Login In
2021 Volume 40 Issue 6
2021, 40(6): 689-702
doi: 10.14102/j.cnki.0254–5861.2011–2994
Abstract:
Embryonic ectoderm development (EED) has become a novel target for cancer treatment. In this study, a series of EED inhibitors was subjected to a three-dimensional quantitative structure-activity relationship (3D-QSAR) and molecular docking. Accordingly, this is the first of such 3D-QSAR studies in a series of EED inhibitors displaying anti-cancer pharmacological profiles. The CoMFA (q2 = 0.792, r2 = 0.994, rpred2 = 0.74) and CoMSIA (q2 = 0.873, r2 = 0.994, rpred2 = 0.81) models demonstrated good robustness and predictive ability. Moreover, molecular docking suggested that cation-π, π-π stacking and hydrogen bonding interactions were the main factors affecting the activity of these inhibitors. Five new small molecules were designed based on the CoMFA and CoMSIA contour maps. These molecules were then submitted to further ADME studies, in which the ADME properties of the five designed molecules were found to be within a reasonable range. In view of the corresponding findings, this study may provide theoretical guidance for the rational design of novel EED inhibitors.
Embryonic ectoderm development (EED) has become a novel target for cancer treatment. In this study, a series of EED inhibitors was subjected to a three-dimensional quantitative structure-activity relationship (3D-QSAR) and molecular docking. Accordingly, this is the first of such 3D-QSAR studies in a series of EED inhibitors displaying anti-cancer pharmacological profiles. The CoMFA (q2 = 0.792, r2 = 0.994, rpred2 = 0.74) and CoMSIA (q2 = 0.873, r2 = 0.994, rpred2 = 0.81) models demonstrated good robustness and predictive ability. Moreover, molecular docking suggested that cation-π, π-π stacking and hydrogen bonding interactions were the main factors affecting the activity of these inhibitors. Five new small molecules were designed based on the CoMFA and CoMSIA contour maps. These molecules were then submitted to further ADME studies, in which the ADME properties of the five designed molecules were found to be within a reasonable range. In view of the corresponding findings, this study may provide theoretical guidance for the rational design of novel EED inhibitors.
2021, 40(6): 703-710
doi: 10.14102/j.cnki.0254–5861.2011–3000
Abstract:
Comparative molecular field analysis (CoMFA) techniques were used to perform three-dimensional quantitative structure-activity relationship (3D-QSAR) studies on the anti-tumor activity (pIH and pIC) of 28 fluoroquinolon-3-yl s-triazole sulfide-ketone derivatives (FQTSDs) against two cancer cell lines, including human hepatoma Hep-3B cells and human pancreatic cancer Capan-1 cells. 23 compounds were randomly selected as the training set to establish the prediction models, which were verified by the test set of 6 compounds containing template molecule. The obtained cross-validation (Rcv2) and non-cross-validation correlation coefficients (R2) of the CoMFA models were 0.477 and 0.850 for pIH, and 0.421 and 0.836 for pIC, respectively. The contributions of steric and electrostatic fields to pIH were determined to be 48.1% and 51.9%, and those to pIC were 49.4% and 50.6%, respectively. The CoMFA models were then used to predict the activities of the compounds in the training and testing sets, and the models had a strong stability and good predictability. Based on the 3D contour maps, four novel FQTSDs with a higher anti-tumor activity were designed. However, the effectiveness of these novel FQTSDs is still needed to be verified by experimental results.
Comparative molecular field analysis (CoMFA) techniques were used to perform three-dimensional quantitative structure-activity relationship (3D-QSAR) studies on the anti-tumor activity (pIH and pIC) of 28 fluoroquinolon-3-yl s-triazole sulfide-ketone derivatives (FQTSDs) against two cancer cell lines, including human hepatoma Hep-3B cells and human pancreatic cancer Capan-1 cells. 23 compounds were randomly selected as the training set to establish the prediction models, which were verified by the test set of 6 compounds containing template molecule. The obtained cross-validation (Rcv2) and non-cross-validation correlation coefficients (R2) of the CoMFA models were 0.477 and 0.850 for pIH, and 0.421 and 0.836 for pIC, respectively. The contributions of steric and electrostatic fields to pIH were determined to be 48.1% and 51.9%, and those to pIC were 49.4% and 50.6%, respectively. The CoMFA models were then used to predict the activities of the compounds in the training and testing sets, and the models had a strong stability and good predictability. Based on the 3D contour maps, four novel FQTSDs with a higher anti-tumor activity were designed. However, the effectiveness of these novel FQTSDs is still needed to be verified by experimental results.
2021, 40(6): 711-721
doi: 10.14102/j.cnki.0254–5861.2011–3032
Abstract:
Based on the three-dimensional structures of the compounds, the structures of 48 ester compounds were expressed parametrically. Through multiple linear regression and partial least-squares regression, the relationship models between ester compound structures and aquatic toxicity log(1/IGC50) were established. The correlation coefficients (R2) of the models were 0.9974 and 0.9940, and the standard deviations (SD) were 0.0469 and 0.0646, respectively. The stability of the models was evaluated by the leave-one-out internal cross-test. The correlation coefficients (RCV2) of the models of interactive tests were 0.9939 and 0.8952, and the standard deviation (SDCV) was 0.0715 and 0.0925, respectively. The external samples were used to test the predictive ability of the models, and the correlation coefficients (Rtest2) of the external predictions were 0.9955 and 0.9955, and the standard deviations (SDtest) were 0.0720 and 0.0716, respectively. The molecular structure descriptors could successfully represent the structural characteristics of the compounds, and the built models had good fitting effects, strong stability and high prediction accuracy. The present study has a good reference value for the study of the structure-toxicity relationship of toxic compounds in the environment.
Based on the three-dimensional structures of the compounds, the structures of 48 ester compounds were expressed parametrically. Through multiple linear regression and partial least-squares regression, the relationship models between ester compound structures and aquatic toxicity log(1/IGC50) were established. The correlation coefficients (R2) of the models were 0.9974 and 0.9940, and the standard deviations (SD) were 0.0469 and 0.0646, respectively. The stability of the models was evaluated by the leave-one-out internal cross-test. The correlation coefficients (RCV2) of the models of interactive tests were 0.9939 and 0.8952, and the standard deviation (SDCV) was 0.0715 and 0.0925, respectively. The external samples were used to test the predictive ability of the models, and the correlation coefficients (Rtest2) of the external predictions were 0.9955 and 0.9955, and the standard deviations (SDtest) were 0.0720 and 0.0716, respectively. The molecular structure descriptors could successfully represent the structural characteristics of the compounds, and the built models had good fitting effects, strong stability and high prediction accuracy. The present study has a good reference value for the study of the structure-toxicity relationship of toxic compounds in the environment.
2021, 40(6): 722-728
doi: 10.14102/j.cnki.0254–5861.2011–3046
Abstract:
In the present study, two new Co(Ⅲ)-based coordination polymers (CPs) with chemical formulas of {[Co3(μ3-OH)(L)(H2O)3]·2H2O}n (1) and {[Co3(μ3-OH)(L)(H2O)]·2DMF·3H2O}n (2) have been successfully prepared by the reaction of Co(NO3)2·6H2O with π-electron-rich polycarboxylate aryl ether ligand 5, 5΄-((5-carboxy-1, 3-phenylene)bis(oxy))diisophthalic acid (H5L) under different solvothermal reaction conditions. Both CPs have been studied via single-crystal X-day diffraction, powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA). The photophysical studies indicated that complex 2 with good water stability is a potential semiconductive material, which could be applied for the degradation of methylene blue (MB) under UV light irradiation and exhibit good stability and recyclability.
In the present study, two new Co(Ⅲ)-based coordination polymers (CPs) with chemical formulas of {[Co3(μ3-OH)(L)(H2O)3]·2H2O}n (1) and {[Co3(μ3-OH)(L)(H2O)]·2DMF·3H2O}n (2) have been successfully prepared by the reaction of Co(NO3)2·6H2O with π-electron-rich polycarboxylate aryl ether ligand 5, 5΄-((5-carboxy-1, 3-phenylene)bis(oxy))diisophthalic acid (H5L) under different solvothermal reaction conditions. Both CPs have been studied via single-crystal X-day diffraction, powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA). The photophysical studies indicated that complex 2 with good water stability is a potential semiconductive material, which could be applied for the degradation of methylene blue (MB) under UV light irradiation and exhibit good stability and recyclability.
2021, 40(6): 729-738
doi: 10.14102/j.cnki.0254–5861.2011–3033
Abstract:
Three azide bridged complexes, namely, [Mn2L2(N3)4(H2O)2] (1), [Co2L2(N3)4]·(H2O)3 (2) and [Ni2L2(N3)3(H2O)]N3·(H2O)4 (3) (L = 2-morpholine-4-yl-4, 6-di-pyrazol-1-yl-1, 3, 5-triazine), were synthesized by the reaction of L ligand, sodium azide with Mn(Ⅱ), Co(Ⅱ) and Ni(Ⅱ) chlorides. The copper(Ⅱ) chloride combined with thiocyanate and L ligand to form a mononuclear complex [CuL(CH3OH)(SCN)(NCS)] (4). Complexes 1~4 were characterized by IR, elemental analysis and X-ray crystallographic analysis. It was worth noting that two Mn(Ⅱ) atoms were connected by the end-to-end mode in 1, while Co(Ⅱ) and Ni(Ⅱ) atoms were connected by the end-on mode in 2 and 3. In complex 4, the central copper atom was coordinated with a sulfur atom and a nitrogen atom of the two thiocyanate ligands, respectively. Hydrogen bonds, π-π stacking interactions, thermogravimetric analysis and fluorescence properties of 1~4 were studied.
Three azide bridged complexes, namely, [Mn2L2(N3)4(H2O)2] (1), [Co2L2(N3)4]·(H2O)3 (2) and [Ni2L2(N3)3(H2O)]N3·(H2O)4 (3) (L = 2-morpholine-4-yl-4, 6-di-pyrazol-1-yl-1, 3, 5-triazine), were synthesized by the reaction of L ligand, sodium azide with Mn(Ⅱ), Co(Ⅱ) and Ni(Ⅱ) chlorides. The copper(Ⅱ) chloride combined with thiocyanate and L ligand to form a mononuclear complex [CuL(CH3OH)(SCN)(NCS)] (4). Complexes 1~4 were characterized by IR, elemental analysis and X-ray crystallographic analysis. It was worth noting that two Mn(Ⅱ) atoms were connected by the end-to-end mode in 1, while Co(Ⅱ) and Ni(Ⅱ) atoms were connected by the end-on mode in 2 and 3. In complex 4, the central copper atom was coordinated with a sulfur atom and a nitrogen atom of the two thiocyanate ligands, respectively. Hydrogen bonds, π-π stacking interactions, thermogravimetric analysis and fluorescence properties of 1~4 were studied.
2021, 40(6): 739-745
doi: 10.14102/j.cnki.0254–5861.2011–3012
Abstract:
Researches on multifunctional molecular materials with both nonlinear optical activity and fluorescence properties have received much interest in molecular chemistry since they have wide application prospects. Here a novel ionic compound 2(BPP)+·[Mn(NCS)4]2- (1) was synthesized via the assembly of benzyltriphenylphosphorus chloride, isothiocyanate and manganese chloride, which displays both strong SHG response and purple luminescence. Compound 1 belongs to monoclinic system and crystallizes in Cc space group. X-ray single-crystal diffraction analysis shows that Mn2+ ions are tetra-coordinated with N atoms of four NCS- ions through forming a distorted tetrahedral configuration. The anion Mn(NCS)42- forms a 1D chain structure through strong S···S interaction. At the same time, there are abundant C–H···S and π···π interactions, which further accumulate into a three-dimensional supramolecular structure. Solid-state fluorescence studies show that the complex 1 has strong purple fluorescence with emission wavelength of 396 nm under excitation wavelength 248 nm. In particular, the second harmonic generation (SHG) measurements show that compound 1 has nonlinear optical activity and its SHG response is 2.25 times that of standard potassium dihydrogen phosphate (KDP). This multifunctional molecular material with SHG response and purple fluorescence is of great significance for the development of new metal organic complexes with potential application prospects.
Researches on multifunctional molecular materials with both nonlinear optical activity and fluorescence properties have received much interest in molecular chemistry since they have wide application prospects. Here a novel ionic compound 2(BPP)+·[Mn(NCS)4]2- (1) was synthesized via the assembly of benzyltriphenylphosphorus chloride, isothiocyanate and manganese chloride, which displays both strong SHG response and purple luminescence. Compound 1 belongs to monoclinic system and crystallizes in Cc space group. X-ray single-crystal diffraction analysis shows that Mn2+ ions are tetra-coordinated with N atoms of four NCS- ions through forming a distorted tetrahedral configuration. The anion Mn(NCS)42- forms a 1D chain structure through strong S···S interaction. At the same time, there are abundant C–H···S and π···π interactions, which further accumulate into a three-dimensional supramolecular structure. Solid-state fluorescence studies show that the complex 1 has strong purple fluorescence with emission wavelength of 396 nm under excitation wavelength 248 nm. In particular, the second harmonic generation (SHG) measurements show that compound 1 has nonlinear optical activity and its SHG response is 2.25 times that of standard potassium dihydrogen phosphate (KDP). This multifunctional molecular material with SHG response and purple fluorescence is of great significance for the development of new metal organic complexes with potential application prospects.
2021, 40(6): 746-752
doi: 10.14102/j.cnki.0254–5861.2011–3002
Abstract:
In this work, it is found that 1, 8-dihydroxyimino-1, 2, 7, 8-tetraphenyl-3, 6-diazocta-2, 6-diene (PhdoenH2) could react with nickel(Ⅱ) salt to yield a mononickel complex Ni(Phdoen) (1) with unusual [2N2O]-coordinated mode, while the analogous diimine-dioxime ligands usually form the [4N]-coordinated mode. The novel complex 1 has been carefully characterized by 1H NMR, elemental analysis, and X-ray diffraction structure analysis. The influences of the coordination modes on the structures and redox properties have been further investigated. Theoretical investigations revealed that the different coordination modes were ascribed to the thermodynamic properties of ligands.
In this work, it is found that 1, 8-dihydroxyimino-1, 2, 7, 8-tetraphenyl-3, 6-diazocta-2, 6-diene (PhdoenH2) could react with nickel(Ⅱ) salt to yield a mononickel complex Ni(Phdoen) (1) with unusual [2N2O]-coordinated mode, while the analogous diimine-dioxime ligands usually form the [4N]-coordinated mode. The novel complex 1 has been carefully characterized by 1H NMR, elemental analysis, and X-ray diffraction structure analysis. The influences of the coordination modes on the structures and redox properties have been further investigated. Theoretical investigations revealed that the different coordination modes were ascribed to the thermodynamic properties of ligands.
2021, 40(6): 753-758
doi: 10.14102/j.cnki.0254–5861.2011–3013
Abstract:
A new 2D metal coordination polymer (MCP), [Mn(pzdc)0.5(L)]n (1, pzdc = pyrazine-2, 3-dicarboxylic acid, HL = 3-(2-pyridyl)pyrazole), was synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, powder XRD, FT-IR, TG, fluorescence and elemental analysis techniques. Pale yellow crystals crystallize in orthorhombic system, space group Fdd2 with a = 11.2368(6), b = 38.280(2), c = 10.5682(6) Å, V = 4545.9(4) Å3, C11H7MnN4O2, Mr = 282.15, Dc = 1.649 g/cm3, μ(MoKα) = 1.159 mm-1, F(000) = 2272, Z = 16, the final R = 0.0613 and wR = 0.1773 for 2856 observed reflections (I > 2σ(I)). It shows a two-dimensional network structure and is further assembled into a three-dimensional supramolecular framework via hydrogen bonds and abundant π-π interactions. In addition, we analyzed natural bond orbital (NBO) of 1 in using the PBE0/LANL2DZ method established in Gaussian 03 Program. There is obvious covalent interaction between the coordinated atoms and Mn(Ⅱ) ions.
A new 2D metal coordination polymer (MCP), [Mn(pzdc)0.5(L)]n (1, pzdc = pyrazine-2, 3-dicarboxylic acid, HL = 3-(2-pyridyl)pyrazole), was synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, powder XRD, FT-IR, TG, fluorescence and elemental analysis techniques. Pale yellow crystals crystallize in orthorhombic system, space group Fdd2 with a = 11.2368(6), b = 38.280(2), c = 10.5682(6) Å, V = 4545.9(4) Å3, C11H7MnN4O2, Mr = 282.15, Dc = 1.649 g/cm3, μ(MoKα) = 1.159 mm-1, F(000) = 2272, Z = 16, the final R = 0.0613 and wR = 0.1773 for 2856 observed reflections (I > 2σ(I)). It shows a two-dimensional network structure and is further assembled into a three-dimensional supramolecular framework via hydrogen bonds and abundant π-π interactions. In addition, we analyzed natural bond orbital (NBO) of 1 in using the PBE0/LANL2DZ method established in Gaussian 03 Program. There is obvious covalent interaction between the coordinated atoms and Mn(Ⅱ) ions.
2021, 40(6): 759-766
doi: 10.14102/j.cnki.0254–5861.2011–3011
Abstract:
In this paper, two compounds [Zn22+(2, 6-bis(4΄-pyridyl)-TTF)(TPA)22-] (1) and [Cd2+(2, 6(7)-bis(4΄-pyridyl)-TTF)(TPA)2-(H2O)2] (TTF = tetrathiafulvalene, TPA = terephthalic acid) (2) were synthesized by using solvothermal method and characterized by single-crystal X-ray. The purity of the two compounds was confirmed by their PXRD data. We also tested the photocurrent responses of these two compounds, and found they could generate photocurrent signal when exposed to light, but the photocurrent intensity of compound 2 is significantly greater than that of 1. From the crystal structure analysis, the possible reason for this phenomenon is that 2 has a more compact ligand arrangement than 1, leading to a higher carrier density and easier excitation.
In this paper, two compounds [Zn22+(2, 6-bis(4΄-pyridyl)-TTF)(TPA)22-] (1) and [Cd2+(2, 6(7)-bis(4΄-pyridyl)-TTF)(TPA)2-(H2O)2] (TTF = tetrathiafulvalene, TPA = terephthalic acid) (2) were synthesized by using solvothermal method and characterized by single-crystal X-ray. The purity of the two compounds was confirmed by their PXRD data. We also tested the photocurrent responses of these two compounds, and found they could generate photocurrent signal when exposed to light, but the photocurrent intensity of compound 2 is significantly greater than that of 1. From the crystal structure analysis, the possible reason for this phenomenon is that 2 has a more compact ligand arrangement than 1, leading to a higher carrier density and easier excitation.
2021, 40(6): 767-774
doi: 10.14102/j.cnki.0254–5861.2011–3008
Abstract:
One-dimensional (1D) chiral chain complexes [CuLSCu(Pydc)] (2S) and [CuLRCu(Pydc)] (2R) (LS = (E)-3-(((1S, 2S)-2-(((E)-3-oxo-3-(4-pyridin-4-yl)phenyl)propylidene)amono)-1, 2-diphenyl)imino)-1-(4-(pyridi-4-yl)phenyl)butan-1-one) and LR = (E)-3-(((1R, 2R)-2-(((E)-3-oxo-3-(4-pyridin-4-yl)phenyl)propylidene)amono)-1, 2-diphenyl)imino)-1-(4-(pyridi-4-yl)phenyl)butan-1-one and Pydc = 2, 6-pyridinedicarboxylic acid) have been synthesized vis mononuclear chiral enantiomer precursors CuLS (1S) and CuLR (1R). Their different chiral configurations of 1S, 1R, 2S and 2R were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, infrared spectra (IR), powder X-ray diffraction (PXRD), thermal gravimetric analyses (TGA) and circular dichroism spectra (CD).
One-dimensional (1D) chiral chain complexes [CuLSCu(Pydc)] (2S) and [CuLRCu(Pydc)] (2R) (LS = (E)-3-(((1S, 2S)-2-(((E)-3-oxo-3-(4-pyridin-4-yl)phenyl)propylidene)amono)-1, 2-diphenyl)imino)-1-(4-(pyridi-4-yl)phenyl)butan-1-one) and LR = (E)-3-(((1R, 2R)-2-(((E)-3-oxo-3-(4-pyridin-4-yl)phenyl)propylidene)amono)-1, 2-diphenyl)imino)-1-(4-(pyridi-4-yl)phenyl)butan-1-one and Pydc = 2, 6-pyridinedicarboxylic acid) have been synthesized vis mononuclear chiral enantiomer precursors CuLS (1S) and CuLR (1R). Their different chiral configurations of 1S, 1R, 2S and 2R were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, infrared spectra (IR), powder X-ray diffraction (PXRD), thermal gravimetric analyses (TGA) and circular dichroism spectra (CD).
2021, 40(6): 775-784
doi: 10.14102/j.cnki.0254–5861.2011–3009
Abstract:
Two triphenylmethylphosphonium/haloplumbate hybrids, i.e., [(PPh3Me)2(Pb2I6)∙CH3CN]n (1) and [(PPh3Me)(PbBr3)]n (2), have been prepared, in which the (PbX3)nn- nanochains built from face-sharing PbX6 octahedra are surrounded by organic templates to assemble the core-shell quantum well. Besides, C−H…π interactions among Ph3PMe+ cations can also be detected, which give rise to the 2-D organic layer of 1 and 1-D chain for 2. The good water stabilities could be induced by the strong C−H…π interactions, which can deter the hydrolysis reaction. The energy band gaps of this work mainly derive from the charge transfer of organic components, but their luminescence stems from the inorganic (PbX3)nn- nanochains with co-existence of free excitons and self-trapped excitons. At temperature lower than 117 K, strong quantum confinement will rule out the free excitons, and self-trapped excitons will dominate, resulting in red-shift luminescence. Moreover, effective and repeatable photocurrent responses can be found in these hybrids.
Two triphenylmethylphosphonium/haloplumbate hybrids, i.e., [(PPh3Me)2(Pb2I6)∙CH3CN]n (1) and [(PPh3Me)(PbBr3)]n (2), have been prepared, in which the (PbX3)nn- nanochains built from face-sharing PbX6 octahedra are surrounded by organic templates to assemble the core-shell quantum well. Besides, C−H…π interactions among Ph3PMe+ cations can also be detected, which give rise to the 2-D organic layer of 1 and 1-D chain for 2. The good water stabilities could be induced by the strong C−H…π interactions, which can deter the hydrolysis reaction. The energy band gaps of this work mainly derive from the charge transfer of organic components, but their luminescence stems from the inorganic (PbX3)nn- nanochains with co-existence of free excitons and self-trapped excitons. At temperature lower than 117 K, strong quantum confinement will rule out the free excitons, and self-trapped excitons will dominate, resulting in red-shift luminescence. Moreover, effective and repeatable photocurrent responses can be found in these hybrids.
2021, 40(6): 785-796
doi: 10.14102/j.cnki.0254–5861.2011–3052
Abstract:
Two coordination polymers, namely [Mn(μ-Hcpia)(bipy)(H2O)2]n (1) and [Cd3(μ3-Hcpia)2(μ-Hbiim)2(μ-H2biim)(H2O)2]n (2), have been constructed hydrothermally using H2cbia (H2cbia = 5-(4΄-cyanobenzoxy)isophthalic acid), bipy (bipy = 4, 4΄-bipyridine), H2biim (H2biim = 2, 2΄-biimidazole), and manganese or cadmium chlorides at 160 ℃. Interestingly, the H3cpia (H3cpia = 5-(4΄-carboxylphenoxy)isophthalic acid) ligand was generated by in situ hydrolysis of cyano group in H2cbia. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses (TGA), and single-crystal X-ray diffraction analyses. Both compounds crystallize in the triclinic system, space group P\begin{document}$ \overline 1 $\end{document}
Two coordination polymers, namely [Mn(μ-Hcpia)(bipy)(H2O)2]n (1) and [Cd3(μ3-Hcpia)2(μ-Hbiim)2(μ-H2biim)(H2O)2]n (2), have been constructed hydrothermally using H2cbia (H2cbia = 5-(4΄-cyanobenzoxy)isophthalic acid), bipy (bipy = 4, 4΄-bipyridine), H2biim (H2biim = 2, 2΄-biimidazole), and manganese or cadmium chlorides at 160 ℃. Interestingly, the H3cpia (H3cpia = 5-(4΄-carboxylphenoxy)isophthalic acid) ligand was generated by in situ hydrolysis of cyano group in H2cbia. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses (TGA), and single-crystal X-ray diffraction analyses. Both compounds crystallize in the triclinic system, space group P
2021, 40(6): 797-805
doi: 10.14102/j.cnki.0254–5861.2011–3054
Abstract:
Volume change during the insertion/extraction of Li+ in electrode materials is an important issue to affect the safety and stability of Li-ion batteries. Here, we prepare a near-zero volume change material of COF derived mesh-liked carbon/TiO2 (MC/TiO2) composite by using a layered TiO2 as a template, and a two-dimensional COF material is inserted into the interlayers by the Schiff base polymerization between melamine and terephthalaldehyde, followed by carbonization at 500 ℃ to convert COF to mesh-liked carbon nanosheets. Due to the introduction of mesh-liked carbon nanosheets, the interlayer conductivity of TiO2 is improved, and the nanocavities in mesh-liked carbon nanosheets provide additional chambers for the insertion/extraction of Li-ions without any change of the interlayer distance. The MC/TiO2 shows a specific capacity of 472.7 mAh/g at a current density of 0.1 A/g, and good specific capacity retention of 65% remains after 1000 cycles at a current of 1 A/g.
Volume change during the insertion/extraction of Li+ in electrode materials is an important issue to affect the safety and stability of Li-ion batteries. Here, we prepare a near-zero volume change material of COF derived mesh-liked carbon/TiO2 (MC/TiO2) composite by using a layered TiO2 as a template, and a two-dimensional COF material is inserted into the interlayers by the Schiff base polymerization between melamine and terephthalaldehyde, followed by carbonization at 500 ℃ to convert COF to mesh-liked carbon nanosheets. Due to the introduction of mesh-liked carbon nanosheets, the interlayer conductivity of TiO2 is improved, and the nanocavities in mesh-liked carbon nanosheets provide additional chambers for the insertion/extraction of Li-ions without any change of the interlayer distance. The MC/TiO2 shows a specific capacity of 472.7 mAh/g at a current density of 0.1 A/g, and good specific capacity retention of 65% remains after 1000 cycles at a current of 1 A/g.
2021, 40(6): 806-810
doi: 10.14102/j.cnki.0254–5861.2011–3016
Abstract:
In this study, S-doped g-C3N4 nanoparticles were successfully prepared by one-step solid-state microwave synthesis. The detailed characterizations through XRD, FT-IR, SEM and XPS were studied. In addition, the electrochemical properties as supercapacitor of the sample were tested by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS) techniques. The results showed a high specific capacitance of 691 F/g at current density of 4 A/g in 2 M KOH + 0.15 M K3[Fe(CN)6] electrolyte. This study shows that the microwave synthesis is a promising way to design carbon-based electrodes for supercapacitor.
In this study, S-doped g-C3N4 nanoparticles were successfully prepared by one-step solid-state microwave synthesis. The detailed characterizations through XRD, FT-IR, SEM and XPS were studied. In addition, the electrochemical properties as supercapacitor of the sample were tested by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS) techniques. The results showed a high specific capacitance of 691 F/g at current density of 4 A/g in 2 M KOH + 0.15 M K3[Fe(CN)6] electrolyte. This study shows that the microwave synthesis is a promising way to design carbon-based electrodes for supercapacitor.
2021, 40(6): 811-820
doi: 10.14102/j.cnki.0254–5861.2011–3042
Abstract:
Organoboryl germanium(Ⅱ) oxides were synthesized from the 1, 4-addition reaction of L′Ge (L′ = HC[C(CH2)N(Ar)]C(Me)N(Ar), Ar = 2, 6-iPr2C6H3) with selected monosubstituted arylboronic acids RB(OH)2 (R = 2, 6-Me2C6H3, 2, 4, 6-Me3C6H2, 1-Naph) at the molar ratios of 1:1 and 2:1. The mononuclear products RB(OH)OGeL (L = CH[C(Me)N(Ar)]2, Ar = 2, 6-iPr2C6H3; R = 2, 6-Me2C6H3 (1), 2, 4, 6-Me3C6H2 (2), 1-Naph (3)) containing the Ge–O–B core were obtained smoothly through the 1:1 reaction. However, the reaction of L′Ge with 2, 6-Me2C6H3B(OH)2 in a 2:1 ratio gave only the mononuclear product (1) instead of the expected binuclear one. What's more, a new borate compound [(2, 6-Me2C6H3)4B5O6]-[H: C]+ (4) (: C = C[N(iPr)C(Me)]2) was concomitantly formed when the in situ prepared L′Ge was used as the precursor. In contrast, the use of 2, 4, 6-Me3C6H2B(OH)2 or 1-NaphB(OH)2 as the organoboryl source in the similar reaction led to the formation and isolation of the binuclear products RB(OGeL)2 (R = 2, 4, 6-Me3C6H2 (5), 1-Naph (6)) containing the Ge–O–B–O–Ge core in a straight way. Compounds 1~6 were determined by single-crystal X-ray diffraction analysis.
Organoboryl germanium(Ⅱ) oxides were synthesized from the 1, 4-addition reaction of L′Ge (L′ = HC[C(CH2)N(Ar)]C(Me)N(Ar), Ar = 2, 6-iPr2C6H3) with selected monosubstituted arylboronic acids RB(OH)2 (R = 2, 6-Me2C6H3, 2, 4, 6-Me3C6H2, 1-Naph) at the molar ratios of 1:1 and 2:1. The mononuclear products RB(OH)OGeL (L = CH[C(Me)N(Ar)]2, Ar = 2, 6-iPr2C6H3; R = 2, 6-Me2C6H3 (1), 2, 4, 6-Me3C6H2 (2), 1-Naph (3)) containing the Ge–O–B core were obtained smoothly through the 1:1 reaction. However, the reaction of L′Ge with 2, 6-Me2C6H3B(OH)2 in a 2:1 ratio gave only the mononuclear product (1) instead of the expected binuclear one. What's more, a new borate compound [(2, 6-Me2C6H3)4B5O6]-[H: C]+ (4) (: C = C[N(iPr)C(Me)]2) was concomitantly formed when the in situ prepared L′Ge was used as the precursor. In contrast, the use of 2, 4, 6-Me3C6H2B(OH)2 or 1-NaphB(OH)2 as the organoboryl source in the similar reaction led to the formation and isolation of the binuclear products RB(OGeL)2 (R = 2, 4, 6-Me3C6H2 (5), 1-Naph (6)) containing the Ge–O–B–O–Ge core in a straight way. Compounds 1~6 were determined by single-crystal X-ray diffraction analysis.
2021, 40(6): 821-826
doi: 10.14102/j.cnki.0254–5861.2011–3001
Abstract:
A pair of Z-E enaminonitrile isomerisms 2-(3, 4-dimethoxyphenyl)-3-((3-methoxyphenyl)amino)acrylonitrile (C18H18N2O3, Mr = 310.34) were synthesized and separated by flash column chromatography, and their structures were determined by IR, 1H NMR, 13C NMR, MS and single-crystal X-ray diffraction. The crystal of compound 2a belongs to the monoclinic system, space group C2/c with a = 33.805(7), b = 5.4496(12), c = 18.401(4) Å, β = 112.45(2)º, V = 3133.1(12) Å3, Z = 8, μ = 0.091 mm-1, Dc = 1.143 g⋅cm-3, the final R = 0.0491 and wR = 0.1439 for 2764 observed reflections (I > 2σ(I)). The crystal of compound 2b belongs to the triclinic system, space group P1, with a = 8.8403(7), b = 9.0390(6), c = 12.0044(74) Å, α = 72.075(5), β = 86.291(5), γ = 81.216(5)º, V = 901.82(10) Å3, Z = 2, T = 293(2) K, μ = 0.079 mm-1, Dc = 1.143 g⋅cm-3, the final R = 0.0474 and wR = 0.1377 for 3176 observed reflections (I > 2σ(I)). The crystal packing of 2a and 2b is governed by intermolecular N(2)–H(2)…N(1) and N(2)–H(2)…O(2) interactions respectively to stabilize the structure.
A pair of Z-E enaminonitrile isomerisms 2-(3, 4-dimethoxyphenyl)-3-((3-methoxyphenyl)amino)acrylonitrile (C18H18N2O3, Mr = 310.34) were synthesized and separated by flash column chromatography, and their structures were determined by IR, 1H NMR, 13C NMR, MS and single-crystal X-ray diffraction. The crystal of compound 2a belongs to the monoclinic system, space group C2/c with a = 33.805(7), b = 5.4496(12), c = 18.401(4) Å, β = 112.45(2)º, V = 3133.1(12) Å3, Z = 8, μ = 0.091 mm-1, Dc = 1.143 g⋅cm-3, the final R = 0.0491 and wR = 0.1439 for 2764 observed reflections (I > 2σ(I)). The crystal of compound 2b belongs to the triclinic system, space group P1, with a = 8.8403(7), b = 9.0390(6), c = 12.0044(74) Å, α = 72.075(5), β = 86.291(5), γ = 81.216(5)º, V = 901.82(10) Å3, Z = 2, T = 293(2) K, μ = 0.079 mm-1, Dc = 1.143 g⋅cm-3, the final R = 0.0474 and wR = 0.1377 for 3176 observed reflections (I > 2σ(I)). The crystal packing of 2a and 2b is governed by intermolecular N(2)–H(2)…N(1) and N(2)–H(2)…O(2) interactions respectively to stabilize the structure.
2021, 40(6): 827-835
doi: 10.14102/j.cnki.0254–5861.2011–3007
Abstract:
Di-2, 4-dichlorobenzyltin-2-(2-(thiophen-2-formyl)hydrazono)-propanoic carboxylate complex Ⅰ {[C4H3S(O)C=N-N=C(CH3)COO]2[(2, 4-Cl2-C6H3CH2)2Sn]2(CH3OH)2} and di-2, 4-dichlorobenzyltin-2-(2-(thiophen-2-formyl)hydrazono)-3-phenylpropanoic carboxylate complex Ⅱ {[C4H3S(O)C=N-N=C(PhCH2)COO](2, 4-Cl2-C6H3CH2)2Sn}n were synthesized and characterized by IR, 1H, 13C and 119Sn NMR spectra, HRMS, elemental analysis and thermal stability analysis, and the crystal structures were determined by X-ray diffraction. The crystal of complex Ⅰ belongs to monoclinic system, space group P21/n with a = 11.987(3), b = 35.359(9), c = 12.982(3) Å, β = 103.028(5)°, Z = 4, V = 5361(2) Å3, Dc = 1. 688 Mg·m–3, μ(MoKα) = 1.463 mm–1, F(000) = 2704, R = 0.0572 and wR = 0.1423. The crystal of complex Ⅱ is of monoclinic system, space group P21/n with a = 15.5758(17), b = 9.6020(10), c = 19.599(2) Å, β = 98.886(2)°, Z = 4, V = 2896.0(5) Å3, Dc = 1.663 Mg·m–3, μ(MoKα) = 1.357 mm–1, F(000) = 1440, R = 0.0341 and wR = 0.0936. In vitro antitumor activities of both complexes were evaluated by MTT against three human cancer cell lines (MCF7, NCI-H460 and HepG2), and they all exhibited good antitumor activity. The interaction between complexes and calf thymus DNA was studied by UV-vis and fluorescence spectroscopy, it indicated intercalation as probable mode of interaction.
Di-2, 4-dichlorobenzyltin-2-(2-(thiophen-2-formyl)hydrazono)-propanoic carboxylate complex Ⅰ {[C4H3S(O)C=N-N=C(CH3)COO]2[(2, 4-Cl2-C6H3CH2)2Sn]2(CH3OH)2} and di-2, 4-dichlorobenzyltin-2-(2-(thiophen-2-formyl)hydrazono)-3-phenylpropanoic carboxylate complex Ⅱ {[C4H3S(O)C=N-N=C(PhCH2)COO](2, 4-Cl2-C6H3CH2)2Sn}n were synthesized and characterized by IR, 1H, 13C and 119Sn NMR spectra, HRMS, elemental analysis and thermal stability analysis, and the crystal structures were determined by X-ray diffraction. The crystal of complex Ⅰ belongs to monoclinic system, space group P21/n with a = 11.987(3), b = 35.359(9), c = 12.982(3) Å, β = 103.028(5)°, Z = 4, V = 5361(2) Å3, Dc = 1. 688 Mg·m–3, μ(MoKα) = 1.463 mm–1, F(000) = 2704, R = 0.0572 and wR = 0.1423. The crystal of complex Ⅱ is of monoclinic system, space group P21/n with a = 15.5758(17), b = 9.6020(10), c = 19.599(2) Å, β = 98.886(2)°, Z = 4, V = 2896.0(5) Å3, Dc = 1.663 Mg·m–3, μ(MoKα) = 1.357 mm–1, F(000) = 1440, R = 0.0341 and wR = 0.0936. In vitro antitumor activities of both complexes were evaluated by MTT against three human cancer cell lines (MCF7, NCI-H460 and HepG2), and they all exhibited good antitumor activity. The interaction between complexes and calf thymus DNA was studied by UV-vis and fluorescence spectroscopy, it indicated intercalation as probable mode of interaction.
