83777(17) nm, V=4.5160(7) nm3 and Z=8. In the presence of methylaluminoxane (MAO), the catalytic properties as precatalysts for ethylene polymerization is investigated. At 0℃ polymerization temperature, branched polymers as well as short oligomers was simultaneously produced, the Mw of the obtained branched polyethylene is about 1.09×104, in which the branching chains are mainly methyl, butyl and long branching chians with 58.5 branching density (branches/1000C).
Based on a series of chemical reaction, the bulk substituent group tBu and the formyl group are introduced to the pyridine ring, which reacts with 2,6-diisopropylaniline to form the 2-(N-2,6-diisopropylphenylimino) methylene-6-tert-butylpyridine (g) ligand, and then the corresponding [NiBr2(g)] (h) complex is synthesized. From the single-crystal X-ray diffraction analysis, the structure of complex h is the single ligand for the single metal. The h complex crystallizes in orthorhombic with a=1.52776(14) nm, b=1.60846(15) nm, c=1.83777(17) nm, V=4.5160(7) nm3 and Z=8. In the presence of methylaluminoxane (MAO), the catalytic properties as precatalysts for ethylene polymerization is investigated. At 0℃ polymerization temperature, branched polymers as well as short oligomers was simultaneously produced, the Mw of the obtained branched polyethylene is about 1.09×104, in which the branching chains are mainly methyl, butyl and long branching chians with 58.5 branching density (branches/1000C).
2014, 30(5): 1056-1062
doi: 10.11862/CJIC.2014.167
Abstract:
Li2MnSiO4/C nanospheres were prepared by combining the sol-gel and solvothermal processing using ethylene diamine tetraacetic acid (EDTA) as a chelating agent. After calcined under Ar atmosphere at 700 ℃, the (Li, Mn, Si)precursor complexed by EDTAtransformed into Li2MnSiO4/C nanocomposite particles approximately 50 nm in diameter. The initial charge and discharge specific capacities of the sample are 223 and 140 mAh·g-1 at a current density of 33 mA·g-1 (0.1C), respectively, and fifth discharge specific capacity can be achieved 138 mAh·g-1. The discharge specific capacity still is stabilized at around 80 mAh·g-1 at a current density of 66 mA·g-1 (0.2C) after 20 cycles. These results indicate that EDTAcan prevent secondary crystalline phase of forming during calcinations. Such well-dispersed nano-powder exhibits improved cycleability for Li2MnSiO4 cathode.
Li2MnSiO4/C nanospheres were prepared by combining the sol-gel and solvothermal processing using ethylene diamine tetraacetic acid (EDTA) as a chelating agent. After calcined under Ar atmosphere at 700 ℃, the (Li, Mn, Si)precursor complexed by EDTAtransformed into Li2MnSiO4/C nanocomposite particles approximately 50 nm in diameter. The initial charge and discharge specific capacities of the sample are 223 and 140 mAh·g-1 at a current density of 33 mA·g-1 (0.1C), respectively, and fifth discharge specific capacity can be achieved 138 mAh·g-1. The discharge specific capacity still is stabilized at around 80 mAh·g-1 at a current density of 66 mA·g-1 (0.2C) after 20 cycles. These results indicate that EDTAcan prevent secondary crystalline phase of forming during calcinations. Such well-dispersed nano-powder exhibits improved cycleability for Li2MnSiO4 cathode.
2014, 30(5): 1063-1067
doi: 10.11862/CJIC.2014.138
Abstract:
Aseries of Ti-SBA-15 with different titanium loadings were synthesized under conventional hydrothermal conditions, using tetra-n-butyl titanate as the titanium source. The Ti-Co-SBA-15 catalysts were synthesized by using the impregnation method. The catalyst samples were characterized using XRD, UV-Raman, FTIR, low temperature N2 adsorption-desorption. The catalytic performance of the catalysts was evaluated for oxidation of 4-tert-butyltoluene into 4-tert-butylbenzaldehyde under mild conditions. The results show that the prepared catalysts have larger surface area and pore size, and they contain four coordinated titanium and cobalt. The catalysts have higher activity, selectivity and yield of 4-tert-butylbenzaldehyde in the oxidation reaction of 4-tert-butyltoluene.
Aseries of Ti-SBA-15 with different titanium loadings were synthesized under conventional hydrothermal conditions, using tetra-n-butyl titanate as the titanium source. The Ti-Co-SBA-15 catalysts were synthesized by using the impregnation method. The catalyst samples were characterized using XRD, UV-Raman, FTIR, low temperature N2 adsorption-desorption. The catalytic performance of the catalysts was evaluated for oxidation of 4-tert-butyltoluene into 4-tert-butylbenzaldehyde under mild conditions. The results show that the prepared catalysts have larger surface area and pore size, and they contain four coordinated titanium and cobalt. The catalysts have higher activity, selectivity and yield of 4-tert-butylbenzaldehyde in the oxidation reaction of 4-tert-butyltoluene.
2014, 30(5): 1068-1072
doi: 10.11862/CJIC.2014.131
Abstract:
In this paper, light-burned dolomite was used as the raw material to prepare fibroid nano-Mg(OH)2. First of all, basic magnesium carbonate(BMC) was prepared by carbonizing light-burned dolomite. Secondly by adding ammonia water used as precipitator to BMC which was acidulated, Mg(OH)2 was prepared by chemical precipitation method. At last, ethanediamine was used to reprocess Mg(OH)2 to control the recrystallization for fibroid nano-Mg(OH)2. The fibroid nano-Mg(OH)2 was characterized by SEM, XRD and TG-DTA methods. The XRD results indicated that the fibroid nano-Mg(OH)2 with perfect crystal were obtained when the recrystallization temperature was above 180 ℃. SEM analysis showed that the grain size increased with the increase of ethanediamine. The effect of recrystallization time on the Mg(OH)2 crystal showed that fibroid nano-Mg(OH)2, with 20~30 nm in diameter and 400~700 nm in length, were observed after 21 hours heating retreatment. The TG-DTA results showed that Mg(OH)2 would decompose to MgO at temperature range of 318~416 ℃.
In this paper, light-burned dolomite was used as the raw material to prepare fibroid nano-Mg(OH)2. First of all, basic magnesium carbonate(BMC) was prepared by carbonizing light-burned dolomite. Secondly by adding ammonia water used as precipitator to BMC which was acidulated, Mg(OH)2 was prepared by chemical precipitation method. At last, ethanediamine was used to reprocess Mg(OH)2 to control the recrystallization for fibroid nano-Mg(OH)2. The fibroid nano-Mg(OH)2 was characterized by SEM, XRD and TG-DTA methods. The XRD results indicated that the fibroid nano-Mg(OH)2 with perfect crystal were obtained when the recrystallization temperature was above 180 ℃. SEM analysis showed that the grain size increased with the increase of ethanediamine. The effect of recrystallization time on the Mg(OH)2 crystal showed that fibroid nano-Mg(OH)2, with 20~30 nm in diameter and 400~700 nm in length, were observed after 21 hours heating retreatment. The TG-DTA results showed that Mg(OH)2 would decompose to MgO at temperature range of 318~416 ℃.
2014, 30(5): 1073-1078
doi: 10.11862/CJIC.2014.180
Abstract:
Dentate organic ester ligandsmethyl glucoside aromatic ester based ligands (MGAE ligand) (C15H18O9, C15H16O8, C22H30O14, C23H22O12, C31H26O15 or C39H30O18) with complexation ability were, through the catalysis of triethylamine, synthesized using methyl glucoside and phthalic anhydride as selected raw materials. Then, a series of MGAE ligand based metal-organic coordination compounds were prepared in the involvement of triethylamine as a template agent through complexing the new type of organic ligands with metal salt solution,Then the MGAE ligand based complexes were characterized using FT-IR, XRD, TGA, FSEM, EDS and BET. The results showed that the complexation is chiefly due to the involvement of carbonyl in the MGAE ligand and the performance of complexes is mainly influenced by the MGAE ligands and metal cations.
Dentate organic ester ligandsmethyl glucoside aromatic ester based ligands (MGAE ligand) (C15H18O9, C15H16O8, C22H30O14, C23H22O12, C31H26O15 or C39H30O18) with complexation ability were, through the catalysis of triethylamine, synthesized using methyl glucoside and phthalic anhydride as selected raw materials. Then, a series of MGAE ligand based metal-organic coordination compounds were prepared in the involvement of triethylamine as a template agent through complexing the new type of organic ligands with metal salt solution,Then the MGAE ligand based complexes were characterized using FT-IR, XRD, TGA, FSEM, EDS and BET. The results showed that the complexation is chiefly due to the involvement of carbonyl in the MGAE ligand and the performance of complexes is mainly influenced by the MGAE ligands and metal cations.
2014, 30(5): 1079-1086
doi: 10.11862/CJIC.2014.173
Abstract:
The interaction between cyclic porphyrin dimmer and four kinds of pyrrolidine di-functionalized C60 (bis-C60) isomers, namely trans-2, trans-3, trans-4, and e, has been studied by UV-Visible absorption spectroscopy. The introduction of pyrrolidine ring weakens the interaction between porphyrin dimer and fullerene in the order of C60 >mono-functionalized C60 >di-functionalized C60. Four kinds of bisadduct isomers were compared with each other in their interaction with porphyrin dimer, with an order of trans-2> trans-3≈trans-4> e isomer, which is attributed to different steric hindrance caused by different substitution pattern. The density functional theory calculation on the interaction geometry and absorption spectra were performed for the trans-3 bis-C60/cyclic porphyrin dimer complex.
The interaction between cyclic porphyrin dimmer and four kinds of pyrrolidine di-functionalized C60 (bis-C60) isomers, namely trans-2, trans-3, trans-4, and e, has been studied by UV-Visible absorption spectroscopy. The introduction of pyrrolidine ring weakens the interaction between porphyrin dimer and fullerene in the order of C60 >mono-functionalized C60 >di-functionalized C60. Four kinds of bisadduct isomers were compared with each other in their interaction with porphyrin dimer, with an order of trans-2> trans-3≈trans-4> e isomer, which is attributed to different steric hindrance caused by different substitution pattern. The density functional theory calculation on the interaction geometry and absorption spectra were performed for the trans-3 bis-C60/cyclic porphyrin dimer complex.
2014, 30(5): 1087-1096
doi: 10.11862/CJIC.2014.170
Abstract:
For the further research of drug applications of rare earth complexes, four complexes of RE L2 L'Cl·nH2O (RE: Nd3+, Eu3+, La3+, Sc3+; L=all-trans retinoic acid; L'=L-arginine acid ion) were synthesized. The compositions of complexes were tested by IR, UV, fluorescence spectra, elemental analysis and TG-DTA methods. Meanwhile, the antitumor activity against HepG2, A549 and Hela in vitro growth cells was investigated by MTT test method, and the results showed that the synthesized four rare earth complexes have different degrees of inhibition on the growth of HepG2, A549 and Hela cells.And the inhibitory effect of complexes is significantly better than that of nitrate of rare earth and ligands. ScL2L'Cl complex is the best one with inhibition of the four under the concentration of 1 mmol·L-1. The interaction of these complexes with DNA was studied by fluorescence spectra, viscosity and UV spectra, and the results showed that the type of interaction is mainly intercalation, which may be the one of reasons for antitumor activity of the complexes. The research provides certain ideas and experimental basis to design efficient and low toxicity of rare earth antitumor drugs.
For the further research of drug applications of rare earth complexes, four complexes of RE L2 L'Cl·nH2O (RE: Nd3+, Eu3+, La3+, Sc3+; L=all-trans retinoic acid; L'=L-arginine acid ion) were synthesized. The compositions of complexes were tested by IR, UV, fluorescence spectra, elemental analysis and TG-DTA methods. Meanwhile, the antitumor activity against HepG2, A549 and Hela in vitro growth cells was investigated by MTT test method, and the results showed that the synthesized four rare earth complexes have different degrees of inhibition on the growth of HepG2, A549 and Hela cells.And the inhibitory effect of complexes is significantly better than that of nitrate of rare earth and ligands. ScL2L'Cl complex is the best one with inhibition of the four under the concentration of 1 mmol·L-1. The interaction of these complexes with DNA was studied by fluorescence spectra, viscosity and UV spectra, and the results showed that the type of interaction is mainly intercalation, which may be the one of reasons for antitumor activity of the complexes. The research provides certain ideas and experimental basis to design efficient and low toxicity of rare earth antitumor drugs.
2014, 30(5): 1097-1103
doi: 10.11862/CJIC.2014.157
Abstract:
N-doped long bamboo-like carbon nanotubes(NDLBLCNTs) were prepared by DCarc-discharge with the coevaporation of anode and stainless steel sheet(SSS). The morphology, structure, and composition of the products were characterized by using scanning electron microscope(SEM), field emission high resolution transmission electron microscope(HRTEM), energy dispersive X-ray(EDX) spectrometer, electron energy loss spectroscopy (EELS), and transmission electron microscope(TEM). The results show that the lengths of the NDLBLCNTs are between 640 nm and 835 nm, the inner diameters are in the range of 23~35 nm, and the outer diameters are in the range of 28~47 nm. In each of the inner cavities formed at the "bamboo joints" there is a black nanoparticle. Both the diameters of such black nanoparticles and the content of NDLBLCNTs in the product are related with the melted and evaporated area of the SSS. The temperature gradient between the SSSand the center of arc discharge zone is about 87.5~94.4 ℃·mm-1. The coevaporation of the SSS together with the anode is the sufficient and necessary condition for the formation NDLBLCNTs. The growth mechanism of the NDLBLCNTs is discussed briefly.
N-doped long bamboo-like carbon nanotubes(NDLBLCNTs) were prepared by DCarc-discharge with the coevaporation of anode and stainless steel sheet(SSS). The morphology, structure, and composition of the products were characterized by using scanning electron microscope(SEM), field emission high resolution transmission electron microscope(HRTEM), energy dispersive X-ray(EDX) spectrometer, electron energy loss spectroscopy (EELS), and transmission electron microscope(TEM). The results show that the lengths of the NDLBLCNTs are between 640 nm and 835 nm, the inner diameters are in the range of 23~35 nm, and the outer diameters are in the range of 28~47 nm. In each of the inner cavities formed at the "bamboo joints" there is a black nanoparticle. Both the diameters of such black nanoparticles and the content of NDLBLCNTs in the product are related with the melted and evaporated area of the SSS. The temperature gradient between the SSSand the center of arc discharge zone is about 87.5~94.4 ℃·mm-1. The coevaporation of the SSS together with the anode is the sufficient and necessary condition for the formation NDLBLCNTs. The growth mechanism of the NDLBLCNTs is discussed briefly.
2014, 30(5): 1104-1110
doi: 10.11862/CJIC.2014.188
Abstract:
One [Mn8Ce] mixed metal cluster, namely, [Mn8O8Ce(O2CCH3)12(pyr)4]·2CH3OH (2·2CH3OH, pyr=pyrozole) has been obtained by adding (NH4)2Ce(NO3)6 to the acetonitrile/methanol solution containing Mn(O2CCH3)2·4H2O, pyrozole and acetic acid. The complex was fully characterized by X-ray single crystal structural diffraction, IR, elemental analysis and magnetic investigation. The structural analysis indicates that the complex crystallized in the monoclinic system, P21/c space group, and the eight MnⅢ ions formed a nonplanar loop, which was further attached to the central CeⅣ ion via eight μ3-O2- ions. Magnetic studies indicate that, within the cluster, the magnetic coupling interactions between Mn3+ ions are weak ferromagnetic, with the ground state Sbeing 6. Moreover, there are only very weak frequency-dependent signals from ac magnetic susceptibility investigations. By analyzing magneto-structural correlation of a series of [Mn8Ce] complexes, we found that with the angles at monoatomically bridging O2- increasing and with the angle at monoatomically bridging carboxylate Odecreasing, the ferromagnetic interactions between Mn atoms will be strengthened, which further lead to larger S.
One [Mn8Ce] mixed metal cluster, namely, [Mn8O8Ce(O2CCH3)12(pyr)4]·2CH3OH (2·2CH3OH, pyr=pyrozole) has been obtained by adding (NH4)2Ce(NO3)6 to the acetonitrile/methanol solution containing Mn(O2CCH3)2·4H2O, pyrozole and acetic acid. The complex was fully characterized by X-ray single crystal structural diffraction, IR, elemental analysis and magnetic investigation. The structural analysis indicates that the complex crystallized in the monoclinic system, P21/c space group, and the eight MnⅢ ions formed a nonplanar loop, which was further attached to the central CeⅣ ion via eight μ3-O2- ions. Magnetic studies indicate that, within the cluster, the magnetic coupling interactions between Mn3+ ions are weak ferromagnetic, with the ground state Sbeing 6. Moreover, there are only very weak frequency-dependent signals from ac magnetic susceptibility investigations. By analyzing magneto-structural correlation of a series of [Mn8Ce] complexes, we found that with the angles at monoatomically bridging O2- increasing and with the angle at monoatomically bridging carboxylate Odecreasing, the ferromagnetic interactions between Mn atoms will be strengthened, which further lead to larger S.
2014, 30(5): 1111-1118
doi: 10.11862/CJIC.2014.147
Abstract:
Organic-inorganic hybrid silica membranes were prepared by sol-gel technique using1,2-bis(triethoxysilyl)ethane (BTESE) and 1H,1H,2H,2H-perfluorooctyltriethoxysilane (PFOTES) as precursors under acidic condition. The hydrophobic property, sol particle size distribution and pore structure of the modified silica membranes were characterized by contact angle measurement, FT-IR, dynamic light scattering and N2 adsorption, respectively. The hydrogen permeation, separation and hydrothermal stability of the supported membranes were also investigated in detail. The results show that hydrophobic microporous membranes are obtained after modification by perfluorooctyl groups, with a water contact angle of (110.4±0.4)° and a pore size ranging from 0.5 to 0.8 nm at a PFOTES/BTESE molar ratio of 0.6. At 300 ℃, the transport of hydrogen in the modified supported hybrid silica membranes complies with a micropore diffusion mechanism, with a high hydrogen permeance of 8.5×10-7 mol·m-2·s-1·Pa-1, a H2/CO2, H2/CO and H2/SF6 permselectivity of 5.49, 5.90 and 18.36, respectively, higher than those of the corresponding Knudsen value. Under a humid condition with a temperature of 250 ℃ and a water vapor molar ratio of 5%, the hydrogen permeance and H2/CO2 permselectivity of the modified silica membranes remain almost constant, indicative of an excellent hydrothermal stability for the membranes.
Organic-inorganic hybrid silica membranes were prepared by sol-gel technique using1,2-bis(triethoxysilyl)ethane (BTESE) and 1H,1H,2H,2H-perfluorooctyltriethoxysilane (PFOTES) as precursors under acidic condition. The hydrophobic property, sol particle size distribution and pore structure of the modified silica membranes were characterized by contact angle measurement, FT-IR, dynamic light scattering and N2 adsorption, respectively. The hydrogen permeation, separation and hydrothermal stability of the supported membranes were also investigated in detail. The results show that hydrophobic microporous membranes are obtained after modification by perfluorooctyl groups, with a water contact angle of (110.4±0.4)° and a pore size ranging from 0.5 to 0.8 nm at a PFOTES/BTESE molar ratio of 0.6. At 300 ℃, the transport of hydrogen in the modified supported hybrid silica membranes complies with a micropore diffusion mechanism, with a high hydrogen permeance of 8.5×10-7 mol·m-2·s-1·Pa-1, a H2/CO2, H2/CO and H2/SF6 permselectivity of 5.49, 5.90 and 18.36, respectively, higher than those of the corresponding Knudsen value. Under a humid condition with a temperature of 250 ℃ and a water vapor molar ratio of 5%, the hydrogen permeance and H2/CO2 permselectivity of the modified silica membranes remain almost constant, indicative of an excellent hydrothermal stability for the membranes.
2014, 30(5): 1119-1127
doi: 10.11862/CJIC.2014.172
Abstract:
The Effect of divalent metal ion was studied on conversion of M2+/Fe2+/Fe3+-LDHs (M=Co, Ni, Mn, Zn) to spinel ferrites under mild conditions (below 100 ℃ in open air). The results show that the conversion is not only affected by aging temperature but also by position of M2+ in periodic table of elements. Large radius of M2+ ions will result in much easier formation of spinel ferrites from LDH microcrystallines when these ions are in the same period and close to each other. Also the existence of Fe2+ plays an important role in the process, and the conversion could not happen without participation of Fe2+ under the conditions studied.
The Effect of divalent metal ion was studied on conversion of M2+/Fe2+/Fe3+-LDHs (M=Co, Ni, Mn, Zn) to spinel ferrites under mild conditions (below 100 ℃ in open air). The results show that the conversion is not only affected by aging temperature but also by position of M2+ in periodic table of elements. Large radius of M2+ ions will result in much easier formation of spinel ferrites from LDH microcrystallines when these ions are in the same period and close to each other. Also the existence of Fe2+ plays an important role in the process, and the conversion could not happen without participation of Fe2+ under the conditions studied.
2014, 30(5): 1128-1134
doi: 10.11862/CJIC.2014.142
Abstract:
Two transition metal complexes, [M(bipy)(Metha)2]n·nH2O (M=Ni, 1; Co, 2; bipy=4,4'-bipyridine, Metha=methanoic acid), have been synthesized by hydrothermal synthesis and characterized by elemental analyses, IR spectroscopy, and X-ray single-crystal diffraction etc. The single crystal structures show the two complexes belong to monoclinic system, C2/c space group. Complexes 1 and 2 have similar 3Dnetwork structures. Metha have two kinds of different types with M2+ ion, one kind is the two oxygen atoms of the Metha as bridging ligand atoms, connected by chain with bipy, another is the carboxyl oxygen of the Metha with only one oxygen atom with another M2+ ion.
Two transition metal complexes, [M(bipy)(Metha)2]n·nH2O (M=Ni, 1; Co, 2; bipy=4,4'-bipyridine, Metha=methanoic acid), have been synthesized by hydrothermal synthesis and characterized by elemental analyses, IR spectroscopy, and X-ray single-crystal diffraction etc. The single crystal structures show the two complexes belong to monoclinic system, C2/c space group. Complexes 1 and 2 have similar 3Dnetwork structures. Metha have two kinds of different types with M2+ ion, one kind is the two oxygen atoms of the Metha as bridging ligand atoms, connected by chain with bipy, another is the carboxyl oxygen of the Metha with only one oxygen atom with another M2+ ion.
2014, 30(5): 1135-1142
doi: 10.11862/CJIC.2014.152
Abstract:
An organooxotin cluster [(μ-O)(μ-OMe)(L)Sn2(CH2Ph)4]2 (HL=(MeO)2C6H3CO2H) has been synthesized by the dealkylation reaction of (PhCH2)3SnCl with 3,4-dimethoxybenzoic acid in methanol, and was characterized by UV, IR, elemental analysis and X-ray crystal diffraction. The crystal belongs to triclinic system, space group P1 with the cell parameters: a=1.2256(5) nm, b=1.2294(5) nm, c=1.3780(5) nm, α=69.784(7)°, β=68.568(7)°, γ=72.926(7)°, V=1.7801(12) nm3, Z=1, Dc=1.549 g·cm-3, μ(MoKα)=1.447 mm-1, F(000)=832, R1=0.0261 and wR2=0.0606. Crystal structure shows a distorted trigonal bipyramidal configuration with five-coordination for the central tin atom, and the complex has a centrosymmetric structure mode with a four-membered central endocyclic Sn2O2 unit. Due to the C-H…π interactions between phenyl-Hand benzene ring, the adjacent molecules of the complex is linked to generate 1D ribbon structure. Atheoretical investigation of one structural unit of the title complex was carried out using Gaussian 03W at LANL2DZ level. The stability and the composition of the frontier molecular orbitals confirmed the coordination geometry of the crystal structure. Thermogravimetric analysis shows that the complex is stable up to 128 ℃. Moreover, its fluorescence spectra was also investigated.
An organooxotin cluster [(μ-O)(μ-OMe)(L)Sn2(CH2Ph)4]2 (HL=(MeO)2C6H3CO2H) has been synthesized by the dealkylation reaction of (PhCH2)3SnCl with 3,4-dimethoxybenzoic acid in methanol, and was characterized by UV, IR, elemental analysis and X-ray crystal diffraction. The crystal belongs to triclinic system, space group P1 with the cell parameters: a=1.2256(5) nm, b=1.2294(5) nm, c=1.3780(5) nm, α=69.784(7)°, β=68.568(7)°, γ=72.926(7)°, V=1.7801(12) nm3, Z=1, Dc=1.549 g·cm-3, μ(MoKα)=1.447 mm-1, F(000)=832, R1=0.0261 and wR2=0.0606. Crystal structure shows a distorted trigonal bipyramidal configuration with five-coordination for the central tin atom, and the complex has a centrosymmetric structure mode with a four-membered central endocyclic Sn2O2 unit. Due to the C-H…π interactions between phenyl-Hand benzene ring, the adjacent molecules of the complex is linked to generate 1D ribbon structure. Atheoretical investigation of one structural unit of the title complex was carried out using Gaussian 03W at LANL2DZ level. The stability and the composition of the frontier molecular orbitals confirmed the coordination geometry of the crystal structure. Thermogravimetric analysis shows that the complex is stable up to 128 ℃. Moreover, its fluorescence spectra was also investigated.
2014, 30(5): 1143-1150
doi: 10.11862/CJIC.2014.101
Abstract:
High-temperature reaction of Gd2O3, K2CO3 and MoO3 leads to a potassium lanthanide molybdate, namely, KGd(MoO4)2. The structure of KGd(MoO4)2 was investigated by means of single-crystal X-ray diffraction at room temperature. Structural analysis results show that it crystallizes in triclinic space group P1 with a=0.52923(6) nm, b=0.69210(6) nm, c=1.06889(7) nm, α=75.79(8)°, β=76.79(5)°, γ=67.60(4)°, Z=2 and R1(all data)=0.0258. K and Gd atoms occupy their respective crystallographic distinct sites. No occupancy disorder and structural modulation exist in the structure. Furthermore, the obtained crystallographic data are used to calculate the band structure, density of states and dielectric constants with the density functional theory method. The results tend to support the experimental data.
High-temperature reaction of Gd2O3, K2CO3 and MoO3 leads to a potassium lanthanide molybdate, namely, KGd(MoO4)2. The structure of KGd(MoO4)2 was investigated by means of single-crystal X-ray diffraction at room temperature. Structural analysis results show that it crystallizes in triclinic space group P1 with a=0.52923(6) nm, b=0.69210(6) nm, c=1.06889(7) nm, α=75.79(8)°, β=76.79(5)°, γ=67.60(4)°, Z=2 and R1(all data)=0.0258. K and Gd atoms occupy their respective crystallographic distinct sites. No occupancy disorder and structural modulation exist in the structure. Furthermore, the obtained crystallographic data are used to calculate the band structure, density of states and dielectric constants with the density functional theory method. The results tend to support the experimental data.
2014, 30(5): 1151-1159
doi: 10.11862/CJIC.2014.027
Abstract:
Circular dichroism (CD) and Raman spectroscopy were employed to investigate the binding of plumbagin (PLU) to human serum albumin (HSA) in the presence of Cu2+ or Mn2+. The results indicate that PLU changes the secondary structure of HSA and reduces the α-helix content. The binding of PLUalso causes the conformational changes of disulfide bridges and the microenvironment of Tyr, Trp residues. In the presence of the metal ion (Cu2+or Mn2+), the above changes are gradually strengthened.
Circular dichroism (CD) and Raman spectroscopy were employed to investigate the binding of plumbagin (PLU) to human serum albumin (HSA) in the presence of Cu2+ or Mn2+. The results indicate that PLU changes the secondary structure of HSA and reduces the α-helix content. The binding of PLUalso causes the conformational changes of disulfide bridges and the microenvironment of Tyr, Trp residues. In the presence of the metal ion (Cu2+or Mn2+), the above changes are gradually strengthened.
2014, 30(5): 1160-1166
doi: 10.11862/CJIC.2014.176
Abstract:
N,N'-Diisobutyl-2,3-diaminoquinoxaline was synthesized by 2,3-dichloroquinoxaline and isobutylamine. And the complexes ([Co(DIDAQX)Cl2]) (1, DIDAQX=N,N'-Diisobutyl-2,3(1H,4H)-diaminoquinoxaline) and ([Zn(DIDAQX)Cl2]) (2) (Same revision as above)were prepared, which characterized by elemental analysis, IR spectra, single crystal X-ray diffraction, TGanalysis, fluorescence and electrochemical properties. For 1, DFT and TD-DFT calculations have been performed to obtain its UV-Vis absorption spectrum, and a satisfactory theoretical-experimental agreement was achieved. The crystal structures of complexes 1 and 2 show that they crystallize in orthorhombic space group Pbca with a=1.4082(3) nm, b=1.4628(3) nm, c=1.7970(4) nm; V= 3.7017(14) nm3, Z=8 of 1 and a=1.4082(3) nm, b=1.4648(3) nm, c=1.7969(4) nm; V=3.7065(14) nm3, Z=8 of 2. In the structure of complexes, each metal atom is four coordinated. Besides chelated by the DIDAQX with two nitrogen atoms, the atom is also coordinated by two Cl atoms, thus form a distorted tetrahedral geometry.
N,N'-Diisobutyl-2,3-diaminoquinoxaline was synthesized by 2,3-dichloroquinoxaline and isobutylamine. And the complexes ([Co(DIDAQX)Cl2]) (1, DIDAQX=N,N'-Diisobutyl-2,3(1H,4H)-diaminoquinoxaline) and ([Zn(DIDAQX)Cl2]) (2) (Same revision as above)were prepared, which characterized by elemental analysis, IR spectra, single crystal X-ray diffraction, TGanalysis, fluorescence and electrochemical properties. For 1, DFT and TD-DFT calculations have been performed to obtain its UV-Vis absorption spectrum, and a satisfactory theoretical-experimental agreement was achieved. The crystal structures of complexes 1 and 2 show that they crystallize in orthorhombic space group Pbca with a=1.4082(3) nm, b=1.4628(3) nm, c=1.7970(4) nm; V= 3.7017(14) nm3, Z=8 of 1 and a=1.4082(3) nm, b=1.4648(3) nm, c=1.7969(4) nm; V=3.7065(14) nm3, Z=8 of 2. In the structure of complexes, each metal atom is four coordinated. Besides chelated by the DIDAQX with two nitrogen atoms, the atom is also coordinated by two Cl atoms, thus form a distorted tetrahedral geometry.
2014, 30(5): 1167-1173
doi: 10.11862/CJIC.2014.123
Abstract:
Fe3O4/P(N-isopropylacrylamide-co-acrylamide) [P(NIPAAm-co-Am)], magnetic thermosensitive composite particles were prepared by emulsifier free polymerization. The structure and morphology of the as-synthesized composite particles were characterized by using TEM, and the magnetic and thermosensitive properties were investigated by Vibrating Sample Magnetometer (VSM) and Dynamic Light Scattering (DLS). In addition, the heat generation ability of the composite particles was investigated under alternating magnetic field. The results show that Fe3O4 nanoparticles are coated by a thermosensitive P(NIPAAm-co-Am) with an LCSTabout 40 ℃. The composite particles exhibit relatively high magnetic property and heat generation ability. Furthermore, the heat generation ability of the composite particles under alternating magnetic field can be adjusted by controlling the concentration of composite particles and/or the magnetic field.
Fe3O4/P(N-isopropylacrylamide-co-acrylamide) [P(NIPAAm-co-Am)], magnetic thermosensitive composite particles were prepared by emulsifier free polymerization. The structure and morphology of the as-synthesized composite particles were characterized by using TEM, and the magnetic and thermosensitive properties were investigated by Vibrating Sample Magnetometer (VSM) and Dynamic Light Scattering (DLS). In addition, the heat generation ability of the composite particles was investigated under alternating magnetic field. The results show that Fe3O4 nanoparticles are coated by a thermosensitive P(NIPAAm-co-Am) with an LCSTabout 40 ℃. The composite particles exhibit relatively high magnetic property and heat generation ability. Furthermore, the heat generation ability of the composite particles under alternating magnetic field can be adjusted by controlling the concentration of composite particles and/or the magnetic field.
2014, 30(5): 1174-1178
doi: 10.11862/CJIC.2014.141
Abstract:
Three ruthenium complexes, [Ru(bpy)2(SB)](PF6)2, [Ru(bpy)(SB)2](PF6)2 and [Ru(SB)3](PF6)2 (bpy=2,2'-bipyridine, SB=4,5-diaza-9,9'-spirobifluorene), have been synthesized and characterized. [Ru(bpy)2(SB)](PF6)2 has also been characterized by single-crystal X-ray diffraction. Its crystal belongs to orthorhombic system with Pbca space group, in which a=1.8818(2) nm, b=1.9913(3) nm, c=2.4221(3) nm, Z=8. The photophysical properties of these complexes were investigated. [Ru(bpy)2(SB)](PF6)2 shows orange red emission at around 606 nm with a phosphorescence quantum yield of ca. 0.0012, while [Ru(bpy)(SB)2](PF6)2 and [Ru(SB)3](PF6)2 shows rather weak or almolst no emissiom at the same condition. The electrochemiluminescence performance of these complexes has also be studied. With the increase of SB ligand concentration, the peak potential increased from 1.36 Vto 1.58 V, and relative peak intensity decreased from 731 to 52.
Three ruthenium complexes, [Ru(bpy)2(SB)](PF6)2, [Ru(bpy)(SB)2](PF6)2 and [Ru(SB)3](PF6)2 (bpy=2,2'-bipyridine, SB=4,5-diaza-9,9'-spirobifluorene), have been synthesized and characterized. [Ru(bpy)2(SB)](PF6)2 has also been characterized by single-crystal X-ray diffraction. Its crystal belongs to orthorhombic system with Pbca space group, in which a=1.8818(2) nm, b=1.9913(3) nm, c=2.4221(3) nm, Z=8. The photophysical properties of these complexes were investigated. [Ru(bpy)2(SB)](PF6)2 shows orange red emission at around 606 nm with a phosphorescence quantum yield of ca. 0.0012, while [Ru(bpy)(SB)2](PF6)2 and [Ru(SB)3](PF6)2 shows rather weak or almolst no emissiom at the same condition. The electrochemiluminescence performance of these complexes has also be studied. With the increase of SB ligand concentration, the peak potential increased from 1.36 Vto 1.58 V, and relative peak intensity decreased from 731 to 52.
2014, 30(5): 1179-1186
doi: 10.11862/CJIC.2014.161
Abstract:
Adetailed study of the effects of silver nanoparticles on the luminescent properties of the europium complex (Eu(Ⅲ)C7H5NO4, Eu(Ⅲ)DPA), where DPAis dipicolinic acid, in the aqueous solution system was reported. The emission intensity of the Eu(Ⅲ)DPA solution initially increased with increasing of the amount of silver colloids and then decreased. The large silver nanoparticles resulted in the high enhancement efficiency and the low amount at which the enhancement efficiency reaches the maximum. The emission intensity was quenched by silver nanoparticles in high concentration of Eu(Ⅲ)DPA solution. The enhancement for the emission of electric dipole transition was stronger than that of magnetic dipole transition. The observed silver nanoparticles dependences of the luminescent intensity were regarded as the result of a stronger coupling between the surface plasmon resonance and the excited luminescence centers and re-absorption of surface plasmon resonance of silver nanoparticles. Meanwhile, the asymmetric ratio of the europium luminescence affected by silver nanoparticles was discussed in terms of the local electromagnetic field enhancement, refractive index, and the ligand field around europium ion.
Adetailed study of the effects of silver nanoparticles on the luminescent properties of the europium complex (Eu(Ⅲ)C7H5NO4, Eu(Ⅲ)DPA), where DPAis dipicolinic acid, in the aqueous solution system was reported. The emission intensity of the Eu(Ⅲ)DPA solution initially increased with increasing of the amount of silver colloids and then decreased. The large silver nanoparticles resulted in the high enhancement efficiency and the low amount at which the enhancement efficiency reaches the maximum. The emission intensity was quenched by silver nanoparticles in high concentration of Eu(Ⅲ)DPA solution. The enhancement for the emission of electric dipole transition was stronger than that of magnetic dipole transition. The observed silver nanoparticles dependences of the luminescent intensity were regarded as the result of a stronger coupling between the surface plasmon resonance and the excited luminescence centers and re-absorption of surface plasmon resonance of silver nanoparticles. Meanwhile, the asymmetric ratio of the europium luminescence affected by silver nanoparticles was discussed in terms of the local electromagnetic field enhancement, refractive index, and the ligand field around europium ion.
2014, 30(5): 1187-1194
doi: 10.11862/CJIC.2014.139
Abstract:
The synthesis of the two Ni(Ⅱ) mononuclear complexes containing N-donor ligands [Ni(phen)2(H2O)2](1,6-nds)·2H2O (1) and [Ni(phen)3](1,6-nds)·10H2O (2) (1,6-nds=1,6-naphthalene-disulfonate anion, phen=1,10-phenanthroline) was conducted in water by the reflux method. For the complex 1, the nickel ion coordinates with two 1,10-phenanthroline ligands and two water molecules, respectively, forming the [Ni(phen)2(H2O)2]2+ cation, and the two uncoordinated water molecules connect to the [Ni(phen)2(H2O)2]2+ cations and 1,6-nds anions to form a two-dimensional layered structure via the hydrogen bonds. For the complex 2, the nickel ion coordinates with three 1,10-phenanthroline ligands to form the [Ni(phen)3]2+ cation. There are abundant hydrogen bonds between free water molecules and 1,6-nds anions, leading to a three-dimensional network structure. In the two complexes, the 1,6-nds anions don't coordinate with the nickel ions, only balance the charges. The complexes exhibit strong luminescence with emission maximum at 443 and 438 nm at room temperature, respectively.
The synthesis of the two Ni(Ⅱ) mononuclear complexes containing N-donor ligands [Ni(phen)2(H2O)2](1,6-nds)·2H2O (1) and [Ni(phen)3](1,6-nds)·10H2O (2) (1,6-nds=1,6-naphthalene-disulfonate anion, phen=1,10-phenanthroline) was conducted in water by the reflux method. For the complex 1, the nickel ion coordinates with two 1,10-phenanthroline ligands and two water molecules, respectively, forming the [Ni(phen)2(H2O)2]2+ cation, and the two uncoordinated water molecules connect to the [Ni(phen)2(H2O)2]2+ cations and 1,6-nds anions to form a two-dimensional layered structure via the hydrogen bonds. For the complex 2, the nickel ion coordinates with three 1,10-phenanthroline ligands to form the [Ni(phen)3]2+ cation. There are abundant hydrogen bonds between free water molecules and 1,6-nds anions, leading to a three-dimensional network structure. In the two complexes, the 1,6-nds anions don't coordinate with the nickel ions, only balance the charges. The complexes exhibit strong luminescence with emission maximum at 443 and 438 nm at room temperature, respectively.
2014, 30(5): 1195-1200
doi: 10.11862/CJIC.2014.166
Abstract:
Two complexes [Zn2(npa)2(Im)4] (1) and [Cd2(npa)2(2,2'-bipy)2(H2O)2]·2H2O (2) (H2npa=3-nitrophthalic acid, Im=imidazole, 2,2'-bipy=2,2'-bipyridine) were constructed by the use of 3-nitrophthalic acid and imidazole or 2,2'-bipyridine, respectively. The complexes were characterized by elemental analysis, IR, and the crystal structures were determined by single X-ray diffraction. The thermal stabilities of the complexes were studied by thermal gravimetric analysis. The two complexes are dinuclear structures, and both contain M2C8O4 14-membered rings. The dinuclear units extend to 3D network through intermolecular hydrogen bonding interactions for complex 1, while a 2D sheet structure is formed for complex 2 by hydrogen bonding and π-π stacking interactions.
Two complexes [Zn2(npa)2(Im)4] (1) and [Cd2(npa)2(2,2'-bipy)2(H2O)2]·2H2O (2) (H2npa=3-nitrophthalic acid, Im=imidazole, 2,2'-bipy=2,2'-bipyridine) were constructed by the use of 3-nitrophthalic acid and imidazole or 2,2'-bipyridine, respectively. The complexes were characterized by elemental analysis, IR, and the crystal structures were determined by single X-ray diffraction. The thermal stabilities of the complexes were studied by thermal gravimetric analysis. The two complexes are dinuclear structures, and both contain M2C8O4 14-membered rings. The dinuclear units extend to 3D network through intermolecular hydrogen bonding interactions for complex 1, while a 2D sheet structure is formed for complex 2 by hydrogen bonding and π-π stacking interactions.
2014, 30(5): 1201-1211
doi: 10.11862/CJIC.2014.150
Abstract:
Nine zirconyl(Ⅱ) complexes of 3-(2-hydroxynaph-1-ylazo)-1,2,4-triazole (HL1), 3-(2,4-dihydroxyphen-1-ylazo)-1,2,4-triazole (HL2), 3-(2-hydroxy-3-carboxynaph-1-ylazo)-1,2,4-triazole (HL3), 3-(2-hydroxy-5-bromophen-1-ylazo)-1,2,4-triazole (HL4) and 3-(2-hydroxy-5-methylphen-1-ylazo)-1,2,4-triazole (HL5) have been synthesized and characterized by elemental analysis, molar conductance, magnetic moment and spectroscopic data (IR, electronic and 1H-NMR) as well as thermal analyses (TGAand DTA). The results show that HL1-HL5 coordinate to zirconyl(Ⅱ) ions as bidentate monobasic ligands through the azo nitrogen and the oxygen of hydroxyl group yielding mononuclear complexes. The biological activity of the ligands and their complexes were studied on four Gram-negative bacteria Escherichia coli, Serratia marcescens, Enterobacter cloacae and Proteus vulgaris and two Gram-positive bacteria Bacillus subtilis and Staphylococcus aureus as well as two fungi Candida albicans and Aspergillus niger. The minimum inhibitory concentrations (MICs) of the prepared compounds were determined by agar diffusion assay using filter paper disc diffusion method. In most cases, metallization increases the antimicrobial activity compared with the free ligand.
Nine zirconyl(Ⅱ) complexes of 3-(2-hydroxynaph-1-ylazo)-1,2,4-triazole (HL1), 3-(2,4-dihydroxyphen-1-ylazo)-1,2,4-triazole (HL2), 3-(2-hydroxy-3-carboxynaph-1-ylazo)-1,2,4-triazole (HL3), 3-(2-hydroxy-5-bromophen-1-ylazo)-1,2,4-triazole (HL4) and 3-(2-hydroxy-5-methylphen-1-ylazo)-1,2,4-triazole (HL5) have been synthesized and characterized by elemental analysis, molar conductance, magnetic moment and spectroscopic data (IR, electronic and 1H-NMR) as well as thermal analyses (TGAand DTA). The results show that HL1-HL5 coordinate to zirconyl(Ⅱ) ions as bidentate monobasic ligands through the azo nitrogen and the oxygen of hydroxyl group yielding mononuclear complexes. The biological activity of the ligands and their complexes were studied on four Gram-negative bacteria Escherichia coli, Serratia marcescens, Enterobacter cloacae and Proteus vulgaris and two Gram-positive bacteria Bacillus subtilis and Staphylococcus aureus as well as two fungi Candida albicans and Aspergillus niger. The minimum inhibitory concentrations (MICs) of the prepared compounds were determined by agar diffusion assay using filter paper disc diffusion method. In most cases, metallization increases the antimicrobial activity compared with the free ligand.
2014, 30(5): 1212-1220
doi: 10.11862/CJIC.2014.169
Abstract:
Undoped and Sb doped ZnSnO3 thin films were synthesized by a sol-gel spin-coating method. Acomparative study between these films was presented. The structure, electrical and optical properties of ZnSnO3 thin films doped with 0mol%, 1mol%, 8mol% and 30mol% of Sb were investigated by X-ray diffraction (XRD), field emission-scanning electron microscope (FE-SEM), X-ray photoelectron spectroscope (XPS), Hall measurement and ultraviolet-visible spectroscope (UV-Vis). The results show that all films correspond to a pure phase of ZnSnO3 structure and that Sb doped ZnSnO3 films have lower resistivity than those of undoped ZnSnO3 films. The minimum resistivity is obtained in ZnSnO3 films doped with 8.0mol% of Sb. In addition, interstitial zinc ions introduced by antimony ion doping in ZnSnO3 crystal lattice lead to a better conductivity. Furthermore, all doped ZnSnO3 films are with >80% transmittance in the region above 475 nm.
Undoped and Sb doped ZnSnO3 thin films were synthesized by a sol-gel spin-coating method. Acomparative study between these films was presented. The structure, electrical and optical properties of ZnSnO3 thin films doped with 0mol%, 1mol%, 8mol% and 30mol% of Sb were investigated by X-ray diffraction (XRD), field emission-scanning electron microscope (FE-SEM), X-ray photoelectron spectroscope (XPS), Hall measurement and ultraviolet-visible spectroscope (UV-Vis). The results show that all films correspond to a pure phase of ZnSnO3 structure and that Sb doped ZnSnO3 films have lower resistivity than those of undoped ZnSnO3 films. The minimum resistivity is obtained in ZnSnO3 films doped with 8.0mol% of Sb. In addition, interstitial zinc ions introduced by antimony ion doping in ZnSnO3 crystal lattice lead to a better conductivity. Furthermore, all doped ZnSnO3 films are with >80% transmittance in the region above 475 nm.
