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2015 Volume 31 Issue 4
2015, (4): 627-634
doi: 10.11862/CJIC.2015.075
Abstract:
Metal-organic frameworks (MOFs) is a new class of organic-inorganic hybrids. MOFs have exhibited the attractive prospects in many fields, such as the gas adsorption and separation, the catalysts, the magnetism and the bio-medicine. However, its performance will be greatly affected in the humid environment, which hindered its industrialization process. Firstly, this paper describes the destruction mechanism of MOFs at the presence of water molecules, and we summarize the elements of MOFs structure stability at the presence of water based on their two structural elements; And then, this paper summarizes the adsorption mechanism of water molecules on MOFs and the influence of it; Finally, we made a prospect of the MOF-water issue in order to provide a reference for future research.
Metal-organic frameworks (MOFs) is a new class of organic-inorganic hybrids. MOFs have exhibited the attractive prospects in many fields, such as the gas adsorption and separation, the catalysts, the magnetism and the bio-medicine. However, its performance will be greatly affected in the humid environment, which hindered its industrialization process. Firstly, this paper describes the destruction mechanism of MOFs at the presence of water molecules, and we summarize the elements of MOFs structure stability at the presence of water based on their two structural elements; And then, this paper summarizes the adsorption mechanism of water molecules on MOFs and the influence of it; Finally, we made a prospect of the MOF-water issue in order to provide a reference for future research.
2015, (4): 635-640
doi: 10.11862/CJIC.2015.118
Abstract:
Hierarchically porous SiO2 monoliths were prepared via sol-gel process accompanied by phase separation with tetramethoxysilane (TMOS) as precursor, poly (ethylene oxide) (PEO) as phase separation inducer, propylene oxide(PO) as gelation agent, 0.01 mol·L-1 hydrochloric acid as catalyst, and twelve sodium dodecyl sulfate(SDS) as mesopore forming agent. The resultant monoliths were characterized by differential thermal analysis (DTA), thermogravimetry (TG), Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and nitrogen adsorption/desorption analysis, and the effects of SDS on the macroporous and mesoporous structure of the monoliths were investigated. The results show that the SDS uniformly distributes into the skeletons in the form of micelles, which leads to the formation of mesopores. When SDS is 0.21 g, the optimum hierarchically porous structure is obtained with macropore size of 1~3 μm, mesopore size of 4~5 nm, and BET specific surface area as high as 650 m2·g-1. After heat treatment at 800℃, macroporous structure and mesopores on the skeleton basically remain, and the BET specific surface area still maintains at 421 m2·g-1, which indicates good thermal stability.
Hierarchically porous SiO2 monoliths were prepared via sol-gel process accompanied by phase separation with tetramethoxysilane (TMOS) as precursor, poly (ethylene oxide) (PEO) as phase separation inducer, propylene oxide(PO) as gelation agent, 0.01 mol·L-1 hydrochloric acid as catalyst, and twelve sodium dodecyl sulfate(SDS) as mesopore forming agent. The resultant monoliths were characterized by differential thermal analysis (DTA), thermogravimetry (TG), Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and nitrogen adsorption/desorption analysis, and the effects of SDS on the macroporous and mesoporous structure of the monoliths were investigated. The results show that the SDS uniformly distributes into the skeletons in the form of micelles, which leads to the formation of mesopores. When SDS is 0.21 g, the optimum hierarchically porous structure is obtained with macropore size of 1~3 μm, mesopore size of 4~5 nm, and BET specific surface area as high as 650 m2·g-1. After heat treatment at 800℃, macroporous structure and mesopores on the skeleton basically remain, and the BET specific surface area still maintains at 421 m2·g-1, which indicates good thermal stability.
2015, (4): 641-648
doi: 10.11862/CJIC.2015.073
Abstract:
Sulfur-carbon composites as the cathode of Lithium-Sulfur batteries have shown excellent electrochemical performance for high power devices. To enhance rate performance of sulfur cathode for Li-S batteries, a carbon material consisted of non-uniform carbon spheres has been prepared by hydrothermal method. Sulfur disperses evenly on the surface of the carbon spheres via a melt-diffusion method. The as-prepared composite with a sulfur content of 52wt% delivers an initial discharge capacity of 1 174 mAh·g-1 and a reversible discharge capacity of 788 mAh·g-1 after 100 cycles at 0.2C. At a higher rate of 4C, the capacity stabilizes at around 600 mAh·g-1. During cycling, the coulombic efficiency is maintained above 90%. The results show that the carbon-sulfur composites with chain conductive network represents a promising cathode material for rechargeable lithium batteries because of the effective improvement of the electronic conductivity, the restraint of the volume expansion and the reduction of the shuttle effect.
Sulfur-carbon composites as the cathode of Lithium-Sulfur batteries have shown excellent electrochemical performance for high power devices. To enhance rate performance of sulfur cathode for Li-S batteries, a carbon material consisted of non-uniform carbon spheres has been prepared by hydrothermal method. Sulfur disperses evenly on the surface of the carbon spheres via a melt-diffusion method. The as-prepared composite with a sulfur content of 52wt% delivers an initial discharge capacity of 1 174 mAh·g-1 and a reversible discharge capacity of 788 mAh·g-1 after 100 cycles at 0.2C. At a higher rate of 4C, the capacity stabilizes at around 600 mAh·g-1. During cycling, the coulombic efficiency is maintained above 90%. The results show that the carbon-sulfur composites with chain conductive network represents a promising cathode material for rechargeable lithium batteries because of the effective improvement of the electronic conductivity, the restraint of the volume expansion and the reduction of the shuttle effect.
2015, (4): 649-658
doi: 10.11862/CJIC.2015.117
Abstract:
Sulfur doped tin oxide (S-SnO2) nanoparticles with high visible light-driven activity was synthesized by a facile solid state synthesis approach at low temperature using sodium dodecyl benzene sulfonate (SDBS) as a template. The samples were characterized by XRD, XPS, SEM, UV-Vis, HR-TEM, and FTIR. The doping mechanism and photocatalytic degradation of paraquat under visible light irradiation were investigated. The results show that the SDBS has a significant regulating effect on the surficial structure for both SnO2 and S-SnO2 prepared by solid state synthesis. The S element is successfully incorporated into the lattice of SnO2 with S(Ⅳ) and S(Ⅵ) rather than embeds into the interstice of SnO2 lattice. S-doping enhances the photocatalytic activity of SnO2 due to the presence of a large number of hydroxyls on the surface and S(Ⅵ) in the lattice of SnO2 benefiting the light absorption and effective charge separation, and it follows an order of SnO2 < S-SnO2 < SnO2(SDBS) < S-SnO2(SDBS).
Sulfur doped tin oxide (S-SnO2) nanoparticles with high visible light-driven activity was synthesized by a facile solid state synthesis approach at low temperature using sodium dodecyl benzene sulfonate (SDBS) as a template. The samples were characterized by XRD, XPS, SEM, UV-Vis, HR-TEM, and FTIR. The doping mechanism and photocatalytic degradation of paraquat under visible light irradiation were investigated. The results show that the SDBS has a significant regulating effect on the surficial structure for both SnO2 and S-SnO2 prepared by solid state synthesis. The S element is successfully incorporated into the lattice of SnO2 with S(Ⅳ) and S(Ⅵ) rather than embeds into the interstice of SnO2 lattice. S-doping enhances the photocatalytic activity of SnO2 due to the presence of a large number of hydroxyls on the surface and S(Ⅵ) in the lattice of SnO2 benefiting the light absorption and effective charge separation, and it follows an order of SnO2 < S-SnO2 < SnO2(SDBS) < S-SnO2(SDBS).
2015, (4): 659-665
doi: 10.11862/CJIC.2015.111
Abstract:
MoO3 nanobelts/RGO composites were obtained through a facile and efficient hydrothermal procedure by using organic compound sodium salicylate as both structure-directing agent and reducing agent. The crystal structure, morphologies and electrochemical performances of the as-prepared samples were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, galvanostatic charge/discharge test and electrochemical impedance spectroscopy (EIS). The hybrid material shows a high specific capacity of 1 000 mAh·g-1 with a good cycling stability as an anode material for lithium ion batteries, which has a much enhanced performance compared to bare MoO3 nanobelts.
MoO3 nanobelts/RGO composites were obtained through a facile and efficient hydrothermal procedure by using organic compound sodium salicylate as both structure-directing agent and reducing agent. The crystal structure, morphologies and electrochemical performances of the as-prepared samples were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, galvanostatic charge/discharge test and electrochemical impedance spectroscopy (EIS). The hybrid material shows a high specific capacity of 1 000 mAh·g-1 with a good cycling stability as an anode material for lithium ion batteries, which has a much enhanced performance compared to bare MoO3 nanobelts.
2015, (4): 666-672
doi: 10.11862/CJIC.2015.104
Abstract:
An iridium(Ⅲ) complex of Ir(N4)(MDFPPM)2 [MDFPPM=2-(2,4-difluorophenyl)-4,6-dimethylpyrimidine, N4=5-(2-Pridyl)-1H-tetrazole] has been prepared, and characterized by X-ray single crystal diffraction. The photophysical properties and energy-level structure of Ir(N4)(MDFPPM)2 are studied by ultraviolet-visble (UV-Vis) absorption, fluorescence, cyclic voltammetry (CV), and time-dependent density functional theory (TD-DFT) calculation. X-ray diffraction studies have revealed that the complex belongs to monoclinic system with space group of P21/c. A theoretical calculation reveals that the HOMO of Ir(N4)(MDFPPM)2 is mainly distributed on the iridium ion and the phenyl group of the cyclometalated ligand MDFPPM, while the LUMO is mainly centered on the pyrimidine group of the cyclometalated ligand MDFPPM. The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) levels of Ir(N4)(MDFPPM)2 are -5.98 and -3.22 eV, respectively. The complex of Ir(N4)(MDFPPM)2 exhibits blue phosphorescent emission with a peak at 449, 480 and 513 nm in acetonitrile solution at 77 K, and with International Commission on Illumination (CIE) coordinates of (0.15, 0.23). CCDC: 1043237, Ir(N4)(MDFPPM)2; 1043238, Ir(N4)(MDFPPM)2·CH2Cl2.
An iridium(Ⅲ) complex of Ir(N4)(MDFPPM)2 [MDFPPM=2-(2,4-difluorophenyl)-4,6-dimethylpyrimidine, N4=5-(2-Pridyl)-1H-tetrazole] has been prepared, and characterized by X-ray single crystal diffraction. The photophysical properties and energy-level structure of Ir(N4)(MDFPPM)2 are studied by ultraviolet-visble (UV-Vis) absorption, fluorescence, cyclic voltammetry (CV), and time-dependent density functional theory (TD-DFT) calculation. X-ray diffraction studies have revealed that the complex belongs to monoclinic system with space group of P21/c. A theoretical calculation reveals that the HOMO of Ir(N4)(MDFPPM)2 is mainly distributed on the iridium ion and the phenyl group of the cyclometalated ligand MDFPPM, while the LUMO is mainly centered on the pyrimidine group of the cyclometalated ligand MDFPPM. The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) levels of Ir(N4)(MDFPPM)2 are -5.98 and -3.22 eV, respectively. The complex of Ir(N4)(MDFPPM)2 exhibits blue phosphorescent emission with a peak at 449, 480 and 513 nm in acetonitrile solution at 77 K, and with International Commission on Illumination (CIE) coordinates of (0.15, 0.23). CCDC: 1043237, Ir(N4)(MDFPPM)2; 1043238, Ir(N4)(MDFPPM)2·CH2Cl2.
2015, (4): 673-680
doi: 10.11862/CJIC.2015.071
Abstract:
The triethylenetetramine-cobalt complex (trien-Co) was synthesized by solid state reaction. The oxygenation of trien-Co and the structure evolution of the oxygenated complexes were investigated by electrospray ionization tandem mass spectrometry, the UV-Vis spectrophotometry, Raman spectrum and Infrared spectroscopy. The experimental results indicated that the uptaking of dioxygen is a dynamic process, and the structures of the oxygenated complex were changed from dinuclear diperoxo-dibridged complex to dinuclear hydroxo-hydroxo dibridge complex in the evolution of oxygenation. 18O2 isotope labeling experiments proved the existence of Co-O-O-Co. Furthermore, the acid dissociation tests reveal that the development of hydroxo dibridge species was the reason for the poor reversibility of trien-Co complex. These results provide a new method and experimental basis for investigating the oxygenation and auto-oxidation mechanism of polyamine-Co complexes.
The triethylenetetramine-cobalt complex (trien-Co) was synthesized by solid state reaction. The oxygenation of trien-Co and the structure evolution of the oxygenated complexes were investigated by electrospray ionization tandem mass spectrometry, the UV-Vis spectrophotometry, Raman spectrum and Infrared spectroscopy. The experimental results indicated that the uptaking of dioxygen is a dynamic process, and the structures of the oxygenated complex were changed from dinuclear diperoxo-dibridged complex to dinuclear hydroxo-hydroxo dibridge complex in the evolution of oxygenation. 18O2 isotope labeling experiments proved the existence of Co-O-O-Co. Furthermore, the acid dissociation tests reveal that the development of hydroxo dibridge species was the reason for the poor reversibility of trien-Co complex. These results provide a new method and experimental basis for investigating the oxygenation and auto-oxidation mechanism of polyamine-Co complexes.
2015, (4): 681-688
doi: 10.11862/CJIC.2015.094
Abstract:
Ag3PO4/Ni thin films were prepared by electrochemical method. The surface morphology, phase structure, optical characteristics and band structure of the thin film were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), respectively. Its photocatalytic properties and stability were evaluated with Rhodamine B (RhB) as a model compound. Using a method of adding active species scavenger to the solution, mechanism of photocatalytic degradation of the film was explored. The results show that the Ag3PO4/Ni thin film prepared under optimum condition has a compact layer structure composed by polymouphous nanoparticles. The thin film exhibits high photocatalytic activity and excellent photocatalytic stability to decompose Rhodamine B. The photodegradation rate is about 2.3 times that of porous P25 TiO2/ITO nanofilm under the visible light in 60 min. The film maintains nearly 100% of their corresponding initial photocatalytic activity after 6 cycles. Furthermore, the photodegradation mechanism of the film for Rhodamine B under the visible light was proposed.
Ag3PO4/Ni thin films were prepared by electrochemical method. The surface morphology, phase structure, optical characteristics and band structure of the thin film were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), respectively. Its photocatalytic properties and stability were evaluated with Rhodamine B (RhB) as a model compound. Using a method of adding active species scavenger to the solution, mechanism of photocatalytic degradation of the film was explored. The results show that the Ag3PO4/Ni thin film prepared under optimum condition has a compact layer structure composed by polymouphous nanoparticles. The thin film exhibits high photocatalytic activity and excellent photocatalytic stability to decompose Rhodamine B. The photodegradation rate is about 2.3 times that of porous P25 TiO2/ITO nanofilm under the visible light in 60 min. The film maintains nearly 100% of their corresponding initial photocatalytic activity after 6 cycles. Furthermore, the photodegradation mechanism of the film for Rhodamine B under the visible light was proposed.
2015, (4): 689-695
doi: 10.11862/CJIC.2015.076
Abstract:
Gd2O3 samples (S-CA, S-OA, S-EDTA) with different morphologies are obtained via thermal treatment from the precursors Gd(OH)3, which are hydrothermally prepared using different additives: Citrate acid (CA), Oleic Acid (OA) and Ethylenediaminetetraacetic acid (EDTA). XRD patterns show that the structure of the as-prepared samples are typical cubic phase with Ia3 space group and slight differences in lattice constants: 1.082 25 nm (S-CA), 1.081 14 nm (S-OA), 1.083 20 nm (S-EDTA). SEM images show that the average particle sizes with different additives are 70 nm (S-CA), 300 nm (S-OA), 2 μm (S-EDTA), respectively. IR spectra further prove that all the samples are Gd2O3, and samples derived from different additives are coupled with organic groups which have different vibration absorption intensities. Upconversion(UC) luminescent and magnetic properties of Gd0.78Yb0.20Ln0.02O3(Ln=Er, Ho) were also studied. The results show that morphologies have a great impact on lanthanides doped UC luminescence intensity and paramagnetic susceptibility of Gd2O3 samples. Among them, both UC luminescence intensity and paramagnetic susceptibility of rare-earth doped Gd2O3 powders derived from EDTA reach the optimum values.
Gd2O3 samples (S-CA, S-OA, S-EDTA) with different morphologies are obtained via thermal treatment from the precursors Gd(OH)3, which are hydrothermally prepared using different additives: Citrate acid (CA), Oleic Acid (OA) and Ethylenediaminetetraacetic acid (EDTA). XRD patterns show that the structure of the as-prepared samples are typical cubic phase with Ia3 space group and slight differences in lattice constants: 1.082 25 nm (S-CA), 1.081 14 nm (S-OA), 1.083 20 nm (S-EDTA). SEM images show that the average particle sizes with different additives are 70 nm (S-CA), 300 nm (S-OA), 2 μm (S-EDTA), respectively. IR spectra further prove that all the samples are Gd2O3, and samples derived from different additives are coupled with organic groups which have different vibration absorption intensities. Upconversion(UC) luminescent and magnetic properties of Gd0.78Yb0.20Ln0.02O3(Ln=Er, Ho) were also studied. The results show that morphologies have a great impact on lanthanides doped UC luminescence intensity and paramagnetic susceptibility of Gd2O3 samples. Among them, both UC luminescence intensity and paramagnetic susceptibility of rare-earth doped Gd2O3 powders derived from EDTA reach the optimum values.
2015, (4): 696-702
doi: 10.11862/CJIC2015.112
Abstract:
A series of δ-MnO2-coated Fe-pillared bentonite composite materials were synthesized and the samples were used as catalysts for the heterogeneous Fenton degradation of methylene blue.The microstructure of the catalysts was characterized by X-ray diffraction (XRD), specific surface area measurements (SBET),scanning electron microscopy (SEM). The results showed that the pillaring process increased the basal spacing (d001) from 1.47 nm for bentonite (MTT) to 1.51 nm for the Hydroxyl-pillared bentonite(H-Fe-P-E) and 1.55 nm for the δ-MnO2-coated Fe-pillared bentonite(H-Fe-P-E-M). The SBET values of the samples were increased after pillaring compared with bentonite. The catalytic activity of different samples was estimated by measuring the degradation rate of methylene blue(MB) in aqueous solution at MB concentration=50 mg·L-1,catalyst dosage=0.1 g·L-1,T=25℃,and the effects of various experimental parameters such as initial H2O2 concentration, δ-MnO2 content and initial solution pH value on MB degradation were studied. The results showed that the catalytic activity of δ-MnO2-coated Fe- pillared bentonite increased with H2O2 concentration and reached a optimal catalytic result when the molar ratio of nFe/nMn=0.241. The kinetics of degradation reaction can be expressed by the first-order reaction kinetic model. In addition, the recyclability of the prepared catalyst is also confirmed. The catalyst retains high activity after being used three times.
A series of δ-MnO2-coated Fe-pillared bentonite composite materials were synthesized and the samples were used as catalysts for the heterogeneous Fenton degradation of methylene blue.The microstructure of the catalysts was characterized by X-ray diffraction (XRD), specific surface area measurements (SBET),scanning electron microscopy (SEM). The results showed that the pillaring process increased the basal spacing (d001) from 1.47 nm for bentonite (MTT) to 1.51 nm for the Hydroxyl-pillared bentonite(H-Fe-P-E) and 1.55 nm for the δ-MnO2-coated Fe-pillared bentonite(H-Fe-P-E-M). The SBET values of the samples were increased after pillaring compared with bentonite. The catalytic activity of different samples was estimated by measuring the degradation rate of methylene blue(MB) in aqueous solution at MB concentration=50 mg·L-1,catalyst dosage=0.1 g·L-1,T=25℃,and the effects of various experimental parameters such as initial H2O2 concentration, δ-MnO2 content and initial solution pH value on MB degradation were studied. The results showed that the catalytic activity of δ-MnO2-coated Fe- pillared bentonite increased with H2O2 concentration and reached a optimal catalytic result when the molar ratio of nFe/nMn=0.241. The kinetics of degradation reaction can be expressed by the first-order reaction kinetic model. In addition, the recyclability of the prepared catalyst is also confirmed. The catalyst retains high activity after being used three times.
2015, (4): 703-709
doi: 10.11862/CJIC.2015.100
Abstract:
Rechargeable lithium battery cathode materials orthorhombic LiMnO2(o-LiMnO2) was directly synthesized using hydrothermal reaction of MnCl2, LiOH, EDTA and NaClO solutions, and carbon nanotube modified o-LiMnO2(o-LiMnO2/CNTs composite) was further obtained by adding CNTs into the reaction system. The as-prepared samples were characterized by X-ray diffractometer and SEM/TEM, and their electrochemical performance was tested using constant current charge/discharge experiment and cyclic voltammetry. o-LiMnO2 was formed when hydrothermal reaction was performed at 180℃ for 24 h with LiOH/MnCl2 molar ratio as low as 8:1. o-LiMnO2 exhibited the initial discharge capacity of 76.0 mAh·g-1, and cycling capacity of 124.1 mAh·g-1 after 100 cycles. The formation of o-LiMnO2/CNTs composite decreased the particle size and electrochemical resistivity of single o-LiMnO2. The initial discharge capacity was 94.1 mAh·g-1, and increased and then kept stable after 45 cycles, and the cycling capacity was 159.8 mAh·g-1 after 100 cycles. This work facilitates the preparation and electrochemical performance improvement of o-LiMnO2 cathode materials for rechargeable lithium batteries.
Rechargeable lithium battery cathode materials orthorhombic LiMnO2(o-LiMnO2) was directly synthesized using hydrothermal reaction of MnCl2, LiOH, EDTA and NaClO solutions, and carbon nanotube modified o-LiMnO2(o-LiMnO2/CNTs composite) was further obtained by adding CNTs into the reaction system. The as-prepared samples were characterized by X-ray diffractometer and SEM/TEM, and their electrochemical performance was tested using constant current charge/discharge experiment and cyclic voltammetry. o-LiMnO2 was formed when hydrothermal reaction was performed at 180℃ for 24 h with LiOH/MnCl2 molar ratio as low as 8:1. o-LiMnO2 exhibited the initial discharge capacity of 76.0 mAh·g-1, and cycling capacity of 124.1 mAh·g-1 after 100 cycles. The formation of o-LiMnO2/CNTs composite decreased the particle size and electrochemical resistivity of single o-LiMnO2. The initial discharge capacity was 94.1 mAh·g-1, and increased and then kept stable after 45 cycles, and the cycling capacity was 159.8 mAh·g-1 after 100 cycles. This work facilitates the preparation and electrochemical performance improvement of o-LiMnO2 cathode materials for rechargeable lithium batteries.
2015, (4): 710-716
doi: 10.11862/CJIC.2015.041
Abstract:
The tetra-nuclear cluster dibutyltin α-naphthaleneacetic carboxylate {[n-Bu2Sn(O2CCH2C10H7)]2O}2 (1) and the 1D chain tributyltin α-naphthaleneacetic carboxylate [n-Bu3Sn(O2CCH2C10H7)]n (2) were synthesized by the reactions of α-naphthaleneacetic acid with dibutyltin oxide and bis(tributyltin) oxide under the same conditions, respectively. Their structures were characterized by IR, 1H and 13C NMR, elemental analysis and X-ray crystal diffraction. The core structures of 1 are two Sn2O2 four-membered rings which are constructed of Sn atoms with O bridges, and the two Sn2O2 units are dimerized to a Sn4O4 cluster, so the center of central Sn2O2 ring coincides with the symmetry center of whole molecule. Due to the C-H…π interactions, the adjacent molecules of complex 1 is linked to generate 1D ribbon structure. For complex 2, two Sn atoms are bridged by two O atoms of a carboxylate ligand to form 1D infinite chain coordination polymer. Thermogravimetric analysis shows the complexes were stable up to 250 or 175℃, respectively. Moreover, the tests showed that both of them displayed strong in vitro anti-tumor activity against five human tumor cell lines, Colo205, HepG2, MCF-7, Hela and NCI-H460, but the activity order is 2 >1. CCDC: 1026774, 1; 1026775, 2.
The tetra-nuclear cluster dibutyltin α-naphthaleneacetic carboxylate {[n-Bu2Sn(O2CCH2C10H7)]2O}2 (1) and the 1D chain tributyltin α-naphthaleneacetic carboxylate [n-Bu3Sn(O2CCH2C10H7)]n (2) were synthesized by the reactions of α-naphthaleneacetic acid with dibutyltin oxide and bis(tributyltin) oxide under the same conditions, respectively. Their structures were characterized by IR, 1H and 13C NMR, elemental analysis and X-ray crystal diffraction. The core structures of 1 are two Sn2O2 four-membered rings which are constructed of Sn atoms with O bridges, and the two Sn2O2 units are dimerized to a Sn4O4 cluster, so the center of central Sn2O2 ring coincides with the symmetry center of whole molecule. Due to the C-H…π interactions, the adjacent molecules of complex 1 is linked to generate 1D ribbon structure. For complex 2, two Sn atoms are bridged by two O atoms of a carboxylate ligand to form 1D infinite chain coordination polymer. Thermogravimetric analysis shows the complexes were stable up to 250 or 175℃, respectively. Moreover, the tests showed that both of them displayed strong in vitro anti-tumor activity against five human tumor cell lines, Colo205, HepG2, MCF-7, Hela and NCI-H460, but the activity order is 2 >1. CCDC: 1026774, 1; 1026775, 2.
2015, (4): 717-724
doi: 10.11862/CJIC.2015.115
Abstract:
Taking 3-sulfobenzoate (3-SBA) and 2-(4-pyridyl)imidazole[4,5-f]phenanthroline (4-PDIP) as the ligands, three lanthanide complexes, [Ln2(3-SBA)2(4-PDIP)2(OH)2(H2O)4]·2H2O (Ln=Sm (1), Eu (2), Gd (3)) were obtained by hydrothermal method. The crystal structures were determined by single crystal X-ray diffraction. The three complexes are binuclear molecules. In the complexes, two Ln(Ⅲ) ions are linked by two hydroxyl groups in bridging-bidentate coordination mode. 3-SBA and 4-PDIP ligands are coordinated with Ln(Ⅲ) ions by the chelating bidentate coordination mode. The three-dimensional supramolecular structure is formed through the hydrogen bonds between binuclear molecules. Complexes 1 and 3 display intense broad emission bands at 545 nm and 529 nm, respectively, which correspond to the π*-π transition of the ligands. Complex 2 presents the characteristics emission of Eu(Ⅲ) ion. The narrow emission bands at 579, 592, 612, 650 and 696 nm are attributed to 5D0→7Fj (j=0~4) transitions of the Eu(Ⅲ) ion, respectively. CCDC: 1046171, 1; 1046169, 2; 1046170, 3.
Taking 3-sulfobenzoate (3-SBA) and 2-(4-pyridyl)imidazole[4,5-f]phenanthroline (4-PDIP) as the ligands, three lanthanide complexes, [Ln2(3-SBA)2(4-PDIP)2(OH)2(H2O)4]·2H2O (Ln=Sm (1), Eu (2), Gd (3)) were obtained by hydrothermal method. The crystal structures were determined by single crystal X-ray diffraction. The three complexes are binuclear molecules. In the complexes, two Ln(Ⅲ) ions are linked by two hydroxyl groups in bridging-bidentate coordination mode. 3-SBA and 4-PDIP ligands are coordinated with Ln(Ⅲ) ions by the chelating bidentate coordination mode. The three-dimensional supramolecular structure is formed through the hydrogen bonds between binuclear molecules. Complexes 1 and 3 display intense broad emission bands at 545 nm and 529 nm, respectively, which correspond to the π*-π transition of the ligands. Complex 2 presents the characteristics emission of Eu(Ⅲ) ion. The narrow emission bands at 579, 592, 612, 650 and 696 nm are attributed to 5D0→7Fj (j=0~4) transitions of the Eu(Ⅲ) ion, respectively. CCDC: 1046171, 1; 1046169, 2; 1046170, 3.
2015, (4): 725-730
doi: 10.11862/CJIC.2015.107
Abstract:
The composite Multi-walled carbon nanotubes/Polyacrylic acid (MWCNTs/PAA) was prepared by chemical functionalization, and Zn4O(1,4-benzenedicarboxylate)3(MOF-5) and hybrid materials MWCNTs/PAA/MOF-5 were obtained by solvothermal method. The resulted samples were characterized by XRD, FTIR, TG, HRTEM, the specific surface area and porosity analyze. The experimental results show that the content of PAA uniformly coated on the surface of MWCNTs is 4.3%; the absorbance peaks of functional groups in PAA occured in the FTIR spectrum of composite MWCNTs/PAA; the morphology of MWCNTs/PAA/MOF-5 was similar to that of MOF-5; the thermal decomposition temperature of MWCNTs/PAA/MOF-5 raised 49℃ than MOF-5; N2 adsorption curves of MOF-5 and MWCNTs/PAA/MOF-5 were typical Ⅰ; the maximum N2 adsorption capacity of MWCNTs/PAA/MOF-5 and MOF-5 were respectively 265 and 299 cm3·g-1 at 77 K and 100 kPa.
The composite Multi-walled carbon nanotubes/Polyacrylic acid (MWCNTs/PAA) was prepared by chemical functionalization, and Zn4O(1,4-benzenedicarboxylate)3(MOF-5) and hybrid materials MWCNTs/PAA/MOF-5 were obtained by solvothermal method. The resulted samples were characterized by XRD, FTIR, TG, HRTEM, the specific surface area and porosity analyze. The experimental results show that the content of PAA uniformly coated on the surface of MWCNTs is 4.3%; the absorbance peaks of functional groups in PAA occured in the FTIR spectrum of composite MWCNTs/PAA; the morphology of MWCNTs/PAA/MOF-5 was similar to that of MOF-5; the thermal decomposition temperature of MWCNTs/PAA/MOF-5 raised 49℃ than MOF-5; N2 adsorption curves of MOF-5 and MWCNTs/PAA/MOF-5 were typical Ⅰ; the maximum N2 adsorption capacity of MWCNTs/PAA/MOF-5 and MOF-5 were respectively 265 and 299 cm3·g-1 at 77 K and 100 kPa.
2015, (4): 731-738
doi: 10.11862/CJIC.2015.106
Abstract:
The cathode material LiFePO4 with high tap density of 1.3 g·cm-3 was synthesized via a solvothermal technique, using ammonium tartrate as additive and carbon source, and ethylene glycol/water as solvent. The as-prepared samples were characterized by X-ray diffraction, Fourier-transform infrared spectroscopy, scanning and transmission electron microscopies. The results show that the as-prepared samples were flowerlike LiFePO4 which consists of single-crystalline nanoplates with an open porous hierarchical structure. A reasonable formation mechanism is proposed based on time dependent experiments. The main evolving process involves the following steps: nucleation, growth and oriented assembling. The electrochemical properties of the LiFePO4 cathode is found to exhibit excellent rate capability (i.e., discharge capacity of 74.8 mAh·g-1 at 10C) and cycling performance (i.e., > 93% of capacity retention rate after 50 cycles).
The cathode material LiFePO4 with high tap density of 1.3 g·cm-3 was synthesized via a solvothermal technique, using ammonium tartrate as additive and carbon source, and ethylene glycol/water as solvent. The as-prepared samples were characterized by X-ray diffraction, Fourier-transform infrared spectroscopy, scanning and transmission electron microscopies. The results show that the as-prepared samples were flowerlike LiFePO4 which consists of single-crystalline nanoplates with an open porous hierarchical structure. A reasonable formation mechanism is proposed based on time dependent experiments. The main evolving process involves the following steps: nucleation, growth and oriented assembling. The electrochemical properties of the LiFePO4 cathode is found to exhibit excellent rate capability (i.e., discharge capacity of 74.8 mAh·g-1 at 10C) and cycling performance (i.e., > 93% of capacity retention rate after 50 cycles).
2015, (4): 739-748
doi: 10.11862/CJIC.2015.110
Abstract:
Two complexes, Zn4(Hhpa)4(phen)4 (1) and {[Cd8(cnam)2(bpy)4(C2O4)6(H2O)8]·2H2O}n(2) (H2hpa=2-hydroxy-isophthalic acid, phen=phenanthroline, H2cnam=4-oxo-4H-pyran-2,6-dicarboxylic acid and bpy=2,2'-bipyridyl), were synthesized under hydrothermal conditions and were characterized by elemental analysis, IR spectrum, single-crystal X-ray diffraction, Fluorescence, TGA and XRD. Complex 1 shows a cyclic tetranuclear structure. The neighboring tetranuclear structures are linked into 3D supramolecular network through π…π stacking interactions. While complex 2 is unprecedented 3D polymer based on tetranuclear cadmium clusters cross-linked by C2O42- ions and cnam2- ligands. In 1 and 2, Hhpa2-, cnam2- ligand and C2O42- ion display colorful coordination modes. In addition, the thermal stabilities and luminescence properties of 1 and 2 were also studied. CCDC:1024511, 1; 1024510, 2.
Two complexes, Zn4(Hhpa)4(phen)4 (1) and {[Cd8(cnam)2(bpy)4(C2O4)6(H2O)8]·2H2O}n(2) (H2hpa=2-hydroxy-isophthalic acid, phen=phenanthroline, H2cnam=4-oxo-4H-pyran-2,6-dicarboxylic acid and bpy=2,2'-bipyridyl), were synthesized under hydrothermal conditions and were characterized by elemental analysis, IR spectrum, single-crystal X-ray diffraction, Fluorescence, TGA and XRD. Complex 1 shows a cyclic tetranuclear structure. The neighboring tetranuclear structures are linked into 3D supramolecular network through π…π stacking interactions. While complex 2 is unprecedented 3D polymer based on tetranuclear cadmium clusters cross-linked by C2O42- ions and cnam2- ligands. In 1 and 2, Hhpa2-, cnam2- ligand and C2O42- ion display colorful coordination modes. In addition, the thermal stabilities and luminescence properties of 1 and 2 were also studied. CCDC:1024511, 1; 1024510, 2.
2015, (4): 749-754
doi: 10.11862/CJIC.2015.063
Abstract:
The crystal morphology and size of CrCoAPO-5 molecular sieves were regulated by controlling gel preparation temperature and crystallization rate. The synthesized molecular sieves were characterized by SEM, XRD, FT-IR, UV-vis, TG, BET and ICP-OES. It was shown that hexagonal plate-like CrCoAPO-5 molecular sieves could be synthesized by conventional hydrothermal crystallization at 150℃ for 4.5 h through introducing seeds into the synthetic gels that were prepared at 5℃. The 3 μm-sized CrCoAPO-5 crystals with the aspect ratio less than 0.2 could be obtained, resulting in shorter diffusion distance and better catalytic activity compared with larger ones.
The crystal morphology and size of CrCoAPO-5 molecular sieves were regulated by controlling gel preparation temperature and crystallization rate. The synthesized molecular sieves were characterized by SEM, XRD, FT-IR, UV-vis, TG, BET and ICP-OES. It was shown that hexagonal plate-like CrCoAPO-5 molecular sieves could be synthesized by conventional hydrothermal crystallization at 150℃ for 4.5 h through introducing seeds into the synthetic gels that were prepared at 5℃. The 3 μm-sized CrCoAPO-5 crystals with the aspect ratio less than 0.2 could be obtained, resulting in shorter diffusion distance and better catalytic activity compared with larger ones.
2015, (4): 755-760
doi: 10.11862/CJIC.2015.103
Abstract:
In order to solve the weak oxidation resistance of carbonyl iron powder at higher temperature, carbonyl iron powders with core-shell coated ZnO were prepared using hydrothermal method and then the composites were fabricated by mixing the absorbent in the paraffin matrix. The results show that the carbonyl iron powders are coated by ZnO nano-roads, forming core-shell urchin-like composite particles. Due to this structure, the carbonyl iron powders are isolated from oxygen and thus the oxidation resistance can be improved. Compared with the absorbing materials consisting of pure carbonyl iron powders, the absorption peak for ZnO/carbonyl iron powder shifts towards the low frequency slightly, but the bandwidth of reflection loss below -5 dB is almost unchanged. The results suggest an alternative approach to improve the oxidation resistance of the carbonyl iron powders without influencing their microwave absorption properties.
In order to solve the weak oxidation resistance of carbonyl iron powder at higher temperature, carbonyl iron powders with core-shell coated ZnO were prepared using hydrothermal method and then the composites were fabricated by mixing the absorbent in the paraffin matrix. The results show that the carbonyl iron powders are coated by ZnO nano-roads, forming core-shell urchin-like composite particles. Due to this structure, the carbonyl iron powders are isolated from oxygen and thus the oxidation resistance can be improved. Compared with the absorbing materials consisting of pure carbonyl iron powders, the absorption peak for ZnO/carbonyl iron powder shifts towards the low frequency slightly, but the bandwidth of reflection loss below -5 dB is almost unchanged. The results suggest an alternative approach to improve the oxidation resistance of the carbonyl iron powders without influencing their microwave absorption properties.
2015, (4): 761-766
doi: 10.11862/CJIC.2015.085
Abstract:
The two organotin 4-iodobenzoates, Ph3Sn(p-I-C6H4O2) (1) and {[n-Bu2Sn(p-I-C6H4O2)]2O}2 (2) have been synthesized by the reaction of triphenyltin hydroxide and dibutyltin oxide with 4-Iodobenzoic acid in ethanol and benzene, respectively. IR, 1H NMR, Elemental analysis and X-ray diffraction for the title complexes were presented. The crystal of complex 1 belongs to triclinic, space group P1. The tin atom has a distorted tetrahedral geometry and the dimeric structure is formed by intermolecular hydrogen bonds and C-I…π. The crystal of complex 2 belongs to monoclinic, space group C2/c. The dimer structure is shaped by one Sn2O2 planar four-membered ring and one-dimensional coordination polymer chain is formed by intermolecular I…I interaction. The thermal gravimetric analysis has showed that: the complexes 1 and 2 are stable below 230℃. It is found that the inhibitory activity of compounds 1 and 2 on weeds Amaranthus spinosus and Portulaca oleracea are greater than the effect on crop mung bean, and inhibitory activity of the compound 2 is higher than 1. It provides a method to study the herbicide for Amaranthus spinosus and Portulaca oleracea. CCDC: 1039846, 1; 1039847, 2.
The two organotin 4-iodobenzoates, Ph3Sn(p-I-C6H4O2) (1) and {[n-Bu2Sn(p-I-C6H4O2)]2O}2 (2) have been synthesized by the reaction of triphenyltin hydroxide and dibutyltin oxide with 4-Iodobenzoic acid in ethanol and benzene, respectively. IR, 1H NMR, Elemental analysis and X-ray diffraction for the title complexes were presented. The crystal of complex 1 belongs to triclinic, space group P1. The tin atom has a distorted tetrahedral geometry and the dimeric structure is formed by intermolecular hydrogen bonds and C-I…π. The crystal of complex 2 belongs to monoclinic, space group C2/c. The dimer structure is shaped by one Sn2O2 planar four-membered ring and one-dimensional coordination polymer chain is formed by intermolecular I…I interaction. The thermal gravimetric analysis has showed that: the complexes 1 and 2 are stable below 230℃. It is found that the inhibitory activity of compounds 1 and 2 on weeds Amaranthus spinosus and Portulaca oleracea are greater than the effect on crop mung bean, and inhibitory activity of the compound 2 is higher than 1. It provides a method to study the herbicide for Amaranthus spinosus and Portulaca oleracea. CCDC: 1039846, 1; 1039847, 2.
2015, (4): 767-773
doi: 10.11862/CJIC.2015.105
Abstract:
Ordered hexagonal supermicroporous silica with nanosheet morphology was successfully synthesized using rosin-based quaternary ammonium salt (dehydroabietyltrimethyl ammonium bromine, short for DTAB) as template agent, tetraethyl orthosilicate as silicate source, and ammonia as alkaline medium. XRD, N2 adsorption-desorption, TEM, and SEM were used to characterize the samples. The results indicated that the dosage amount of template agent, silicate source, alkaline medium, crystallization temperature and stirring time had great effects on the regularity of the pore structure. When the mole ratio of nSiO2:nDTAB:nNH3:nH2O was 1.0:0.1:11.3:924.0; crystallization temperature was 373 K; stirring time was 24 h, the sample got the hightest regularity. After the calcination, the synthesized material possessed large surface area (1 024 m2·g-1), high pore volume (0.56 cm3·g-1) and narrow pore size distribution (centered at about 1.80 nm).
Ordered hexagonal supermicroporous silica with nanosheet morphology was successfully synthesized using rosin-based quaternary ammonium salt (dehydroabietyltrimethyl ammonium bromine, short for DTAB) as template agent, tetraethyl orthosilicate as silicate source, and ammonia as alkaline medium. XRD, N2 adsorption-desorption, TEM, and SEM were used to characterize the samples. The results indicated that the dosage amount of template agent, silicate source, alkaline medium, crystallization temperature and stirring time had great effects on the regularity of the pore structure. When the mole ratio of nSiO2:nDTAB:nNH3:nH2O was 1.0:0.1:11.3:924.0; crystallization temperature was 373 K; stirring time was 24 h, the sample got the hightest regularity. After the calcination, the synthesized material possessed large surface area (1 024 m2·g-1), high pore volume (0.56 cm3·g-1) and narrow pore size distribution (centered at about 1.80 nm).
2015, (4): 774-780
doi: 10.11862/CJIC.2015.088
Abstract:
Reactions of the alkyl-substituted indenyl ligands [C9H7R] (R=CH2CH2CH3 (1), CH(CH3)2 (2), C5H9 (3), CH2C6H5 (4), CH2CH=CH2 (5)) with Ru3(CO)12 in refluxing xylene or heptane gave the responding dinuclear metal carbonyl complexes [(η5-C9H6R)Ru(CO)(μ-CO)]2 (R=CH2CH2CH3 (6), CH(CH3)2 (7), C5H9 (8), CH2C6H5 (9), CH2CH=CH2 (10)), respectively, as well as the bridged diruthenium complex [(η5-C9H6)(H3CH2C)CHCH(CH2CH3)(η5-C9H6)][Ru(CO)(μ-CO)]2 (11). These complexes have been characterized by elemental analysis, IR, and 1H NMR spectroscopy. The molecular structures of 6, 9, 10 and 11 were determined by X-ray diffraction analysis. CCDC: 937499, 6; 972340, 9; 944111, 10; 970734, 11.
Reactions of the alkyl-substituted indenyl ligands [C9H7R] (R=CH2CH2CH3 (1), CH(CH3)2 (2), C5H9 (3), CH2C6H5 (4), CH2CH=CH2 (5)) with Ru3(CO)12 in refluxing xylene or heptane gave the responding dinuclear metal carbonyl complexes [(η5-C9H6R)Ru(CO)(μ-CO)]2 (R=CH2CH2CH3 (6), CH(CH3)2 (7), C5H9 (8), CH2C6H5 (9), CH2CH=CH2 (10)), respectively, as well as the bridged diruthenium complex [(η5-C9H6)(H3CH2C)CHCH(CH2CH3)(η5-C9H6)][Ru(CO)(μ-CO)]2 (11). These complexes have been characterized by elemental analysis, IR, and 1H NMR spectroscopy. The molecular structures of 6, 9, 10 and 11 were determined by X-ray diffraction analysis. CCDC: 937499, 6; 972340, 9; 944111, 10; 970734, 11.
2015, (4): 781-788
doi: 10.11862/CJIC.2015.095
Abstract:
Two metal-organic frameworks (MOFs), formulated as [Cd2(CH3COO)(L)(H2O)3]n (2) and [Na(H2L)]n (2) (H3L=1,3-bis(4'-carboxylphenoxy)benzoic acid) were successfully prepared by hydrothermal reaction of H3L ligand with metal salts. Because of the various coordination modes of the H3L ligand, these compounds display structural diversity. Compound 1 crystallizes in triclinic system with P1 space group and 2 in monoclinic system with C2/c space group. The single crystal structures show that 1 possesses a 3D structural framework, in which the secondary building units(SBUs) are bridged by the L3- ligands, 2 features a 3D 5-connected network with (46·64) topology. Moreover, the luminescent property of compound 1 has been investigated. CCDC: 1009539, 1; 1009540, 2.
Two metal-organic frameworks (MOFs), formulated as [Cd2(CH3COO)(L)(H2O)3]n (2) and [Na(H2L)]n (2) (H3L=1,3-bis(4'-carboxylphenoxy)benzoic acid) were successfully prepared by hydrothermal reaction of H3L ligand with metal salts. Because of the various coordination modes of the H3L ligand, these compounds display structural diversity. Compound 1 crystallizes in triclinic system with P1 space group and 2 in monoclinic system with C2/c space group. The single crystal structures show that 1 possesses a 3D structural framework, in which the secondary building units(SBUs) are bridged by the L3- ligands, 2 features a 3D 5-connected network with (46·64) topology. Moreover, the luminescent property of compound 1 has been investigated. CCDC: 1009539, 1; 1009540, 2.
2015, (4): 789-797
doi: 10.11862/CJIC.2015.099
Abstract:
Large particle ammonium molybdophosphate (AMP) was prepared by slowly dropping a nitric acid solution of potassium pyrophosphate into an ammonium molybdate solution. The nucleation rate (G) and crystal growth rate for AMP were studied. Compared with crystal growth, the nucleation has a higher reaction order. Initially, large particle AMP crystallizes in the kinetic region controlled by phase transfer reaction when the growing speed of supersaturation is higher than the removing speed. The crystal linear growth rate (L) and supersaturation degree (ΔC) of the solution increases first and decreases thereafter. In the medium dropping stage, the increase in removing speed of supersaturation is the same as the growing speed. During the late dropping stage, the nucleation rate rises rapidly when the crystal linear growth rate decreases and the nucleation rate is the only control step for the removing speed of supersaturation. Therefore, the nucleation of AMP almost completes in local solution as soon as meeting the nitric acid solution.
Large particle ammonium molybdophosphate (AMP) was prepared by slowly dropping a nitric acid solution of potassium pyrophosphate into an ammonium molybdate solution. The nucleation rate (G) and crystal growth rate for AMP were studied. Compared with crystal growth, the nucleation has a higher reaction order. Initially, large particle AMP crystallizes in the kinetic region controlled by phase transfer reaction when the growing speed of supersaturation is higher than the removing speed. The crystal linear growth rate (L) and supersaturation degree (ΔC) of the solution increases first and decreases thereafter. In the medium dropping stage, the increase in removing speed of supersaturation is the same as the growing speed. During the late dropping stage, the nucleation rate rises rapidly when the crystal linear growth rate decreases and the nucleation rate is the only control step for the removing speed of supersaturation. Therefore, the nucleation of AMP almost completes in local solution as soon as meeting the nitric acid solution.
2015, (4): 798-806
doi: 10.11862/CJIC.2015.097
Abstract:
Two Zn(Ⅱ) compounds, [Zn(L)2(phen)]·H2O (1) and {[Zn(L)2(bpy)]·2EtOH}n (2) (L=sulfaquinoxaline, phen=phenanthroline, bpy=4,4'-bipyridine)have been synthesized and characterized by single crystal X-ray diffraction, thermal analysis, elemental analysis, IR, UV-Vis and fluorescence. Single crystal X-ray diffraction reveals that complex 1 is a mononuclear structure and complex 2 is one-dimensional structure. Thermal analyses show that complex 1 and 2 have high thermal stability. CCDC: 991934, 1; 991935, 2.
Two Zn(Ⅱ) compounds, [Zn(L)2(phen)]·H2O (1) and {[Zn(L)2(bpy)]·2EtOH}n (2) (L=sulfaquinoxaline, phen=phenanthroline, bpy=4,4'-bipyridine)have been synthesized and characterized by single crystal X-ray diffraction, thermal analysis, elemental analysis, IR, UV-Vis and fluorescence. Single crystal X-ray diffraction reveals that complex 1 is a mononuclear structure and complex 2 is one-dimensional structure. Thermal analyses show that complex 1 and 2 have high thermal stability. CCDC: 991934, 1; 991935, 2.
2015, (4): 807-812
doi: 10.11862/CJIC.2015.102
Abstract:
An antiferromagnetic complexes based on Co(Ⅱ) or Mn(Ⅱ) and chiral ligand L-thioproline (LTP) with formula of [Co(LTP)2]n (1) and [Mn(LTP)2]n (2) were synthesized and structurally characterized. The ligand LTP forms a five-membered ring upon chelation to the metal ions. In the 2-D structure, each octahedral metal ion is linked to another four metal ions by four LTP ligands adopting a μ2-N1O2:O3 coordination mode. Complexes 1 and 2 are same in the coordination mode and network structure, and crystallize in the orthorhombic crystal system. Magnetic measurements show that a weak antiferromagnetic coupling occurs in the complexes. CCDC: 1042934, 1; 1042935, 2.
An antiferromagnetic complexes based on Co(Ⅱ) or Mn(Ⅱ) and chiral ligand L-thioproline (LTP) with formula of [Co(LTP)2]n (1) and [Mn(LTP)2]n (2) were synthesized and structurally characterized. The ligand LTP forms a five-membered ring upon chelation to the metal ions. In the 2-D structure, each octahedral metal ion is linked to another four metal ions by four LTP ligands adopting a μ2-N1O2:O3 coordination mode. Complexes 1 and 2 are same in the coordination mode and network structure, and crystallize in the orthorhombic crystal system. Magnetic measurements show that a weak antiferromagnetic coupling occurs in the complexes. CCDC: 1042934, 1; 1042935, 2.
2015, (4): 813-823
doi: 10.11862/CJIC.2015.113
Abstract:
Two mixed-ligand complexes [Ni(IM)(DCA)(H2O)2]·2H2O (1) and [Cd2(IM)4(DCA)2]·2H2O (2) (DCA=demethylcantharate, 7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylate, C8H8O5; IM=imidazole, C3H4N2) were synthesized and characterized by elemental analysis, infrared spectra, thermogravimetric analysis, and X-ray diffraction. Complex 1 was a mononuclear molecule, with Ni(Ⅱ) ion six-coordinated by one nitrogen atom from imidazole, three oxygen atoms from DCA and two water molecules. The complex 1 crystallized in the monoclinic crystal system with P21/m. Complex 2 was a binuclear molecule, each Cd(Ⅱ) ion was six-coordinated by two nitrogen atoms from two imidazole, one ether oxygen atom and three oxygen atoms of carboxyl groups from DCA. The complex 2 crystallized in the triclinic crystal system with P1 space group. The DNA binding properties of the complexes were investigated by electronic absorption spectra, fluorescence spectra and viscosity measurements. These two complexes could bind to DNA with moderate intensity via partial intercalation. The binding constants Kb were 5.51×103 (1) and 1.01×103 L·mol-1 (2) at 298 K, respectively. Meanwhile, the binding intensity of complex with bovine serum albumin (BSA) is high, with binding constants KA equal to 1.91×105 (1) and 6.17×105 L·mol-1 (2), respectively. Experimental results showed that complexes and BSA formed a 1:1 compound with conforma-tional changes in BSA. The antiproliferative activities of the complex (1) against human hepatoma cells (SMMC7721) lines and human breast cancer cells (MCF-7) lines were tested with MTT assay in vitro. The results showed that the inhibition effect had selectivity against cancer cells after forming complexes. The antiproliferative activities of the complex (IC50=(86.8±6.1) μmol·L-1) against the human hepatoma cells lines was more intense than Na2(DCA) (IC50=(152.8±15.6) μmol·L-1), which suggests potential application in anti-cancer drug development. CCDC: 822330, 1; 822328, 2.
Two mixed-ligand complexes [Ni(IM)(DCA)(H2O)2]·2H2O (1) and [Cd2(IM)4(DCA)2]·2H2O (2) (DCA=demethylcantharate, 7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylate, C8H8O5; IM=imidazole, C3H4N2) were synthesized and characterized by elemental analysis, infrared spectra, thermogravimetric analysis, and X-ray diffraction. Complex 1 was a mononuclear molecule, with Ni(Ⅱ) ion six-coordinated by one nitrogen atom from imidazole, three oxygen atoms from DCA and two water molecules. The complex 1 crystallized in the monoclinic crystal system with P21/m. Complex 2 was a binuclear molecule, each Cd(Ⅱ) ion was six-coordinated by two nitrogen atoms from two imidazole, one ether oxygen atom and three oxygen atoms of carboxyl groups from DCA. The complex 2 crystallized in the triclinic crystal system with P1 space group. The DNA binding properties of the complexes were investigated by electronic absorption spectra, fluorescence spectra and viscosity measurements. These two complexes could bind to DNA with moderate intensity via partial intercalation. The binding constants Kb were 5.51×103 (1) and 1.01×103 L·mol-1 (2) at 298 K, respectively. Meanwhile, the binding intensity of complex with bovine serum albumin (BSA) is high, with binding constants KA equal to 1.91×105 (1) and 6.17×105 L·mol-1 (2), respectively. Experimental results showed that complexes and BSA formed a 1:1 compound with conforma-tional changes in BSA. The antiproliferative activities of the complex (1) against human hepatoma cells (SMMC7721) lines and human breast cancer cells (MCF-7) lines were tested with MTT assay in vitro. The results showed that the inhibition effect had selectivity against cancer cells after forming complexes. The antiproliferative activities of the complex (IC50=(86.8±6.1) μmol·L-1) against the human hepatoma cells lines was more intense than Na2(DCA) (IC50=(152.8±15.6) μmol·L-1), which suggests potential application in anti-cancer drug development. CCDC: 822330, 1; 822328, 2.
2015, (4): 824-838
doi: 10.11862/CJIC.2015.119
Abstract:
The bioactive nanowire of sodium hydrogen titanium oxide (Na0.8H1.2Ti3O7) was obtained by Chemical treating the surface of TiO2-based coating containing Si and Ca (SC) prepared by microarc oxidation (MAO). During the chemical treatment, the dissolution of Ca and Si, and the deposition of Na appear on the surface of the SC coating. The chemically treated SC coating shows better hydrophilic and apatite-formation ability than those of the SC coating, which could be associated with the special structure such as OH group in the sodium hydrogen titanium oxide (SHTO) as well as the Ti-OH group formation during the simulated body fluid immersion. At the same time, the SHTO nanowire is more suitable for the MC3T3-E1 cell adhesion and proliferation due to surface morphology, phase composition, OH group structure and better wetting ability.
The bioactive nanowire of sodium hydrogen titanium oxide (Na0.8H1.2Ti3O7) was obtained by Chemical treating the surface of TiO2-based coating containing Si and Ca (SC) prepared by microarc oxidation (MAO). During the chemical treatment, the dissolution of Ca and Si, and the deposition of Na appear on the surface of the SC coating. The chemically treated SC coating shows better hydrophilic and apatite-formation ability than those of the SC coating, which could be associated with the special structure such as OH group in the sodium hydrogen titanium oxide (SHTO) as well as the Ti-OH group formation during the simulated body fluid immersion. At the same time, the SHTO nanowire is more suitable for the MC3T3-E1 cell adhesion and proliferation due to surface morphology, phase composition, OH group structure and better wetting ability.
2015, (4): 839-847
doi: 10.11862/CJIC.114
Abstract:
Through using two kinds of ligands (biimidazole and its derivative), two polyoxometalate-based compounds, [Ag4(biz)4][H2P2Mo5O23]·2H2O (1) and [Ag4(bbiz)4][HPW10ⅥW2ⅤO40] (2) (biz=2,2-biimidazole, bbiz=5-butyl-2,2-biimidazole), have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analyses and IR spectra. Compound 1 contains bi-nuclear [Ag2(biz)2]2+ clusters, which are linked by [P2Mo5O23]6- anions through terminal O atoms to construct a 1D chain. In compound 2, each Keggin anion offers four bridging O atoms to link four bi-nuclear [Ag2(bbiz)2]2+ clusters and a 2D layer of 2 is constructed. Additionally, the electrochemical, photocatalytic and fluorescent properties of the title compounds have been studied. CCDC: 1027614, 1; 1027615, 2.
Through using two kinds of ligands (biimidazole and its derivative), two polyoxometalate-based compounds, [Ag4(biz)4][H2P2Mo5O23]·2H2O (1) and [Ag4(bbiz)4][HPW10ⅥW2ⅤO40] (2) (biz=2,2-biimidazole, bbiz=5-butyl-2,2-biimidazole), have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analyses and IR spectra. Compound 1 contains bi-nuclear [Ag2(biz)2]2+ clusters, which are linked by [P2Mo5O23]6- anions through terminal O atoms to construct a 1D chain. In compound 2, each Keggin anion offers four bridging O atoms to link four bi-nuclear [Ag2(bbiz)2]2+ clusters and a 2D layer of 2 is constructed. Additionally, the electrochemical, photocatalytic and fluorescent properties of the title compounds have been studied. CCDC: 1027614, 1; 1027615, 2.
2015, (4): 848-856
doi: 10.11862/CJIC.2015.068
Abstract:
Two coordination polymers, {[Zn7(L)4(bpe)2(μ3-OH)2(H2O)8]·4H2O}n (1), and {[Cd3(L)2(bpy)2.5(H2O)]·5.5H2O}n (2) (H3L=3-(carboxymethoxy)benzene-1,2-dioic acid, bpe=1,2-bis(4-pyridyl)-ethene, and bpy=4,4'-bipyridine), have been synthesized under hydrothermal condition. Both complexes were characterized by elemental analysis, IR spectra, thermogravimetric analysis (TGA), and single-crystal X-ray crystallography. Complex 1 features a three-dimensional supramolecular architecture linked through hydrogen bonding interactions in which the secondary building unit (SBU) is [Zn5(μ3-OH)2] cluster. Complex 2 features three-dimensional metal-organic framework with (3,3,6)-connected topology. The luminescence behaviors of 1 and 2 were also discussed. CCDC: 965303, 1; 965304, 2.
Two coordination polymers, {[Zn7(L)4(bpe)2(μ3-OH)2(H2O)8]·4H2O}n (1), and {[Cd3(L)2(bpy)2.5(H2O)]·5.5H2O}n (2) (H3L=3-(carboxymethoxy)benzene-1,2-dioic acid, bpe=1,2-bis(4-pyridyl)-ethene, and bpy=4,4'-bipyridine), have been synthesized under hydrothermal condition. Both complexes were characterized by elemental analysis, IR spectra, thermogravimetric analysis (TGA), and single-crystal X-ray crystallography. Complex 1 features a three-dimensional supramolecular architecture linked through hydrogen bonding interactions in which the secondary building unit (SBU) is [Zn5(μ3-OH)2] cluster. Complex 2 features three-dimensional metal-organic framework with (3,3,6)-connected topology. The luminescence behaviors of 1 and 2 were also discussed. CCDC: 965303, 1; 965304, 2.
