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2020 Volume 39 Issue 10
2020, 39(10): 1747-1752
doi: 10.14102/j.cnki.0254–5861.2011–2669
Abstract:
Binding energies and geometrical and electronic structures for adsorptions of CO and NO on metal M (Pd or Pt) loaded or M and di-vacancy co-decorated (5, 5) single-walled carbon nanotubes (M-CNTs or M-V2-CNTs) are studied using a GGA-PBE method in the work. The calculated results show that the di-vacancy defect in a perfect (5, 5) tube opens the band gap, makes the (5, 5) tube transform from a conductor into a semiconductor, and strengthens the adsorption of metal M on the (5, 5) tube. For the adsorptions of CO and NO on M-CNT and M-V2-CNT, the CO and NO molecules can be both chemically adsorbed on loaded Pd or Pt atoms due to their active adsorption sites. NO is easily adsorbed on M-V2-CNT because of its electron configuration with a high 2π energy level and its adsorption significantly changes the band gap of M-V2-CNT and makes M-V2-CNT transform from a semiconductor to a conductor. However, the adsorption of CO can not cause the conductivity of M-V2-CNT change. M-V2-CNT has a good sensitivity to the NO gas, suitable as a sensor for detecting the NO gas molecule. In addition, the existence of di-vacancy defect decreases the interaction between CO or NO and Pt-CNT, which will contribute to the desorption of CO and NO gases. The work is expected to provide a theoretical basis for designing NO sensing devices.
Binding energies and geometrical and electronic structures for adsorptions of CO and NO on metal M (Pd or Pt) loaded or M and di-vacancy co-decorated (5, 5) single-walled carbon nanotubes (M-CNTs or M-V2-CNTs) are studied using a GGA-PBE method in the work. The calculated results show that the di-vacancy defect in a perfect (5, 5) tube opens the band gap, makes the (5, 5) tube transform from a conductor into a semiconductor, and strengthens the adsorption of metal M on the (5, 5) tube. For the adsorptions of CO and NO on M-CNT and M-V2-CNT, the CO and NO molecules can be both chemically adsorbed on loaded Pd or Pt atoms due to their active adsorption sites. NO is easily adsorbed on M-V2-CNT because of its electron configuration with a high 2π energy level and its adsorption significantly changes the band gap of M-V2-CNT and makes M-V2-CNT transform from a semiconductor to a conductor. However, the adsorption of CO can not cause the conductivity of M-V2-CNT change. M-V2-CNT has a good sensitivity to the NO gas, suitable as a sensor for detecting the NO gas molecule. In addition, the existence of di-vacancy defect decreases the interaction between CO or NO and Pt-CNT, which will contribute to the desorption of CO and NO gases. The work is expected to provide a theoretical basis for designing NO sensing devices.
2020, 39(10): 1753-1762
doi: 10.14102/j.cnki.0254–5861.2011–2727
Abstract:
By classifying non-hydrogen atoms of organic compounds, parametric dyeing, and establishing the relationship between non-hydrogen atoms, new structure descriptors were obtained. The structures of 48 common allergenic fragrance organic compounds were parametrically characterized. The multiple linear regression (MLR) and partial least-squares regression (PLS) methods were used to build two models of relationship between the compound structure and chromatographic retention time. The stability of the models was evaluated by the "leave-one-out" cross test, and the predictive ability of the models was tested using an external sample set. The correlation coefficients (R2) of the two models are 0.9791 and 0.9744, those (RCV2) of the cross test are 0.8542 and 0.7464, and those (Rtest2) of the external prediction are 0.9802 and 0.9367, indicating that the models built have good fitting ability, stability and external forecasting capabilities. The structural factors affecting the chromatographic retention time of the compounds were analyzed. The results show that the compound with more secondary carbon atoms may have larger chromatographic retention time (tR) value. This paper has certain reference value for the study on the relationship between the structures and properties of allergenic fragrance organic compounds.
By classifying non-hydrogen atoms of organic compounds, parametric dyeing, and establishing the relationship between non-hydrogen atoms, new structure descriptors were obtained. The structures of 48 common allergenic fragrance organic compounds were parametrically characterized. The multiple linear regression (MLR) and partial least-squares regression (PLS) methods were used to build two models of relationship between the compound structure and chromatographic retention time. The stability of the models was evaluated by the "leave-one-out" cross test, and the predictive ability of the models was tested using an external sample set. The correlation coefficients (R2) of the two models are 0.9791 and 0.9744, those (RCV2) of the cross test are 0.8542 and 0.7464, and those (Rtest2) of the external prediction are 0.9802 and 0.9367, indicating that the models built have good fitting ability, stability and external forecasting capabilities. The structural factors affecting the chromatographic retention time of the compounds were analyzed. The results show that the compound with more secondary carbon atoms may have larger chromatographic retention time (tR) value. This paper has certain reference value for the study on the relationship between the structures and properties of allergenic fragrance organic compounds.
2020, 39(10): 1763-1769
doi: 10.14102/j.cnki.0254–5861.2011–2690
Abstract:
Using density functional theory (DFT) combined with nonequilibrium Green΄s function investigates the electron-transport properties of several molecular junctions based on the [2, 5΄]bipyrimidinyl(biphenyl isocyanide)gold(I) molecule (BPM-Au(I)CN-BP), which is modified by one to three alkyl groups forming BPM-Au(I)CN-BP(CH2)n. The asymmetric current-voltage characteristics have been obtained for the molecular junctions. Rectifying performance of Au/S-BPM-Au(I)CN-BP-S/Au molecular junction can be regulated by introducing alkyl chain. The M1 molecular junction exhibits the best rectifying effect. Its maximum rectifying ratio is 2109, which is about 150 times more than that of the molecular junction based on the original M. Moreover, all the systems modified by alkyl group have obvious negative differential resistance behavior (NDR). The current-voltage (I-V) curves of all the systems in this work are illustrated by transmission spectra.
Using density functional theory (DFT) combined with nonequilibrium Green΄s function investigates the electron-transport properties of several molecular junctions based on the [2, 5΄]bipyrimidinyl(biphenyl isocyanide)gold(I) molecule (BPM-Au(I)CN-BP), which is modified by one to three alkyl groups forming BPM-Au(I)CN-BP(CH2)n. The asymmetric current-voltage characteristics have been obtained for the molecular junctions. Rectifying performance of Au/S-BPM-Au(I)CN-BP-S/Au molecular junction can be regulated by introducing alkyl chain. The M1 molecular junction exhibits the best rectifying effect. Its maximum rectifying ratio is 2109, which is about 150 times more than that of the molecular junction based on the original M. Moreover, all the systems modified by alkyl group have obvious negative differential resistance behavior (NDR). The current-voltage (I-V) curves of all the systems in this work are illustrated by transmission spectra.
2020, 39(10): 1770-1780
doi: 10.14102/j.cnki.0254–5861.2011–2724
Abstract:
Two new rare-earth metal chalcogenides, namely RbLu5Te8 and CsMnGdTe3, have been successfully synthesized under high-temperature solid-state reaction conditions and structurally characterized by single-crystal X-ray diffraction analysis. RbLu5Te8 belongs to the monoclinic space group C2/m (no. 12) with two formula units in a unit cell: a = 22.075(5), b = 4.2987(8), c = 10.588(2) Å, β = 103.89(2)°, V = 975.4(4) Å3, whereas CsMnGdTe3 crystallizes in the orthorhombic space group Cmcm (no. 63) with four formula units in a unit cell: a = 4.4872(8), b = 16.769(3), c = 11.807(2) Å and V = 888.4(3) Å3. In the structure of RbLu5Te8, face-, edge- and vertex-sharing [LuTe6] octahedra are interconnected to produce a three-dimensional (3D) framework with Rb+ lying in the tunnels. The crystal structure of CsMnGdTe3 consists of two-dimensional (2D) [MnGdTe3]– layers of edge- and vertex-sharing [GdTe6] octahedra with Mn atoms filling the tetrahedral interstices, which stack along the b-axis. The Cs atoms are located between the [MnGdTe3]– layers and surrounded by eight Te atoms to form a [CsTe8] bicapped trigonal prism. Moreover, theoretical studies have aided the understanding of their electronic structures.
Two new rare-earth metal chalcogenides, namely RbLu5Te8 and CsMnGdTe3, have been successfully synthesized under high-temperature solid-state reaction conditions and structurally characterized by single-crystal X-ray diffraction analysis. RbLu5Te8 belongs to the monoclinic space group C2/m (no. 12) with two formula units in a unit cell: a = 22.075(5), b = 4.2987(8), c = 10.588(2) Å, β = 103.89(2)°, V = 975.4(4) Å3, whereas CsMnGdTe3 crystallizes in the orthorhombic space group Cmcm (no. 63) with four formula units in a unit cell: a = 4.4872(8), b = 16.769(3), c = 11.807(2) Å and V = 888.4(3) Å3. In the structure of RbLu5Te8, face-, edge- and vertex-sharing [LuTe6] octahedra are interconnected to produce a three-dimensional (3D) framework with Rb+ lying in the tunnels. The crystal structure of CsMnGdTe3 consists of two-dimensional (2D) [MnGdTe3]– layers of edge- and vertex-sharing [GdTe6] octahedra with Mn atoms filling the tetrahedral interstices, which stack along the b-axis. The Cs atoms are located between the [MnGdTe3]– layers and surrounded by eight Te atoms to form a [CsTe8] bicapped trigonal prism. Moreover, theoretical studies have aided the understanding of their electronic structures.
2020, 39(10): 1781-1787
doi: 10.14102/j.cnki.0254–5861.2011–2768
Abstract:
Lewis acid-catalyzed [1,3]-sigmatropic O→C rearrangement was used to synthesize C-glycosides derivatives. The structure of the target compound was characterized by NMR and HR-ESI-MS, and its absolute configuration was confirmed. Compound 8 (C29H29ClN4O7): monoclinic system, space group P212121, a = 6.1484(2), b = 12.3625(3), c = 37.0127(8) Å, V = 2813.32(13) Å3, Z = 4, F(000) = 1216.0, Dc = 1.372 g/cm3, μ = 1.662 mm−1, R = 0.0522 and wR = 0.1358 for 5611 independent reflections (Rint = 0.0778) and 5169 observed ones (I > 2σ(I)).
Lewis acid-catalyzed [1,3]-sigmatropic O→C rearrangement was used to synthesize C-glycosides derivatives. The structure of the target compound was characterized by NMR and HR-ESI-MS, and its absolute configuration was confirmed. Compound 8 (C29H29ClN4O7): monoclinic system, space group P212121, a = 6.1484(2), b = 12.3625(3), c = 37.0127(8) Å, V = 2813.32(13) Å3, Z = 4, F(000) = 1216.0, Dc = 1.372 g/cm3, μ = 1.662 mm−1, R = 0.0522 and wR = 0.1358 for 5611 independent reflections (Rint = 0.0778) and 5169 observed ones (I > 2σ(I)).
2020, 39(10): 1788-1794
doi: 10.14102/j.cnki.0254–5861.2011–2707
Abstract:
A novel two-dimensional nanosheet fluorescent probe embedded with rare earth Eu(Ⅲ) was developed to detect dipicolinic acid (DPA), a biomarker of Bacillus anthracis bacterial spores. DPA, a major component of Bacillus anthracis spores which were highly toxic to humans, was not found in other common bacteria. The ability to detect ultra-low concentrations of DPA would therefore be of great significance. Eu(Ⅲ)-doped ytterbium hydroxide nanosheets were obtained by mechanical exfoliation from layered rare-earth hydroxide (LRH) materials. The crystallinities, layered structure and morphology of the as-synthesized nanosheets were studied by power X-ray diffraction, transmission electron microscopy and atomic force microscopy. Eu(Ⅲ) emission increased linearly with DPA addition in the range of 0.1~30 μmol/L. Based on the antenna effect, the detection limit of DPA was 0.078 μmol/L and much lower than the infective dose of Bacillus anthracis in humans of 60 μmol/L. The nanosheet fluorescent probe exhibited good specificity toward DPA, and the interferences with selected aromatic ligands and amino acids were observed to be negligibly small in comparison with that of DPA. Our findings provide a basis for the application of Eu(Ⅲ)-doped nanosheets for accurate, sensitive, and selective monitoring of DPA as a biomarker of anthrax.
A novel two-dimensional nanosheet fluorescent probe embedded with rare earth Eu(Ⅲ) was developed to detect dipicolinic acid (DPA), a biomarker of Bacillus anthracis bacterial spores. DPA, a major component of Bacillus anthracis spores which were highly toxic to humans, was not found in other common bacteria. The ability to detect ultra-low concentrations of DPA would therefore be of great significance. Eu(Ⅲ)-doped ytterbium hydroxide nanosheets were obtained by mechanical exfoliation from layered rare-earth hydroxide (LRH) materials. The crystallinities, layered structure and morphology of the as-synthesized nanosheets were studied by power X-ray diffraction, transmission electron microscopy and atomic force microscopy. Eu(Ⅲ) emission increased linearly with DPA addition in the range of 0.1~30 μmol/L. Based on the antenna effect, the detection limit of DPA was 0.078 μmol/L and much lower than the infective dose of Bacillus anthracis in humans of 60 μmol/L. The nanosheet fluorescent probe exhibited good specificity toward DPA, and the interferences with selected aromatic ligands and amino acids were observed to be negligibly small in comparison with that of DPA. Our findings provide a basis for the application of Eu(Ⅲ)-doped nanosheets for accurate, sensitive, and selective monitoring of DPA as a biomarker of anthrax.
2020, 39(10): 1795-1806
doi: 10.14102/j.cnki.0254–5861.2011–2728
Abstract:
Uranium in the environment can damage human health and ecosystem. There is a need for excellent adsorbents to remove U(Ⅵ) from aqueous solutions. Here we synthesized a novel β-cyclodextrin/poly(acrylic acid)/permutite (CAP) hydrogel composite by a simple method. Physicochemical characterizations of the materials were conducted by XRD, FTIR, SEM, EDX, and TGA. The effect of pH value, contact time, initial U(Ⅵ) concentration, and temperature were researched. A pseudo-second-order kinetic model, intra-particle diffusion model, and Langmuir isotherm model were used to describe the U(Ⅵ) adsorption behavior, and the maximum adsorption capacity of U(Ⅵ) was 833.33 mg/g at 25 ℃. Thermodynamic analysis showed that the adsorption process of U(Ⅵ) was endothermic and spontaneous. Furthermore, the excellent reusability indicated that CAP hydrogel composite could be potentially used as a promising sorbent for the removal of U (Ⅵ) in wastewater.
Uranium in the environment can damage human health and ecosystem. There is a need for excellent adsorbents to remove U(Ⅵ) from aqueous solutions. Here we synthesized a novel β-cyclodextrin/poly(acrylic acid)/permutite (CAP) hydrogel composite by a simple method. Physicochemical characterizations of the materials were conducted by XRD, FTIR, SEM, EDX, and TGA. The effect of pH value, contact time, initial U(Ⅵ) concentration, and temperature were researched. A pseudo-second-order kinetic model, intra-particle diffusion model, and Langmuir isotherm model were used to describe the U(Ⅵ) adsorption behavior, and the maximum adsorption capacity of U(Ⅵ) was 833.33 mg/g at 25 ℃. Thermodynamic analysis showed that the adsorption process of U(Ⅵ) was endothermic and spontaneous. Furthermore, the excellent reusability indicated that CAP hydrogel composite could be potentially used as a promising sorbent for the removal of U (Ⅵ) in wastewater.
2020, 39(10): 1807-1816
doi: 10.14102/j.cnki.0254–5861.2011–2729
Abstract:
Highly active electrocatalysts based on Layered Double Hydroxides (LDH) towards oxygen evolution reactions (OER) are required for the applications of renewable energy-conversion technology. The improvement of conductivity and electron-transporting capability for LDH materials remains an enormous challenge yet. Here, we synthesized carbon nanotube supported quaternary FeCoNiW-LDH ultrathin nanosheets with 1 nm thickness via one-pot hydrothermal methods, which exhibit enhanced OER activity due to the synergistic effect of modified CNTs and doped W6+ onto LDH nanosheets catalysts. The loaded carbon nanotubes can directly result in the improved conductivity. In addition, W6+ doping in LDH can modify the electronic structure and further enhance the conductivity of electrocatalysts. FeCoNiW-LDH/CNT exhibits a small overpotential (258 mV) at a current density of 10 mA·cm–2 and low Tafel slope (41 mV decade–1) towards OER in alkaline solutions, outperforming the noble metal RuO2 catalysts.
Highly active electrocatalysts based on Layered Double Hydroxides (LDH) towards oxygen evolution reactions (OER) are required for the applications of renewable energy-conversion technology. The improvement of conductivity and electron-transporting capability for LDH materials remains an enormous challenge yet. Here, we synthesized carbon nanotube supported quaternary FeCoNiW-LDH ultrathin nanosheets with 1 nm thickness via one-pot hydrothermal methods, which exhibit enhanced OER activity due to the synergistic effect of modified CNTs and doped W6+ onto LDH nanosheets catalysts. The loaded carbon nanotubes can directly result in the improved conductivity. In addition, W6+ doping in LDH can modify the electronic structure and further enhance the conductivity of electrocatalysts. FeCoNiW-LDH/CNT exhibits a small overpotential (258 mV) at a current density of 10 mA·cm–2 and low Tafel slope (41 mV decade–1) towards OER in alkaline solutions, outperforming the noble metal RuO2 catalysts.
2020, 39(10): 1817-1823
doi: 10.14102/j.cnki.0254–5861.2011–2681
Abstract:
A novel konjac glucomannan (KGM)/poly(galacturonic acid) (PGuA) mixed aerogel (KGM/PGuA) was prepared via a vacuum freeze-drying method, and its interaction mechanism was studied. The rheology results showed that KGM/PGuA mixed gels are typical non-Newtonian pseudoplastic fluids, and PGuA increased the viscosity of the composite aerogel and strengthened the molecular entanglement between KGM and PGuA molecules. The structures of KGM/PGuA aerogels were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that the intermolecular interactions were mainly hydrogen bonding. Dense and uniform porous structures were found in the aerogel microstructures. All these findings indicate that PGuA has the effect of enhancing the KGM gel structure, and KGM/PGuA gels with porous structures might be potential materials for use in food and biomedical areas for loading active materials.
A novel konjac glucomannan (KGM)/poly(galacturonic acid) (PGuA) mixed aerogel (KGM/PGuA) was prepared via a vacuum freeze-drying method, and its interaction mechanism was studied. The rheology results showed that KGM/PGuA mixed gels are typical non-Newtonian pseudoplastic fluids, and PGuA increased the viscosity of the composite aerogel and strengthened the molecular entanglement between KGM and PGuA molecules. The structures of KGM/PGuA aerogels were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that the intermolecular interactions were mainly hydrogen bonding. Dense and uniform porous structures were found in the aerogel microstructures. All these findings indicate that PGuA has the effect of enhancing the KGM gel structure, and KGM/PGuA gels with porous structures might be potential materials for use in food and biomedical areas for loading active materials.
2020, 39(10): 1824-1834
doi: 10.14102/j.cnki.0254–5861.2011–2702
Abstract:
In this work, three stable dumbbell-shaped silver clusters 1~3, formed by a novel bifunctional ligand Ph2P-C6H4-3-C≡CH, are presented. All three complexes have cage structures constructed with thirty-six silver atoms, which are templated by chloride anions. During the self-assembly process of silver acetylides, argentophilic interactions and Ag(I)-ethynide interactions are important for the formation of silver cores to yield a diversity of silver clusters. Weak molecular interactions (π-π, C−H···π, C−H···F, C−H···O) are also found in these complexes, which are crucial to stabilizing these silver clusters. Compared with simple alkynyl ligands (RC≡C−), the introduction of phosphine groups into alkynyl ligand can effectively control the undesired infinite growth of silver acetylides. The photophysical behaviors of complexes 1~3 are studied, showing intense orange room-temperature luminescence in the solid state upon the exposure to UV light. The luminescence mainly arises from ligand-to-metal charge transfer (LMCT) and metal-cluster-lefted transitions (MC) within the silver clusters.
In this work, three stable dumbbell-shaped silver clusters 1~3, formed by a novel bifunctional ligand Ph2P-C6H4-3-C≡CH, are presented. All three complexes have cage structures constructed with thirty-six silver atoms, which are templated by chloride anions. During the self-assembly process of silver acetylides, argentophilic interactions and Ag(I)-ethynide interactions are important for the formation of silver cores to yield a diversity of silver clusters. Weak molecular interactions (π-π, C−H···π, C−H···F, C−H···O) are also found in these complexes, which are crucial to stabilizing these silver clusters. Compared with simple alkynyl ligands (RC≡C−), the introduction of phosphine groups into alkynyl ligand can effectively control the undesired infinite growth of silver acetylides. The photophysical behaviors of complexes 1~3 are studied, showing intense orange room-temperature luminescence in the solid state upon the exposure to UV light. The luminescence mainly arises from ligand-to-metal charge transfer (LMCT) and metal-cluster-lefted transitions (MC) within the silver clusters.
2020, 39(10): 1835-1840
doi: 10.14102/j.cnki.0254–5861.2011–2708
Abstract:
A new zinc coordination polymer {[Zn2(ttmb)2(dca)4(H2O)]·H2O}n (1·H2O) was synthesized by the reaction of 1, 3, 5-tris(1, 2, 4-triazol-1-ylmethyl)benzene (ttmb), Zn(II) salt and sodium dicyanamide (Na(dca)). The structure of the title compound was determined by single-crystal X-ray diffraction, elemental analyses and IR spectra. 1 exhibits a (3, 4)-connected 2D double-layer network with the point symbol of {63}{(66}. The solid-state luminescence shows a strong emission band at 485 nm upon excitation at 384 nm. The thermal stability properties were also studied.
A new zinc coordination polymer {[Zn2(ttmb)2(dca)4(H2O)]·H2O}n (1·H2O) was synthesized by the reaction of 1, 3, 5-tris(1, 2, 4-triazol-1-ylmethyl)benzene (ttmb), Zn(II) salt and sodium dicyanamide (Na(dca)). The structure of the title compound was determined by single-crystal X-ray diffraction, elemental analyses and IR spectra. 1 exhibits a (3, 4)-connected 2D double-layer network with the point symbol of {63}{(66}. The solid-state luminescence shows a strong emission band at 485 nm upon excitation at 384 nm. The thermal stability properties were also studied.
2020, 39(10): 1841-1848
doi: 10.14102/j.cnki.0254–5861.2011–2714
Abstract:
Combination of D-π-A stilbazolium-type dye DANP (DANP = trans-4-(4΄-(N, N-diethylaminostyryl))-N-methyl-pyridinium) with zinc chloride results in a new hybrid (DANP-H)(ZnCl4) (1), and its structure was determined by single-crystal X-ray diffraction method. In the hybrid, two independent DANP-H2+ cations exhibit two kinds of configurations, i.e., conjugation-broken and conjugation-maintained fashions, and the X-aggregation mode of (DANP-H)2+ cations is driven by strong C–H···Cl hydrogen bonds and C–H···π interactions. Consequently, blue-shift was observed in its adsorption spectrum, and unquenched red photoluminescence can be monitored. Interestingly, dual stimuli-responsive performance and reversible photo/thermochromic behaviors appeared, which can be assigned to the electron transfer from Cl-3p/DANP-π to π* antibonding orbitals of the conjugation-maintained DANP.
Combination of D-π-A stilbazolium-type dye DANP (DANP = trans-4-(4΄-(N, N-diethylaminostyryl))-N-methyl-pyridinium) with zinc chloride results in a new hybrid (DANP-H)(ZnCl4) (1), and its structure was determined by single-crystal X-ray diffraction method. In the hybrid, two independent DANP-H2+ cations exhibit two kinds of configurations, i.e., conjugation-broken and conjugation-maintained fashions, and the X-aggregation mode of (DANP-H)2+ cations is driven by strong C–H···Cl hydrogen bonds and C–H···π interactions. Consequently, blue-shift was observed in its adsorption spectrum, and unquenched red photoluminescence can be monitored. Interestingly, dual stimuli-responsive performance and reversible photo/thermochromic behaviors appeared, which can be assigned to the electron transfer from Cl-3p/DANP-π to π* antibonding orbitals of the conjugation-maintained DANP.
2020, 39(10): 1849-1854
doi: 10.14102/j.cnki.0254–5861.2011–2411
Abstract:
Two new Cu(II) and Co(II)-based coordination polymers with the chemical formulae of {Cu(L)2]·DMF}n (1) and {[Co(L)2]·2DMF}n (2) have been successfully constructed from a pyridine-substituted N-heterocyclic thioamide ligand, namely [3, 4΄-bipyridine]-2΄-thiol (HL). Complex 1 is composed of two identical coordination networks with dia topology interpenetrating into each other, and shows 1-D microporous channels along the a axis. Complex 2 is assembled by 2-D square-grid layers stacked in an eclipsed fashion to give 1-D large square channels along the b axis. CCK-8 was used for the detection of cancer cells. Results indicated that compound 1 exhibited stronger anti-cancer activity than compound 2 on the H1650 cancer cells. The Annexin V-FITC/PI was recommended for cancer cell apoptosis, and the western blot was applied for the detection of PI3K/AKT pathway activation.
Two new Cu(II) and Co(II)-based coordination polymers with the chemical formulae of {Cu(L)2]·DMF}n (1) and {[Co(L)2]·2DMF}n (2) have been successfully constructed from a pyridine-substituted N-heterocyclic thioamide ligand, namely [3, 4΄-bipyridine]-2΄-thiol (HL). Complex 1 is composed of two identical coordination networks with dia topology interpenetrating into each other, and shows 1-D microporous channels along the a axis. Complex 2 is assembled by 2-D square-grid layers stacked in an eclipsed fashion to give 1-D large square channels along the b axis. CCK-8 was used for the detection of cancer cells. Results indicated that compound 1 exhibited stronger anti-cancer activity than compound 2 on the H1650 cancer cells. The Annexin V-FITC/PI was recommended for cancer cell apoptosis, and the western blot was applied for the detection of PI3K/AKT pathway activation.
2020, 39(10): 1855-1861
doi: 10.14102/j.cnki.0254–5861.2011–2723
Abstract:
A new complex {[Zn2(L)(cpa)2]·H2O}n (1) was prepared under hydrothermal conditions based on 4-carbonylphenylacetic acid (H2cpa) with multi-N-donor ligand 1, 4-di(1H-imidazol-4-yl)benzene (L). The complex was characterized by IR spectroscopy, TGA, X-ray powder and single-crystal diffraction. It crystallizes in the orthorhombic system, space group Pbca with a = 8.6427(9), b = 16.1616(17), c = 20.941(2) Å, V = 2925.0(5) Å3, Z = 8, C15H13N2O5Zn, Mr = 366.64, Dc = 1.665 g/cm3, μ = 1.707 mm-1, S = 1.011, F(000) = 1496, the final R = 0.0385 and wR = 0.0945 for 3360 observed reflections (I > 2σ(I)). The central metal Zn(II) atom with distorted ZnO3N tetrahedral coordination geometry is four-coordinated by three oxygen and one nitrogen atoms. The cpa2- ligands connect Zn(II) atoms to form two-dimensional (2D) double-layer networks which are further pillared by L ligands into a binodal (3, 4)-connected three-dimensional (3D) architecture with a (63·103)(63) tcj/hc topology. Solid-state luminescent property together with quantum yield (QY) and luminescence lifetime is also investigated for compound 1.
A new complex {[Zn2(L)(cpa)2]·H2O}n (1) was prepared under hydrothermal conditions based on 4-carbonylphenylacetic acid (H2cpa) with multi-N-donor ligand 1, 4-di(1H-imidazol-4-yl)benzene (L). The complex was characterized by IR spectroscopy, TGA, X-ray powder and single-crystal diffraction. It crystallizes in the orthorhombic system, space group Pbca with a = 8.6427(9), b = 16.1616(17), c = 20.941(2) Å, V = 2925.0(5) Å3, Z = 8, C15H13N2O5Zn, Mr = 366.64, Dc = 1.665 g/cm3, μ = 1.707 mm-1, S = 1.011, F(000) = 1496, the final R = 0.0385 and wR = 0.0945 for 3360 observed reflections (I > 2σ(I)). The central metal Zn(II) atom with distorted ZnO3N tetrahedral coordination geometry is four-coordinated by three oxygen and one nitrogen atoms. The cpa2- ligands connect Zn(II) atoms to form two-dimensional (2D) double-layer networks which are further pillared by L ligands into a binodal (3, 4)-connected three-dimensional (3D) architecture with a (63·103)(63) tcj/hc topology. Solid-state luminescent property together with quantum yield (QY) and luminescence lifetime is also investigated for compound 1.
2020, 39(10): 1862-1870
doi: 10.14102/j.cnki.0254–5861.2011–2926
Abstract:
A robust microporous praseodymium-organic framework, {[Pr3(NTB)3(H2O)3]·(DMF)3(H2O)4}n (Pr-NTB, 1), was solvothermally synthesized based on 4, 4΄, 4΄΄-nitrilotribenzoic acid (H3NTB) and fully characterized. Single-crystal X-ray diffraction analysis reveals compound 1 possesses a three-dimensional porous coordination network, in which discrete cages are connected through microporous windows. 1 shows extraordinary thermal and water stability; in particular, it is stable in aqueous media from pH = 3 to 11, which is outstanding in benzyl-carboxylate based MOFs. Furthermore, 1 exhibits permanent porosity with the BET surface area of 156.2 m2·g-1 and can adsorb suitable CO2 (1.14 mmol·g-1 at 273 K/1 bar) with isosteric heat of adsorption (Qst) of 28.5 kJ·mol-1. These features suggest that the porous material 1 is a good candidate for CO2 capture in real-world application. Notably, the integration of fluorescent property, porosity and water stability in 1 promises it as a selective fluorescent sensor for Fe3+ cation in water.
A robust microporous praseodymium-organic framework, {[Pr3(NTB)3(H2O)3]·(DMF)3(H2O)4}n (Pr-NTB, 1), was solvothermally synthesized based on 4, 4΄, 4΄΄-nitrilotribenzoic acid (H3NTB) and fully characterized. Single-crystal X-ray diffraction analysis reveals compound 1 possesses a three-dimensional porous coordination network, in which discrete cages are connected through microporous windows. 1 shows extraordinary thermal and water stability; in particular, it is stable in aqueous media from pH = 3 to 11, which is outstanding in benzyl-carboxylate based MOFs. Furthermore, 1 exhibits permanent porosity with the BET surface area of 156.2 m2·g-1 and can adsorb suitable CO2 (1.14 mmol·g-1 at 273 K/1 bar) with isosteric heat of adsorption (Qst) of 28.5 kJ·mol-1. These features suggest that the porous material 1 is a good candidate for CO2 capture in real-world application. Notably, the integration of fluorescent property, porosity and water stability in 1 promises it as a selective fluorescent sensor for Fe3+ cation in water.
2020, 39(10): 1871-1876
doi: 10.14102/j.cnki.0254–5861.2011–2924
Abstract:
X-ray single-crystal structure analysis, UV-Vis, and photoluminescent properties of organic compound, 9-(4-(5-(6-methylpyridin-2-yl)-3-phenyl-1H-1, 2, 4-triazol-1-yl)phenyl)-9H-carbazole (compound 1) were studied. Compound 1 crystallizes in monoclinic system, space group P21/c with a = 16.0434(9), b = 17.920(1), c = 8.3453(5) Å, β = 94.142(5)°, V = 2393.0(2), Z = 4, Mr = 477.55, Dc = 1.326 g/cm3, F(000) = 1000, μ = 0.080 mm–1, GOOF = 1.025, the final R = 0.0505 and wR = 0.1226 for 4921 observed reflections with I > 2σ(I). Compound 1 is a donor-acceptor type molecule, in which the carbazolyl group (cz) acts as an electron donor, and the group of 2-(1, 3-diphenyl-1H-1, 2, 4-triazol-5-yl)-6-methylpyridine (MePyTz) as an electron acceptor. In methylene chloride, compound 1 exhibits deep blue luminescence with maximum at 440 nm, lifetime of 4.2 ns under N2 and quantum yield of ф = 0.18 at room temperature. The experimental and computational results show that the emission of compound 1 originates from the lowest singlet excited state (S1) with charge transfer character.
X-ray single-crystal structure analysis, UV-Vis, and photoluminescent properties of organic compound, 9-(4-(5-(6-methylpyridin-2-yl)-3-phenyl-1H-1, 2, 4-triazol-1-yl)phenyl)-9H-carbazole (compound 1) were studied. Compound 1 crystallizes in monoclinic system, space group P21/c with a = 16.0434(9), b = 17.920(1), c = 8.3453(5) Å, β = 94.142(5)°, V = 2393.0(2), Z = 4, Mr = 477.55, Dc = 1.326 g/cm3, F(000) = 1000, μ = 0.080 mm–1, GOOF = 1.025, the final R = 0.0505 and wR = 0.1226 for 4921 observed reflections with I > 2σ(I). Compound 1 is a donor-acceptor type molecule, in which the carbazolyl group (cz) acts as an electron donor, and the group of 2-(1, 3-diphenyl-1H-1, 2, 4-triazol-5-yl)-6-methylpyridine (MePyTz) as an electron acceptor. In methylene chloride, compound 1 exhibits deep blue luminescence with maximum at 440 nm, lifetime of 4.2 ns under N2 and quantum yield of ф = 0.18 at room temperature. The experimental and computational results show that the emission of compound 1 originates from the lowest singlet excited state (S1) with charge transfer character.
2020, 39(10): 1877-1884
doi: 10.14102/j.cnki.0254–5861.2011–2815
Abstract:
A pair of nickel(II) complexes monomer and dimer, namely [NiCl2(L)] (1) and [Ni2Cl2(L)2(μ-Cl)2] (2) (L = 2-morpholine-4-yl-4, 6-di-pyrazol-1-yl-1, 3, 5-triazine), were synthesized by using L to react with NiCl2·2H2O at 35 and 65 ℃, respectively. X-ray crystal structures of complexes 1 and 2 were determined. Complex 1 is mononuclear and its nickel(II) center resides in a distorted square-pyramidal environment with a NiN3Cl2 donor set, but complex 2 is binuclear and its nickel(II) center shows a distorted octahedral geometry with a NiN3Cl3 donor set. In complex 2, two adjacent nickel(II) centers are connected by two bridging chloride anions. Complexes 1 and 2 form different three-dimensional supramolecular structures through non-covalent interactions such as π-π stacking interactions, anion-π interactions and weak hydrogen bonds. Both complexes were further characterized by thermal gravimetric analyses and spectroscopic methods.
A pair of nickel(II) complexes monomer and dimer, namely [NiCl2(L)] (1) and [Ni2Cl2(L)2(μ-Cl)2] (2) (L = 2-morpholine-4-yl-4, 6-di-pyrazol-1-yl-1, 3, 5-triazine), were synthesized by using L to react with NiCl2·2H2O at 35 and 65 ℃, respectively. X-ray crystal structures of complexes 1 and 2 were determined. Complex 1 is mononuclear and its nickel(II) center resides in a distorted square-pyramidal environment with a NiN3Cl2 donor set, but complex 2 is binuclear and its nickel(II) center shows a distorted octahedral geometry with a NiN3Cl3 donor set. In complex 2, two adjacent nickel(II) centers are connected by two bridging chloride anions. Complexes 1 and 2 form different three-dimensional supramolecular structures through non-covalent interactions such as π-π stacking interactions, anion-π interactions and weak hydrogen bonds. Both complexes were further characterized by thermal gravimetric analyses and spectroscopic methods.
2020, 39(10): 1885-1891
doi: 10.14102/j.cnki.0254–5861.2011–2709
Abstract:
Two new complexes [Zn(nph)(bix)]n·nH2O (1) and [Zn(nba)2(bix)]n (2) (H2nph = 4-nitrophthalic acid, Hnba = 4-nitrobenzoic acid, bix = 1, 4-bis(imidazol-1-yl)-benzene) have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, fluorescence spectrum, single-crystal and power X-ray diffraction. Complex 1 exhibits a three-dimensional (3D) framework, which is stabilized through C–H···O hydrogen bonds and π-π stacking interactions. Complex 2 shows a zero-dimensional structure, which is further extended into a three-dimensional supramolecular structure through C–H···O and C–H···N hydrogen bonding interactions.
Two new complexes [Zn(nph)(bix)]n·nH2O (1) and [Zn(nba)2(bix)]n (2) (H2nph = 4-nitrophthalic acid, Hnba = 4-nitrobenzoic acid, bix = 1, 4-bis(imidazol-1-yl)-benzene) have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, fluorescence spectrum, single-crystal and power X-ray diffraction. Complex 1 exhibits a three-dimensional (3D) framework, which is stabilized through C–H···O hydrogen bonds and π-π stacking interactions. Complex 2 shows a zero-dimensional structure, which is further extended into a three-dimensional supramolecular structure through C–H···O and C–H···N hydrogen bonding interactions.
2020, 39(10): 1892-1897
doi: 10.14102/j.cnki.0254–5861.2011–2682
Abstract:
The heterocyclic compound 2-amino-N-(2-chloro-6-methylphenyl)thiazole-5-carboxamide (1), designed using 2-chloro-6-methylaniline (2) as the start material, was successfully obtained via multiple synthesis route and finally characterized by IR, 1H NMR, and single-cystal X-ray crystallography. To select the suitable candidates for tissue regeneration, the induction activity of the compound on the dental pulp mesenchymal stem cells (DP-MSCs) was evaluated. Firstly, the DP-MSCs cells were isolated and the cell colon formation ability was measured after compound treatment with cell colony determination. After that, the RT-PCT assay was conducted and the relative expression level of the genes related with cell osteogenesis and proliferation was further detected.
The heterocyclic compound 2-amino-N-(2-chloro-6-methylphenyl)thiazole-5-carboxamide (1), designed using 2-chloro-6-methylaniline (2) as the start material, was successfully obtained via multiple synthesis route and finally characterized by IR, 1H NMR, and single-cystal X-ray crystallography. To select the suitable candidates for tissue regeneration, the induction activity of the compound on the dental pulp mesenchymal stem cells (DP-MSCs) was evaluated. Firstly, the DP-MSCs cells were isolated and the cell colon formation ability was measured after compound treatment with cell colony determination. After that, the RT-PCT assay was conducted and the relative expression level of the genes related with cell osteogenesis and proliferation was further detected.
2020, 39(10): 1898-1905
doi: 10.14102/j.cnki.0254–5861.2011–2791
Abstract:
In order to improve the water solubility and bioavailability of 5-hydroxy-7-methoxyflavone, argentum 5-hydroxy-7-methoxy-2-phenyl-4H-chromen-4-one-6-sulfonate [Ag4(H2O)6](C16H11O4SO3)4·H2O (1, C16H11O4SO3 = 5-hydroxy-7-methoxy-2-phenyl-4H-chromen-4-one-6-sulfonate) was synthesized by sulfonation reaction. The structure of 1 was characterized by FT-IR, elemental analysis and X-ray single-crystal diffraction. Complex 1 belongs to the triclinic system, space group P\begin{document}$ \overline 1 $\end{document}
In order to improve the water solubility and bioavailability of 5-hydroxy-7-methoxyflavone, argentum 5-hydroxy-7-methoxy-2-phenyl-4H-chromen-4-one-6-sulfonate [Ag4(H2O)6](C16H11O4SO3)4·H2O (1, C16H11O4SO3 = 5-hydroxy-7-methoxy-2-phenyl-4H-chromen-4-one-6-sulfonate) was synthesized by sulfonation reaction. The structure of 1 was characterized by FT-IR, elemental analysis and X-ray single-crystal diffraction. Complex 1 belongs to the triclinic system, space group P
2020, 39(10): 1906-1911
doi: 10.14102/j.cnki.0254–5861.2011–2699
Abstract:
Two novel substituted phenyl oxazole isoxazole carboxamides have been synthesized by microwave assistant technology. The target compounds were characterized by IR, 1H NMR, 13C NMR and HRMS, and their single-crystal structures were further determined by X-ray diffraction. 3-Phenyl-4-(2΄-methyl-2΄-isopropyl-1΄, 3΄-oxazole)-5-methyl isoxazole carboxamide (6a) crystallizes in monoclinic system, space group P21/c with a = 6.2137(12), b = 19.923(4), c = 13.748(3) Å, β = 92.30(3)°, V = 1700.6(6) Å3, Dc = 1.228 Mg/m3, Z = 4, F(000) = 672, μ(MoKα) = 0.084 mm-1, R = 0.0526 and wR = 0.1259. 3-(2΄-Fluoro-6΄-chloro-phenyl)-4-(2΄-methyl-2΄-ethyl-1΄, 3΄-oxazole)-5-methyl isoxazole carboxamide (6b) crystallizes in triclinic system, space group P\begin{document}$ \overline 1 $\end{document}
Two novel substituted phenyl oxazole isoxazole carboxamides have been synthesized by microwave assistant technology. The target compounds were characterized by IR, 1H NMR, 13C NMR and HRMS, and their single-crystal structures were further determined by X-ray diffraction. 3-Phenyl-4-(2΄-methyl-2΄-isopropyl-1΄, 3΄-oxazole)-5-methyl isoxazole carboxamide (6a) crystallizes in monoclinic system, space group P21/c with a = 6.2137(12), b = 19.923(4), c = 13.748(3) Å, β = 92.30(3)°, V = 1700.6(6) Å3, Dc = 1.228 Mg/m3, Z = 4, F(000) = 672, μ(MoKα) = 0.084 mm-1, R = 0.0526 and wR = 0.1259. 3-(2΄-Fluoro-6΄-chloro-phenyl)-4-(2΄-methyl-2΄-ethyl-1΄, 3΄-oxazole)-5-methyl isoxazole carboxamide (6b) crystallizes in triclinic system, space group P
2020, 39(10): 1912-1917
doi: 10.14102/j.cnki.0254–5861.2011–2700
Abstract:
The title compound 3-(2, 4-difluorobenzyl)-5-(p-tolyl)-7-(trifluoromethyl)pyrazolo[1, 5-a]pyrimidin-2-amine (6) was synthesized by the condensation of 4, 4, 4-trifluoro-1-(p-tolyl)butane-1, 3-dione (5) with 4-(2, 4-difluorobenzyl)-1H-pyrazole-3, 5-diamine (4). The latter was prepared from 2, 4-difluorobenzaldehyde (1) and malononitrile through Knoevenagel condensation and NaBH3CN reduction and then cyclisation with hydrazine hydrate. The crystal structure of the title compound was determined and its crystal belongs to the triclinic system, space group P\begin{document}$ \overline 1 $\end{document}
The title compound 3-(2, 4-difluorobenzyl)-5-(p-tolyl)-7-(trifluoromethyl)pyrazolo[1, 5-a]pyrimidin-2-amine (6) was synthesized by the condensation of 4, 4, 4-trifluoro-1-(p-tolyl)butane-1, 3-dione (5) with 4-(2, 4-difluorobenzyl)-1H-pyrazole-3, 5-diamine (4). The latter was prepared from 2, 4-difluorobenzaldehyde (1) and malononitrile through Knoevenagel condensation and NaBH3CN reduction and then cyclisation with hydrazine hydrate. The crystal structure of the title compound was determined and its crystal belongs to the triclinic system, space group P
