Login In
2014 Volume 33 Issue 2
2014, 33(2): 171-178
Abstract:
Amino-Konjacglucomannan (NH2-KGM) was prepared through the reaction of ammonium hydroxide with KGM by ultrasonic. The influence of amount of ammonium hydroxide, concentration of KGM and ultrasonic time on the extent of amination was studied. Then, NH2-KGM and zinc sulfate were used as materials for the preparation of NH2-KGM-Zn complex. The results indicated that the extent of amination increases with increasing the ammonium hydroxide. The optimum concentration of KGM and ultrasonic time are 0.3% and 75 min respectively. IR showed KGM is successfully aminated and NH2-KGM forms stable complex with zinc(Ⅱ). The hydrogen bonding network structures of NH2-KGM-Zn are more stable and the key linking points of hydrogen bonding network are at the OH(6) and O(3) positions of mannose and OH(2) of glucose and O(3) of mannose on the KGM ring. It is more favorable for NH2-KGM-Zn to form intermolecular hydrogen bonds between KGM.
Amino-Konjacglucomannan (NH2-KGM) was prepared through the reaction of ammonium hydroxide with KGM by ultrasonic. The influence of amount of ammonium hydroxide, concentration of KGM and ultrasonic time on the extent of amination was studied. Then, NH2-KGM and zinc sulfate were used as materials for the preparation of NH2-KGM-Zn complex. The results indicated that the extent of amination increases with increasing the ammonium hydroxide. The optimum concentration of KGM and ultrasonic time are 0.3% and 75 min respectively. IR showed KGM is successfully aminated and NH2-KGM forms stable complex with zinc(Ⅱ). The hydrogen bonding network structures of NH2-KGM-Zn are more stable and the key linking points of hydrogen bonding network are at the OH(6) and O(3) positions of mannose and OH(2) of glucose and O(3) of mannose on the KGM ring. It is more favorable for NH2-KGM-Zn to form intermolecular hydrogen bonds between KGM.
2014, 33(2): 179-188
Abstract:
Three-dimensional (3D) quantitative structure-activity relationship (QSAR) studies of 44 curcumin-related compounds have been carried out based on our previously reported result for their anticancer activity against pancreas cancer Panc-1 cells and colon cancer HT-29 cells. The established 3D-QSAR models from the comparative molecular field analysis (CoMFA) in training set showed not only significant statistical quality, but also satisfying predictive ability, with high correlation coefficient values (R12=0.911, R22=0.985) and cross-validation coefficient values (q12=0.580, q22=0.722). Based on the CoMFA contour maps, some key structural factors responsible for anticancer activity of these series of compounds were revealed. The results provide some useful theoretical references for understanding the mechanism of action, designing new curcumin-related compounds with anticancer activity and predicting their activities prior to synthesis.
Three-dimensional (3D) quantitative structure-activity relationship (QSAR) studies of 44 curcumin-related compounds have been carried out based on our previously reported result for their anticancer activity against pancreas cancer Panc-1 cells and colon cancer HT-29 cells. The established 3D-QSAR models from the comparative molecular field analysis (CoMFA) in training set showed not only significant statistical quality, but also satisfying predictive ability, with high correlation coefficient values (R12=0.911, R22=0.985) and cross-validation coefficient values (q12=0.580, q22=0.722). Based on the CoMFA contour maps, some key structural factors responsible for anticancer activity of these series of compounds were revealed. The results provide some useful theoretical references for understanding the mechanism of action, designing new curcumin-related compounds with anticancer activity and predicting their activities prior to synthesis.
2014, 33(2): 189-192
Abstract:
The complex DtbpNiCl2 (Dtbp=2,9-di-tert-butyl-1,10-phenanthroline) was synthesized and characterized by X-ray single-crystal structure analysis. For the complex:C20H24C12N2Ni·CH2Cl2, Mr=506.95, monoclinic, space group P21/c, a=9.5905(3), b=13.7587(3), c=17.3364(5) Å, β=94.244(2)°, V=2281.31(11) Å3, Z=4, Dc=1.476 g/cm3, λ=1.54184 Å, μ=5.606 mm-1, F(000)=1048,S=1.079, R=0.0402 and wR=0.1010 for 3223 observed reflections with I>2σ(I). In complex DtbpNiCl2, the nickel adopts a distorted tetrahedral geometry coordinated by two nitrogen atoms of Dtbp and two chlorine ions. The complex is connected by intermolecular C-H…Cl hydrogen bonds to form a 1D structure in the solid state.
The complex DtbpNiCl2 (Dtbp=2,9-di-tert-butyl-1,10-phenanthroline) was synthesized and characterized by X-ray single-crystal structure analysis. For the complex:C20H24C12N2Ni·CH2Cl2, Mr=506.95, monoclinic, space group P21/c, a=9.5905(3), b=13.7587(3), c=17.3364(5) Å, β=94.244(2)°, V=2281.31(11) Å3, Z=4, Dc=1.476 g/cm3, λ=1.54184 Å, μ=5.606 mm-1, F(000)=1048,S=1.079, R=0.0402 and wR=0.1010 for 3223 observed reflections with I>2σ(I). In complex DtbpNiCl2, the nickel adopts a distorted tetrahedral geometry coordinated by two nitrogen atoms of Dtbp and two chlorine ions. The complex is connected by intermolecular C-H…Cl hydrogen bonds to form a 1D structure in the solid state.
2014, 33(2): 193-198
Abstract:
A new coordination polymer, namely[Zn(pdc)(bbi)]n {H2pdc=2,3-pyridine dicar-boxylic acid, bbi=1,1'-(1,4-butanediyl)bis(imidazole)}, has been prepared under hydrothermal conditions and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/n with a=8.436(3), b=16.988(5), c=12.106(4) Å, β=92.204(5)°, V=1733.6(9) Å3, Z=4, C17H17N5O4Zn, Mr=420.73, Dc=1.612 g/cm3, F(000)=864, μ(MoKa)=0.452 mm-1, the R=0.0672 and wR=0.1645. In the mononuclear complex, each Zn(Ⅱ) is five-coordinated by one carboxylate O and one pyridyl N atoms from one pdc anion, one carboxylate O atom from another pdc anion, and two N atoms from two bib ligands. The Zn(Ⅱ) ions are connected by pdc ligands to form skeleton chains, and bbi ligands further link them to construct a 2D framework. The thermal and luminescence properties of the complex were also investigated.
A new coordination polymer, namely[Zn(pdc)(bbi)]n {H2pdc=2,3-pyridine dicar-boxylic acid, bbi=1,1'-(1,4-butanediyl)bis(imidazole)}, has been prepared under hydrothermal conditions and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/n with a=8.436(3), b=16.988(5), c=12.106(4) Å, β=92.204(5)°, V=1733.6(9) Å3, Z=4, C17H17N5O4Zn, Mr=420.73, Dc=1.612 g/cm3, F(000)=864, μ(MoKa)=0.452 mm-1, the R=0.0672 and wR=0.1645. In the mononuclear complex, each Zn(Ⅱ) is five-coordinated by one carboxylate O and one pyridyl N atoms from one pdc anion, one carboxylate O atom from another pdc anion, and two N atoms from two bib ligands. The Zn(Ⅱ) ions are connected by pdc ligands to form skeleton chains, and bbi ligands further link them to construct a 2D framework. The thermal and luminescence properties of the complex were also investigated.
2014, 33(2): 199-203
Abstract:
5,3',4'-Trihydroxy-7-methoxyflavanone was isolated from Artemisia sphaeroce-phala Kraschen and characterized by 1H-NMR, 13C-NMR, EI-MS, IR, UV spectra, and single-crystal X-ray diffraction. The title compound crystallizes in orhtorhombic space group Pca21, with a=14.393(3), b=5.1629(12), c=36.919(9) Å, V=2743.4(11) Å3, Z=8, Mr=302.27, Dc=1.464 g/cm3, F(000)=1264, μ=0.113 mm-1,S=1.015, (Δ/σ)max=0.000, the final R=0.0757 and wR=0.1809. Structural analysis indicates the title compound consists of two 5,3',4'-trihydroxy-7-methoxyflavanone enantiomers in a well-defined arrangement within the crystal lattice, which constructs a three-dimensional network by means of multiple O-H…O hydrogen bonds.
5,3',4'-Trihydroxy-7-methoxyflavanone was isolated from Artemisia sphaeroce-phala Kraschen and characterized by 1H-NMR, 13C-NMR, EI-MS, IR, UV spectra, and single-crystal X-ray diffraction. The title compound crystallizes in orhtorhombic space group Pca21, with a=14.393(3), b=5.1629(12), c=36.919(9) Å, V=2743.4(11) Å3, Z=8, Mr=302.27, Dc=1.464 g/cm3, F(000)=1264, μ=0.113 mm-1,S=1.015, (Δ/σ)max=0.000, the final R=0.0757 and wR=0.1809. Structural analysis indicates the title compound consists of two 5,3',4'-trihydroxy-7-methoxyflavanone enantiomers in a well-defined arrangement within the crystal lattice, which constructs a three-dimensional network by means of multiple O-H…O hydrogen bonds.
2014, 33(2): 204-208
Abstract:
A novel spiro-compound (C20H15N2O3P) has been synthesized and characterized by means of IR and 1H NMR. Its crystal structure was determined by X-ray diffractometry. The crystal belongs to the monoclinic system, space group P21/c with a=9.1628(7), b=12.9490(7), c=15.7898(11) Å, β=103.952(8)°, Mr=36.08, V=1818.2(2) Å3, Z=4, Dc=1.382 g/cm3, F(000)=788, μ=0.179 mm-1, R=0.0701 and wR=0.1513. The preliminary biological test showed that the title compound has activities against Escherichia coli, S.albus, Bacillus subtilis, Staphylocc-ocusaureus and Micrococcus tetragenus with MIC to be 0.038, 0.038, 0.075, 2.48, and 0.15 mg/mL, respectively.
A novel spiro-compound (C20H15N2O3P) has been synthesized and characterized by means of IR and 1H NMR. Its crystal structure was determined by X-ray diffractometry. The crystal belongs to the monoclinic system, space group P21/c with a=9.1628(7), b=12.9490(7), c=15.7898(11) Å, β=103.952(8)°, Mr=36.08, V=1818.2(2) Å3, Z=4, Dc=1.382 g/cm3, F(000)=788, μ=0.179 mm-1, R=0.0701 and wR=0.1513. The preliminary biological test showed that the title compound has activities against Escherichia coli, S.albus, Bacillus subtilis, Staphylocc-ocusaureus and Micrococcus tetragenus with MIC to be 0.038, 0.038, 0.075, 2.48, and 0.15 mg/mL, respectively.
2014, 33(2): 209-215
Abstract:
A new borophosphate compound Cd3BPO7 (Mr=490.98) has been successfully synthesized by conventional high temperature solid state reaction for the first time and its structure was determined by single-crystal X-ray diffraction. It crystallizes in orthorhombic, space group Pna21, with a=13.247(3), b=8.8217(18), c=5.0792(10) Å, V=593.56(20) Å3, Z=4, Dc=5.494 g/cm3, λ(CuKα)=1.5406 Å, F(000)=880, the final R=0.0212 and wR=0.0513 for 1287 observed reflections (I>2σ(I)). In the crystal structure of Cd3BPO7, the Cd(Ⅱ) forms a slightly distorted octahedral geometry, BO33- and PO43- ions linking adjacent Cd(Ⅱ) ions to form a 3D net work. The second harmonic generation (SHG) on powder samples was measured using Kurtz and Perry technique. The result indicates that Cd3BPO7 exhibits a SHG response 2.2 times larger than that of potassium dihydrogen phosphate (KDP) and is phase-matchable.
A new borophosphate compound Cd3BPO7 (Mr=490.98) has been successfully synthesized by conventional high temperature solid state reaction for the first time and its structure was determined by single-crystal X-ray diffraction. It crystallizes in orthorhombic, space group Pna21, with a=13.247(3), b=8.8217(18), c=5.0792(10) Å, V=593.56(20) Å3, Z=4, Dc=5.494 g/cm3, λ(CuKα)=1.5406 Å, F(000)=880, the final R=0.0212 and wR=0.0513 for 1287 observed reflections (I>2σ(I)). In the crystal structure of Cd3BPO7, the Cd(Ⅱ) forms a slightly distorted octahedral geometry, BO33- and PO43- ions linking adjacent Cd(Ⅱ) ions to form a 3D net work. The second harmonic generation (SHG) on powder samples was measured using Kurtz and Perry technique. The result indicates that Cd3BPO7 exhibits a SHG response 2.2 times larger than that of potassium dihydrogen phosphate (KDP) and is phase-matchable.
2014, 33(2): 216-222
Abstract:
Human coagulation Factor V (FV), together with Factor Xa, assembles to prothrombi-nase complex on activated cell surface, which converts prothrombin into thrombin, leading to fibrin deposition. The C2 domain of FV is believed to be a primary anchor for the assembly of prothrombinase on the cell surface, and was proposed as a target to intervene with pathological thrombotic events. We report here the crystal structure of the C2 domain of FV fused to maltose-binding protein (MBP). The fusion tag of MBP is critical to generate the crystal for this study. There is no strong interaction between MBP and FVC2. The overall structure of FVC2 is similar to the previous FVC2 structures, suggesting the MBP fusion does not perturb the molecular structure of FVC2. This crystal form of FVC2 can be used for future study of molecular interaction between FVC2 and its inhibitors.
Human coagulation Factor V (FV), together with Factor Xa, assembles to prothrombi-nase complex on activated cell surface, which converts prothrombin into thrombin, leading to fibrin deposition. The C2 domain of FV is believed to be a primary anchor for the assembly of prothrombinase on the cell surface, and was proposed as a target to intervene with pathological thrombotic events. We report here the crystal structure of the C2 domain of FV fused to maltose-binding protein (MBP). The fusion tag of MBP is critical to generate the crystal for this study. There is no strong interaction between MBP and FVC2. The overall structure of FVC2 is similar to the previous FVC2 structures, suggesting the MBP fusion does not perturb the molecular structure of FVC2. This crystal form of FVC2 can be used for future study of molecular interaction between FVC2 and its inhibitors.
2014, 33(2): 223-227
Abstract:
A new crystal of 4-fluoro-N-(2-methyl-5-((2-(p-tolyloxy)acetamido)methyl)pyrimidin-4-yl)benzamide has been prepared at room temperature and characterized by 1H NMR, 13C-NMR, IR, MS, elemental analysis and X-ray single-crystal determination. The compound crystallizes in monoclinic, space group P21/c with a=17.226(5), b=13.934(4), c=17.262(5) Å,β=92.180(5)°, V=4140(2) Å3, Dc=1.311 g/cm3, Z=8, F(000)=1712 and μ=0.095 mm-1. The molecular packing in the crystal is the result of N-H…O hydrogen bonds.
A new crystal of 4-fluoro-N-(2-methyl-5-((2-(p-tolyloxy)acetamido)methyl)pyrimidin-4-yl)benzamide has been prepared at room temperature and characterized by 1H NMR, 13C-NMR, IR, MS, elemental analysis and X-ray single-crystal determination. The compound crystallizes in monoclinic, space group P21/c with a=17.226(5), b=13.934(4), c=17.262(5) Å,β=92.180(5)°, V=4140(2) Å3, Dc=1.311 g/cm3, Z=8, F(000)=1712 and μ=0.095 mm-1. The molecular packing in the crystal is the result of N-H…O hydrogen bonds.
2014, 33(2): 228-236
Abstract:
Density functional theory calculations have been performed to study the interaction of small silver clusters, Ag2~Ag9, with HCN. The adsorption of HCN on-top site of the silver cluster, among various possible sites, is energetically preferred. The adsorption energies of HCN on the silver clusters reach a local maximum at n=4, which is only about 0.450 eV, indicating that the adsorbed HCN molecule is weakly perturbed. The adsorbed C-N and C-H stretching frequencies are blue- and red-shifted compared with the values of free HCN, respectively.
Density functional theory calculations have been performed to study the interaction of small silver clusters, Ag2~Ag9, with HCN. The adsorption of HCN on-top site of the silver cluster, among various possible sites, is energetically preferred. The adsorption energies of HCN on the silver clusters reach a local maximum at n=4, which is only about 0.450 eV, indicating that the adsorbed HCN molecule is weakly perturbed. The adsorbed C-N and C-H stretching frequencies are blue- and red-shifted compared with the values of free HCN, respectively.
2014, 33(2): 237-243
Abstract:
6,8-Di-tert-butyl-3-(2,4-dimethyl-quinolin-7-yl)-3,4-dihydro-2H-benzo[e] [1,3]oxa-zine (1) was obtained by one-pot reaction starting from 2,4-di-tert-butylphenol, 7-amino-2,4-dimethyl-quinoline and paraformaldehyde. The compound was structurally characterized by NMR, IR and single-crystal X-ray diffraction along with the elemental analysis. Compound 1 crystallizes as solvate with chloroform. The solvate 1·CHCl3 (C28H35Cl3N2O, Mr=521.93) belongs to the triclinic system, space group P1 with a=10.852(2), b=11.352(2), c=13.050(3) Å, α=101.95(3), β=92.94(3), γ=114.64(3)o, V=1412.4(5) Å3, Z=2, Dc=1.227 g/cm3, F(000)=552, μ=0.347 mm-1, R=0.0959 and wR=0.2725 (I>2σ(I)). The chloroform molecule displays a rotational disorder as one chloro atom can be located at two different positions. The packing of 1·CHCl3 was further stabilized by intramolecular C-H…O interactions, intermolecular C-H…N interactions, C-H…π interactions, and π…π interactions. The luminescent properties of compound 1 in both methylene chloride solution and the solid state were studied.
6,8-Di-tert-butyl-3-(2,4-dimethyl-quinolin-7-yl)-3,4-dihydro-2H-benzo[e] [1,3]oxa-zine (1) was obtained by one-pot reaction starting from 2,4-di-tert-butylphenol, 7-amino-2,4-dimethyl-quinoline and paraformaldehyde. The compound was structurally characterized by NMR, IR and single-crystal X-ray diffraction along with the elemental analysis. Compound 1 crystallizes as solvate with chloroform. The solvate 1·CHCl3 (C28H35Cl3N2O, Mr=521.93) belongs to the triclinic system, space group P1 with a=10.852(2), b=11.352(2), c=13.050(3) Å, α=101.95(3), β=92.94(3), γ=114.64(3)o, V=1412.4(5) Å3, Z=2, Dc=1.227 g/cm3, F(000)=552, μ=0.347 mm-1, R=0.0959 and wR=0.2725 (I>2σ(I)). The chloroform molecule displays a rotational disorder as one chloro atom can be located at two different positions. The packing of 1·CHCl3 was further stabilized by intramolecular C-H…O interactions, intermolecular C-H…N interactions, C-H…π interactions, and π…π interactions. The luminescent properties of compound 1 in both methylene chloride solution and the solid state were studied.
2014, 33(2): 244-252
Abstract:
In current paper, a quantitative structure-activity relationship (QSAR) study was performed for the prediction of acute toxicity of aromatic amines. A set of 56 compounds was randomly divided into a training set of 46 compounds and a test set of 10 compounds. The electronic and topological descriptors computed by the Scigress package and Dragon software were used as predictor variables. Multiple linear regression (MLR) and support vector machine (SVM) were utilized to build the linear and nonlinear QSAR models, respectively. The obtained models with five descriptors show strong predictive ability. The linear model fits the training set with R2=0.71, with higher SVM values of R2=0.77. The validation results obtained from the test set indicate that the SVM model is comparable or superior to that obtained by MLR, both in terms of prediction ability and robustness.
In current paper, a quantitative structure-activity relationship (QSAR) study was performed for the prediction of acute toxicity of aromatic amines. A set of 56 compounds was randomly divided into a training set of 46 compounds and a test set of 10 compounds. The electronic and topological descriptors computed by the Scigress package and Dragon software were used as predictor variables. Multiple linear regression (MLR) and support vector machine (SVM) were utilized to build the linear and nonlinear QSAR models, respectively. The obtained models with five descriptors show strong predictive ability. The linear model fits the training set with R2=0.71, with higher SVM values of R2=0.77. The validation results obtained from the test set indicate that the SVM model is comparable or superior to that obtained by MLR, both in terms of prediction ability and robustness.
Synthesis, Structure and Biological Activity of 5-Benzyl-4-amino-1,2,4-triazole-3-thione Schiff Base
2014, 33(2): 253-257
Abstract:
A novel Schiff base was synthesized via 5-benzyl-4-amino-1,2,4-triazole-3-thione with 3-phenoxy-benzaldehyde under refluxing. The structure was characterized by elemental analysis, IR, 1H NMR, ESI-MS and single-crystal X-ray diffraction. This compound crystallizes in monoclinic, space group P21/c with a=16.0289(16), b=5.8022(6), c=20.542(2) Å, β=95.667(2)°, C22H18N4OS, Mr=386.46, V=1901.1(3) Å3, Z=4, Dc=1.347 g/cm3, F(000)=804, μ=0.191 mm-1, the final R=0.0453 and wR=0.1307 for 2456 observed reflections with I>2σ(I). The crystal packing of the compound is stabilized by classical intermolecular N-H…S hydrogen bonds. Furthermore, the biological activity to four vegetable pathogens has been tested. The title compound exhibited good fungicidal activities to Gibberlla nicotiancola.
A novel Schiff base was synthesized via 5-benzyl-4-amino-1,2,4-triazole-3-thione with 3-phenoxy-benzaldehyde under refluxing. The structure was characterized by elemental analysis, IR, 1H NMR, ESI-MS and single-crystal X-ray diffraction. This compound crystallizes in monoclinic, space group P21/c with a=16.0289(16), b=5.8022(6), c=20.542(2) Å, β=95.667(2)°, C22H18N4OS, Mr=386.46, V=1901.1(3) Å3, Z=4, Dc=1.347 g/cm3, F(000)=804, μ=0.191 mm-1, the final R=0.0453 and wR=0.1307 for 2456 observed reflections with I>2σ(I). The crystal packing of the compound is stabilized by classical intermolecular N-H…S hydrogen bonds. Furthermore, the biological activity to four vegetable pathogens has been tested. The title compound exhibited good fungicidal activities to Gibberlla nicotiancola.
2014, 33(2): 258-262
Abstract:
Reaction of (NH4)2Ce(NO3)6 first with NaOtBu in a 1:6 molar ratio in THF, then with an equivalent of 2-bis(salicylidieneamino)methylphenol (H3salmp) affords the (salmp)2Ce2(O)Na4(OtBu)4(THF)4·2C6H6 complex. It crystallizes in monoclinic, space group C2/c with a=16.5218(14), b=23.992(2), c=21.9454(18) Å, β=97.470(1)°, V=8625.1(12) Å3, Z=4, Mr=1811.96, Dc=1.395 g/cm3, μ=1.126 mm-1, F(000)=3736,S=1.061, R=0.0405 and wR=0.0932 (I>2σ(I)).
Reaction of (NH4)2Ce(NO3)6 first with NaOtBu in a 1:6 molar ratio in THF, then with an equivalent of 2-bis(salicylidieneamino)methylphenol (H3salmp) affords the (salmp)2Ce2(O)Na4(OtBu)4(THF)4·2C6H6 complex. It crystallizes in monoclinic, space group C2/c with a=16.5218(14), b=23.992(2), c=21.9454(18) Å, β=97.470(1)°, V=8625.1(12) Å3, Z=4, Mr=1811.96, Dc=1.395 g/cm3, μ=1.126 mm-1, F(000)=3736,S=1.061, R=0.0405 and wR=0.0932 (I>2σ(I)).
2014, 33(2): 263-269
Abstract:
A hollow tubular copper removal adsorbent was prepared with oyster shell and cement as the main raw materials. The effects of different formulas, different initial copper concentrations and different pH values of samples on the copper removal efficiency were investigated to determine the optimal conditions for copper removal. The content of copper in the wastewater is determined by Atomic Absorption Spectrophotometer. The microstructure and elemental composition of the samples were characterized by scanning electron microscopy (SEM) and EDS. As a result, the formula with the content of cement to be 8 wt% and the oyster shell powder of 92 wt% is optimal. Under the condition of 30℃, when the pH value was 9.0, the Cu2+ adsorption capacity of the sample could reach 0.59 mg/g at 48 h. SEM analysis revealed that there are abundant pores in the sample, which is beneficial for Cu2+ absorption on the adsorbent.
A hollow tubular copper removal adsorbent was prepared with oyster shell and cement as the main raw materials. The effects of different formulas, different initial copper concentrations and different pH values of samples on the copper removal efficiency were investigated to determine the optimal conditions for copper removal. The content of copper in the wastewater is determined by Atomic Absorption Spectrophotometer. The microstructure and elemental composition of the samples were characterized by scanning electron microscopy (SEM) and EDS. As a result, the formula with the content of cement to be 8 wt% and the oyster shell powder of 92 wt% is optimal. Under the condition of 30℃, when the pH value was 9.0, the Cu2+ adsorption capacity of the sample could reach 0.59 mg/g at 48 h. SEM analysis revealed that there are abundant pores in the sample, which is beneficial for Cu2+ absorption on the adsorbent.
2014, 33(2): 270-276
Abstract:
A new copper complex[Cu(pdc)(bpy)]·H2O (1, H2pdc=3,5-pyridinedicarboxylic acid, bpy=2,2'-bipyridine) has been solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, UV-vis spectroscopy and magnetic measurements. Complex 1 crystallizes in monoclinic system, space group P21/c, a=10.893(2), b=7.3641(15), c=1.9921(4) Å, β=92.16(3)Å, V=1596.9(6) Å3, Dc=1.676 g/cm3, Mr=402.84, Z=4, F(000)=820, μ=1.404 mm-1, the final R=0.0237 and wR=0.0693. The Cu(Ⅱ) ion is five-coordinated by two O atoms from two pdc ligands, one N atom from another pdc ligand and two N atoms from the bpy ligand. The pdc anion, which acts as a tridentate ligand, links three Cu ions, forming (3,3)-connected two-dimensional (2D) sheets. We also studied the electronic structure and orbital energies of complex 1 by DFT methods, and the results are consistent with UV-vis spectrum.
A new copper complex[Cu(pdc)(bpy)]·H2O (1, H2pdc=3,5-pyridinedicarboxylic acid, bpy=2,2'-bipyridine) has been solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, UV-vis spectroscopy and magnetic measurements. Complex 1 crystallizes in monoclinic system, space group P21/c, a=10.893(2), b=7.3641(15), c=1.9921(4) Å, β=92.16(3)Å, V=1596.9(6) Å3, Dc=1.676 g/cm3, Mr=402.84, Z=4, F(000)=820, μ=1.404 mm-1, the final R=0.0237 and wR=0.0693. The Cu(Ⅱ) ion is five-coordinated by two O atoms from two pdc ligands, one N atom from another pdc ligand and two N atoms from the bpy ligand. The pdc anion, which acts as a tridentate ligand, links three Cu ions, forming (3,3)-connected two-dimensional (2D) sheets. We also studied the electronic structure and orbital energies of complex 1 by DFT methods, and the results are consistent with UV-vis spectrum.
2014, 33(2): 277-283
Abstract:
A unique metal-organic framework[Cd2(L)1.5(μ3-OH)(H2O)2]·2H2O (1, H2L=2,5-dibenzoylterephthalic acid) has been synthesized under hydrothermal conditions, and characterized by single-crystal X-ray diffractions, elemental analyses, IR spectra and fluorescence spectrum. The compound is of triclinic system, space group P1, C33H27CdO14, Mr=870.33, a=12.2939(17), b=12.5135(9), c=13.2046(10) Å, α=115.3190(10), β=96.9140(10), γ=109.7950(10)°, V=1641.6(3) Å3, Z=2, Dc=1.761 g/cm3, F(000)=862, μ(MoKα)=1.366 mm-1, Rint=0.0148, R=0.0240 and wR=0.0639 for 5995 observed reflections with I>2σ(I). X-ray analysis shows that the title complex exhibits a 3D framework with (412·63) topology, in which the tetra-nuclear[Cd4(μ3-OH)2] clusters act as 6-connected nodes, and the L ligands can be simplified to be linear connectors. Moreover, the thermal stability and fluorescence have been studied in detail.
A unique metal-organic framework[Cd2(L)1.5(μ3-OH)(H2O)2]·2H2O (1, H2L=2,5-dibenzoylterephthalic acid) has been synthesized under hydrothermal conditions, and characterized by single-crystal X-ray diffractions, elemental analyses, IR spectra and fluorescence spectrum. The compound is of triclinic system, space group P1, C33H27CdO14, Mr=870.33, a=12.2939(17), b=12.5135(9), c=13.2046(10) Å, α=115.3190(10), β=96.9140(10), γ=109.7950(10)°, V=1641.6(3) Å3, Z=2, Dc=1.761 g/cm3, F(000)=862, μ(MoKα)=1.366 mm-1, Rint=0.0148, R=0.0240 and wR=0.0639 for 5995 observed reflections with I>2σ(I). X-ray analysis shows that the title complex exhibits a 3D framework with (412·63) topology, in which the tetra-nuclear[Cd4(μ3-OH)2] clusters act as 6-connected nodes, and the L ligands can be simplified to be linear connectors. Moreover, the thermal stability and fluorescence have been studied in detail.
Synthesis, Crystal Structure and Bioactivity of N-(phenethylcarbamothioyl)cyclopent-1-enecarboxamide
2014, 33(2): 284-288
Abstract:
The compound N-(phenethylcarbamothioyl)cyclopent-1-enecarboxamide was synthesized by the reaction of cyclopent-1-enecarbonyl isothiocyanate with phenethylamine in acetone, and its structure was characterized by IR, 1H NMR and X-ray crystal structure determination. The crystal of the title compound belongs to triclinic, space group P1 with a=6.9500(7), b=9.4618(9), c=11.3256(11) Å, α=71.522(9), β=81.830(8), γ=89.237(8)°, Z=2, V=698.80(12) Å3, Dc=1.304 g/cm3, μ=0.225 mm-1, F(000)=292, R=0.0413 and wR=0.1073 for 1996 observed reflections with I>2σ(I). Intramolecular N(2)-H(2)…O(1) interactions as well as intermolecular N(2)-H(2)…O(1), N(1)-H(1)…S(1) and C(12)-H(12)…S(1) hydrogen bonds help to stabilize the crystal structure. X-ray diffraction analysis reveals that the structure of the new compound exhibits a one-dimensional infinite chain-like structure. The cytotoxicity of the compound was investigated by MTT assay. The results show that the compound is toxic to A549 tumor cell.
The compound N-(phenethylcarbamothioyl)cyclopent-1-enecarboxamide was synthesized by the reaction of cyclopent-1-enecarbonyl isothiocyanate with phenethylamine in acetone, and its structure was characterized by IR, 1H NMR and X-ray crystal structure determination. The crystal of the title compound belongs to triclinic, space group P1 with a=6.9500(7), b=9.4618(9), c=11.3256(11) Å, α=71.522(9), β=81.830(8), γ=89.237(8)°, Z=2, V=698.80(12) Å3, Dc=1.304 g/cm3, μ=0.225 mm-1, F(000)=292, R=0.0413 and wR=0.1073 for 1996 observed reflections with I>2σ(I). Intramolecular N(2)-H(2)…O(1) interactions as well as intermolecular N(2)-H(2)…O(1), N(1)-H(1)…S(1) and C(12)-H(12)…S(1) hydrogen bonds help to stabilize the crystal structure. X-ray diffraction analysis reveals that the structure of the new compound exhibits a one-dimensional infinite chain-like structure. The cytotoxicity of the compound was investigated by MTT assay. The results show that the compound is toxic to A549 tumor cell.
2014, 33(2): 289-293
Abstract:
The title complex bis{1-[[(3-ethyl-6-methyl-2-pyridinyl)imino]methylenyl]-2-naphthalenola-to-N,O}nickel has been synthesized by the reaction of 1-[[(3-ethyl-6-methyl-2-pyridinyl) imino] methylenyl]-2-naphthalenol with Ni(CH3COO)2·4H2O, and characterized by IR spectrum and single-crystal X-ray diffraction analysis. The crystal belongs to the orthorhombic system, space group Pbca with a=11.100(2), b=15.900(3), c=18.000(4) Å, V=3176.8(11) Å3, C38H34N4NiO2, Mr=637.40, Z=4, Dc=1.333 g/cm3, μ=0.651 mm-1, F(000)=1336, the final R=0.0783 and wR=0.2119. This title compound was investigated for the catalytic behavior towards norbornene (NB) vinyl addition polymerization. And the complex exhibited good catalytic activity to catalyze norbornene polymerization using MAO as a cocatalyst.
The title complex bis{1-[[(3-ethyl-6-methyl-2-pyridinyl)imino]methylenyl]-2-naphthalenola-to-N,O}nickel has been synthesized by the reaction of 1-[[(3-ethyl-6-methyl-2-pyridinyl) imino] methylenyl]-2-naphthalenol with Ni(CH3COO)2·4H2O, and characterized by IR spectrum and single-crystal X-ray diffraction analysis. The crystal belongs to the orthorhombic system, space group Pbca with a=11.100(2), b=15.900(3), c=18.000(4) Å, V=3176.8(11) Å3, C38H34N4NiO2, Mr=637.40, Z=4, Dc=1.333 g/cm3, μ=0.651 mm-1, F(000)=1336, the final R=0.0783 and wR=0.2119. This title compound was investigated for the catalytic behavior towards norbornene (NB) vinyl addition polymerization. And the complex exhibited good catalytic activity to catalyze norbornene polymerization using MAO as a cocatalyst.
2014, 33(2): 294-303
Abstract:
The first part of this report describes the data reduction of non-merohedrally twinned crystals measured on Bruker and Agilent area-detector diffractometers. The image frames of methyl-2-aminopyrazine-3-carboxylate were processed with APEX2 to furnish a set of overlapping diffraction indices that were used for solution and refinement. CrysAlisPRO was used for processing the frames of bis(diethyldicarbamato)nickel, which exists in monoclinic and tetragonal polymorphs, and in untwinned and twinned forms. In the second part, the crystal structure of[(3-formyl-4-hydroxyphenyl)methyl]triphenylphosphanium chloride was refined through the ‘HKLF 5’ (based on a combined set of diffraction indices) and PLATON (based on one set of diffraction indices) routes to give identical outcomes because the amount of overlap of the twin domains is small. For the third part, in a proof-of-concept investigation, the diffraction pattern of untwinned and twinned 4-{(E)-(4-aminophenyl)diazenyl]phenylamine was recorded simultaneously in one run; the three domains could be indexed and the crystal structure satisfactorily refined. The refinement was identical to those derived from independent measurements; the crystal structure features two independent centrosymmetric molecules, one of which is ordered and the other whole-molecule-disordered. This two-in-one run opens up the possibility that two or more crystals having different atomic compositions can be measured simultaneously if their reciprocal lattices do not overlap significantly.
The first part of this report describes the data reduction of non-merohedrally twinned crystals measured on Bruker and Agilent area-detector diffractometers. The image frames of methyl-2-aminopyrazine-3-carboxylate were processed with APEX2 to furnish a set of overlapping diffraction indices that were used for solution and refinement. CrysAlisPRO was used for processing the frames of bis(diethyldicarbamato)nickel, which exists in monoclinic and tetragonal polymorphs, and in untwinned and twinned forms. In the second part, the crystal structure of[(3-formyl-4-hydroxyphenyl)methyl]triphenylphosphanium chloride was refined through the ‘HKLF 5’ (based on a combined set of diffraction indices) and PLATON (based on one set of diffraction indices) routes to give identical outcomes because the amount of overlap of the twin domains is small. For the third part, in a proof-of-concept investigation, the diffraction pattern of untwinned and twinned 4-{(E)-(4-aminophenyl)diazenyl]phenylamine was recorded simultaneously in one run; the three domains could be indexed and the crystal structure satisfactorily refined. The refinement was identical to those derived from independent measurements; the crystal structure features two independent centrosymmetric molecules, one of which is ordered and the other whole-molecule-disordered. This two-in-one run opens up the possibility that two or more crystals having different atomic compositions can be measured simultaneously if their reciprocal lattices do not overlap significantly.
2014, 33(2): 304-318
Abstract:
The permeation enhancing activity of Azone for ketoprofen through excised cavia skins was investigated using Franz diffusion cell. The possible hydrogen-bonded complexes formed between ketoprofen and the model molecule of Azone as azacyclopentane-2-one were fully optimized at the B3LYP/6-311++G** level. The intermolecular hydrogen-bonding interactions were calculated using the B3LYP/6-311++G**, B3LYP/6-311++G (2df, 2p), MP2 (full)/6-311++G** and MP2 (full)/6-311++G (2df, 2p) methods, respectively. The results show that the steady-state permeation rate of ketoprofen through excised cavia skins enhances over 9 times in the solvent with 2% Azone as compared with the solvent without Azone. The stable O-H…O=C and N-H…O=C hydrogen-bonded complexes could exist between azacyclopentane and ketoprofen. The hydrogen-bonding interaction energy follows the order of (a) >(b) >(c) >(d) >(g) >(e) >(h) >(f). The formation of the complexes leads to the change of the conformation and molecular polarity of ketoprofen, and thus causes a better percutaneous permeation for the drug. The analyses of AIM (atom in molecule) and shift of electron density were used to further reveal the nature of the enhancing permeation activity of Azone for ketoprofen. The investigations of the temperature and solvent effects confirm that ketoprofen might enter into the skin by means of the Azone complex.
The permeation enhancing activity of Azone for ketoprofen through excised cavia skins was investigated using Franz diffusion cell. The possible hydrogen-bonded complexes formed between ketoprofen and the model molecule of Azone as azacyclopentane-2-one were fully optimized at the B3LYP/6-311++G** level. The intermolecular hydrogen-bonding interactions were calculated using the B3LYP/6-311++G**, B3LYP/6-311++G (2df, 2p), MP2 (full)/6-311++G** and MP2 (full)/6-311++G (2df, 2p) methods, respectively. The results show that the steady-state permeation rate of ketoprofen through excised cavia skins enhances over 9 times in the solvent with 2% Azone as compared with the solvent without Azone. The stable O-H…O=C and N-H…O=C hydrogen-bonded complexes could exist between azacyclopentane and ketoprofen. The hydrogen-bonding interaction energy follows the order of (a) >(b) >(c) >(d) >(g) >(e) >(h) >(f). The formation of the complexes leads to the change of the conformation and molecular polarity of ketoprofen, and thus causes a better percutaneous permeation for the drug. The analyses of AIM (atom in molecule) and shift of electron density were used to further reveal the nature of the enhancing permeation activity of Azone for ketoprofen. The investigations of the temperature and solvent effects confirm that ketoprofen might enter into the skin by means of the Azone complex.
