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2018 Volume 34 Issue 10
2018, 34(10): 1775-1782
doi: 10.11862/CJIC.2018.236
Abstract:
A brand new treatment was reported to cure the cancer triumphantly using the combination of photo-thermal therapy inducing by nitrogen doped carbon dots (N-CDs) and chemotherapy of the doxorubicin (Dox). The experiment results demonstrated that the as-synthesized N-CDs had excellent photo-thermal effect inducing the temperature enhancement as high as about 10℃. Furthermore, the as-prepared N-CDs could load Dox availably and achieve a pH-controlled drug release. Thus, the multifunctional N-CDs-Dox nanocomposites could perform the synergetic effect of photo-thermal therapy and chemotherapy to tumor cells.
A brand new treatment was reported to cure the cancer triumphantly using the combination of photo-thermal therapy inducing by nitrogen doped carbon dots (N-CDs) and chemotherapy of the doxorubicin (Dox). The experiment results demonstrated that the as-synthesized N-CDs had excellent photo-thermal effect inducing the temperature enhancement as high as about 10℃. Furthermore, the as-prepared N-CDs could load Dox availably and achieve a pH-controlled drug release. Thus, the multifunctional N-CDs-Dox nanocomposites could perform the synergetic effect of photo-thermal therapy and chemotherapy to tumor cells.
2018, 34(10): 1864-1874
doi: 10.11862/CJIC.2018.234
Abstract:
A four-coordinated Cu(Ⅱ) complex with Schiff base ligand was synthesized and characterized by the elemental analysis and infrared spectroscopy, and the crystal structure was determined by X-ray diffraction. The crystal of complex belongs to monoclinic system. In vitro antitumor activities of Cu(Ⅱ) complex were evaluated by the 3-(4, 5-dimethylthiazoly-2-yl)-2, 5-diphenyltetrazoliumbromide (MTT) assay against four human cancer cell lines (Hela, SGC-7901, HepG2, MCF-7). Cu(Ⅱ) complex exhibited stronger antitumor activity than carboplatin. The interaction of Cu(Ⅱ) complex with bovine serum albumin (BSA) was studied by spectroscopic method. The analysis of fluorescence data indicates the presence of static quenching mechanism in the binding process. Various binding parameters including binding constants, binding sites, binding distance and thermodynamic parameters ΔH, ΔS and ΔG have been evaluated.
A four-coordinated Cu(Ⅱ) complex with Schiff base ligand was synthesized and characterized by the elemental analysis and infrared spectroscopy, and the crystal structure was determined by X-ray diffraction. The crystal of complex belongs to monoclinic system. In vitro antitumor activities of Cu(Ⅱ) complex were evaluated by the 3-(4, 5-dimethylthiazoly-2-yl)-2, 5-diphenyltetrazoliumbromide (MTT) assay against four human cancer cell lines (Hela, SGC-7901, HepG2, MCF-7). Cu(Ⅱ) complex exhibited stronger antitumor activity than carboplatin. The interaction of Cu(Ⅱ) complex with bovine serum albumin (BSA) was studied by spectroscopic method. The analysis of fluorescence data indicates the presence of static quenching mechanism in the binding process. Various binding parameters including binding constants, binding sites, binding distance and thermodynamic parameters ΔH, ΔS and ΔG have been evaluated.
2018, 34(10): 1875-1882
doi: 10.11862/CJIC.2018.230
Abstract:
2-Methyl-5-(2-pyridyl)-1, 3, 4-oxadiazole(L), [Cu2L2(μ-Cl)2Cl2] (1) and[CdL2(NO3)2] (2) were synthesized and characterized by single crystal X-ray diffraction, IR, UV-Vis, fluorescence and TGA. Ligand L and complex 2 crystallize in monoclinic system. Complex 1 crystallizes in triclinic system. The space groups of compound L, complexes 1 and 2 are P21/c, P1 and C2/c, respectively. Complex 1 is a binuclear Cu(Ⅱ) complex bridged by two Cl atoms (Cl1, Cl1ⅰ) and has a distorted tetragonal pyramidal geometry with[CuCl3N2]. Complex 2 has a distorted octahedral geometry with[CdN4O2].
2-Methyl-5-(2-pyridyl)-1, 3, 4-oxadiazole(L), [Cu2L2(μ-Cl)2Cl2] (1) and[CdL2(NO3)2] (2) were synthesized and characterized by single crystal X-ray diffraction, IR, UV-Vis, fluorescence and TGA. Ligand L and complex 2 crystallize in monoclinic system. Complex 1 crystallizes in triclinic system. The space groups of compound L, complexes 1 and 2 are P21/c, P1 and C2/c, respectively. Complex 1 is a binuclear Cu(Ⅱ) complex bridged by two Cl atoms (Cl1, Cl1ⅰ) and has a distorted tetragonal pyramidal geometry with[CuCl3N2]. Complex 2 has a distorted octahedral geometry with[CdN4O2].
2018, 34(10): 1883-1890
doi: 10.11862/CJIC.2018.212
Abstract:
Four kinds of calcium oxalate monohydrate (COM) crystals with the size of (1.5±0.4), (3.5±0.5), (5.5±0.5) and (9.5±1) μm respectively were synthesized by changing reaction temperature, solvent, additive and stirring speed. Their physiochemical properties were comparatively investigated. It is beneficial to obtain crystal with small size by adding additive Na3Cit, increasing stirring speed, reducing reaction temperature or decreasing dielectric constant of the solvent. The results of X-ray diffraction revealed that all these crystals are single-phase COM crystals. With the increase of crystal size from 1 to 9 μm, COM crystals changed from rough blunt round to smooth thin sheet, the (101) crystal face of COM with high charge density increased, and both the charge density and the absolute value of ζ potential on crystal surface increased, leading an increase of the stability of crystal suspension. The cytotoxicity of these COM crystals to human kidney proximal tubular epithelial (HK-2) cells is negatively correlated with the crystal size.
Four kinds of calcium oxalate monohydrate (COM) crystals with the size of (1.5±0.4), (3.5±0.5), (5.5±0.5) and (9.5±1) μm respectively were synthesized by changing reaction temperature, solvent, additive and stirring speed. Their physiochemical properties were comparatively investigated. It is beneficial to obtain crystal with small size by adding additive Na3Cit, increasing stirring speed, reducing reaction temperature or decreasing dielectric constant of the solvent. The results of X-ray diffraction revealed that all these crystals are single-phase COM crystals. With the increase of crystal size from 1 to 9 μm, COM crystals changed from rough blunt round to smooth thin sheet, the (101) crystal face of COM with high charge density increased, and both the charge density and the absolute value of ζ potential on crystal surface increased, leading an increase of the stability of crystal suspension. The cytotoxicity of these COM crystals to human kidney proximal tubular epithelial (HK-2) cells is negatively correlated with the crystal size.
2018, 34(10): 1891-1898
doi: 10.11862/CJIC.2018.235
Abstract:
Two new sandwich-type di-lanthanide complexes[M2L3(H2O)] (M=Tb (1), Dy (2), H2L=N, N'-bis(4-methyloxysalicylidene)benzene-1, 2-diamine) were synthesized by treating the Schiff-base ligand with M(acac)3·6H2O (M=Tb, Dy) and characterized by elemental analysis, IR spectra and X-ray single crystal diffraction. X-ray single crystal diffraction analysis reveals that 1 and 2 have a similar new triple-deck dinuclear sandwich structure. The magnetic measurements of complexes 1 and 2 indicated that 1 and 2 exhibit the antiferromagnetic interactions between lanthanide ions, and field-induced slow magnetic relaxation. The deduced effective energy barrier (Ueff) and relaxation time (τ0) are 35.45 cm-1 and 2.7×10-10 s for 2.
Two new sandwich-type di-lanthanide complexes[M2L3(H2O)] (M=Tb (1), Dy (2), H2L=N, N'-bis(4-methyloxysalicylidene)benzene-1, 2-diamine) were synthesized by treating the Schiff-base ligand with M(acac)3·6H2O (M=Tb, Dy) and characterized by elemental analysis, IR spectra and X-ray single crystal diffraction. X-ray single crystal diffraction analysis reveals that 1 and 2 have a similar new triple-deck dinuclear sandwich structure. The magnetic measurements of complexes 1 and 2 indicated that 1 and 2 exhibit the antiferromagnetic interactions between lanthanide ions, and field-induced slow magnetic relaxation. The deduced effective energy barrier (Ueff) and relaxation time (τ0) are 35.45 cm-1 and 2.7×10-10 s for 2.
2018, 34(10): 1899-1909
doi: 10.11862/CJIC.2018.251
Abstract:
High performance MoO3-C3N4 photocatalysts were prepared by impregnation method with (NH4)6Mo7O24·4H2O and C3N4 as precursors. The MoO3-C3N4 photocatalysts were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), high resolution transmission electron microscopy (HRTEM) and nitrogen physisorption isotherm. And methyl orange (MO) degradation was chosen to test the photocatalytic performance of MoO3-C3N4. It was found that all MoO3-C3N4 samples showed very high surface area, exhibited high photocatalytic activity for MO degradation under visible light irradiation and the content of MoO3 affected the photocatalytic activity. The rate constant of 1.60%(w/w) MoO3-C3N4 was 50 times higher than that of pure C3N4. The enhancement of photocatalytic activity over the heterojunction catalyst could be directly attributed to the Z-scheme photo-generated charge carrier transfer process, which contributes to suppressed recombination rate of photogenerated electron-hole pairs and prolonged lifetime of charge carriers caused by hybridization of MoO3.
High performance MoO3-C3N4 photocatalysts were prepared by impregnation method with (NH4)6Mo7O24·4H2O and C3N4 as precursors. The MoO3-C3N4 photocatalysts were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), high resolution transmission electron microscopy (HRTEM) and nitrogen physisorption isotherm. And methyl orange (MO) degradation was chosen to test the photocatalytic performance of MoO3-C3N4. It was found that all MoO3-C3N4 samples showed very high surface area, exhibited high photocatalytic activity for MO degradation under visible light irradiation and the content of MoO3 affected the photocatalytic activity. The rate constant of 1.60%(w/w) MoO3-C3N4 was 50 times higher than that of pure C3N4. The enhancement of photocatalytic activity over the heterojunction catalyst could be directly attributed to the Z-scheme photo-generated charge carrier transfer process, which contributes to suppressed recombination rate of photogenerated electron-hole pairs and prolonged lifetime of charge carriers caused by hybridization of MoO3.
2018, 34(10): 1910-1916
doi: 10.11862/CJIC.2018.237
Abstract:
Bulk Ni3Mn-layered double hydroxides (Ni3Mn-LDHs) was exfoliated into single-layer Ni3Mn-LDHs nanosheets via liquid phase exfoliation, and then incorporated with CNT to obtain Ni3Mn-LDHs/CNT composites by self-assemble method. The structure of the composites was characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The electrochemical process was analyzed by galvanostatic tests, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The Ni3Mn-LDHs/CNT composites improved the ORR and OER catalytic activities significantly, the obtained Ni3Mn-LDHs/CNT cathode presented nearly 300% higher discharge capacity, excellent rate and cycling stability than the CNT cathode in lithium-oxygen batteries.
Bulk Ni3Mn-layered double hydroxides (Ni3Mn-LDHs) was exfoliated into single-layer Ni3Mn-LDHs nanosheets via liquid phase exfoliation, and then incorporated with CNT to obtain Ni3Mn-LDHs/CNT composites by self-assemble method. The structure of the composites was characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The electrochemical process was analyzed by galvanostatic tests, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The Ni3Mn-LDHs/CNT composites improved the ORR and OER catalytic activities significantly, the obtained Ni3Mn-LDHs/CNT cathode presented nearly 300% higher discharge capacity, excellent rate and cycling stability than the CNT cathode in lithium-oxygen batteries.
2018, 34(10): 1917-1922
doi: 10.11862/CJIC.2018.215
Abstract:
A complex, namely[Cu4(L)2(CH3O)2(CH3OH)4(SO4)2]SO4·6CH3OH (1) (L=N, N'-bis-(1-(3-ethyl-pyrazin-2-yl)-ethylidene)-hydrazine) has been synthesized and characterized by single-crystal X-ray diffraction, elemental analysis and IR spectroscopy. X-ray diffraction analysis results show that in complex 1, each Cu(Ⅱ) center with a distorted octahedron geometry is coordinated by two N atoms from one pyrazin-2-yl-ethylideneamine subunit, and four O atoms involving one O atom from one neutral methanol, one μ2-bridged O atom from one methoxy anion, one μ2-bridged O and one monodentate O atoms from two independent sulfate anions, thus forming an ideal planar fourmembered Cu4 core. In addition, the fluorescence spectra indicate that the interaction of complex 1 with DNA is stronger than that of the ligand L.
A complex, namely[Cu4(L)2(CH3O)2(CH3OH)4(SO4)2]SO4·6CH3OH (1) (L=N, N'-bis-(1-(3-ethyl-pyrazin-2-yl)-ethylidene)-hydrazine) has been synthesized and characterized by single-crystal X-ray diffraction, elemental analysis and IR spectroscopy. X-ray diffraction analysis results show that in complex 1, each Cu(Ⅱ) center with a distorted octahedron geometry is coordinated by two N atoms from one pyrazin-2-yl-ethylideneamine subunit, and four O atoms involving one O atom from one neutral methanol, one μ2-bridged O atom from one methoxy anion, one μ2-bridged O and one monodentate O atoms from two independent sulfate anions, thus forming an ideal planar fourmembered Cu4 core. In addition, the fluorescence spectra indicate that the interaction of complex 1 with DNA is stronger than that of the ligand L.
2018, 34(10): 1923-1928
doi: 10.11862/CJIC.2018.225
Abstract:
Two new metal-organic supramolecular coordination compounds[Cd(cba)2(bix)]2 (1) and[Zn(cba)2(bix)]2 (2) (Hcba=2-chlorinebenzoic acid, bix=1, 4-bis(imidazol-1-ylmethyl) benzene) have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG, fluorescence spectrum, single-crystal and powder X-ray diffraction. Complexes 1 and 2 are isomorphism, and all exhibit zero-dimensional framework and display three-dimensional supramolecular network via π-π stacking interactions. In addition, natural bond orbital (NBO) of 1 were analyzed by using the PBE0/LANL2DZ method built in Gaussian09 program. The calculation results showed the obvious covalent interaction between the coordinated atoms and Cd(Ⅱ) ion.
Two new metal-organic supramolecular coordination compounds[Cd(cba)2(bix)]2 (1) and[Zn(cba)2(bix)]2 (2) (Hcba=2-chlorinebenzoic acid, bix=1, 4-bis(imidazol-1-ylmethyl) benzene) have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG, fluorescence spectrum, single-crystal and powder X-ray diffraction. Complexes 1 and 2 are isomorphism, and all exhibit zero-dimensional framework and display three-dimensional supramolecular network via π-π stacking interactions. In addition, natural bond orbital (NBO) of 1 were analyzed by using the PBE0/LANL2DZ method built in Gaussian09 program. The calculation results showed the obvious covalent interaction between the coordinated atoms and Cd(Ⅱ) ion.
2018, 34(10): 1929-1935
doi: 10.11862/CJIC.2018.223
Abstract:
The Co3O4 rectangular prism assembled by nanoparticles has been successfully fabricated via a two-step method. The first step involves the synthesis of CoC2O4·2H2O rectangular prism by a simple condensing reflux method. The second step includes the calcination of the as-prepared CoC2O4·2H2O rectangular prism at 350℃ for 2 h, causing its decomposition to form Co3O4 rectangular prism without destructing of the original morphology. The mechanical properties were characterized by powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption-desorption, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and H2 temperature-programmed reduction (H2-TPR). The results showed that the catalytic activity of Co3O4 rectangular prism for the combustion of ventilation air methane was higher than that of commercial Co3O4. The superior catalytic performance could be attributed to the high surface Co3+ content, high surface adsorbed oxygen content, and exposing the {111} planes.
The Co3O4 rectangular prism assembled by nanoparticles has been successfully fabricated via a two-step method. The first step involves the synthesis of CoC2O4·2H2O rectangular prism by a simple condensing reflux method. The second step includes the calcination of the as-prepared CoC2O4·2H2O rectangular prism at 350℃ for 2 h, causing its decomposition to form Co3O4 rectangular prism without destructing of the original morphology. The mechanical properties were characterized by powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption-desorption, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and H2 temperature-programmed reduction (H2-TPR). The results showed that the catalytic activity of Co3O4 rectangular prism for the combustion of ventilation air methane was higher than that of commercial Co3O4. The superior catalytic performance could be attributed to the high surface Co3+ content, high surface adsorbed oxygen content, and exposing the {111} planes.
2018, 34(10): 1936-1942
doi: 10.11862/CJIC.2018.242
Abstract:
Two coordination polymers, namely {[Mn2(L)2(H2O)5]·2H2O}n (1) and[Cd(L)(H2O)2]n (2), have been assembled from the π-conjugated ligand of 3, 3'-(1, 3, 6, 8-tetraoxobenzol[lmn][3, 8]-phenanthroline-2, 7(1H, 3H, 6H, 8H)diyl)-di-benzoic acid) (H2L) under hydrothermal condition. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses (EA), IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Structural analysis reveals that complex 1 is a 2D sheet with 1D { Mn3(COO)2} chain, which was further expanded to a 3D supramolecular structure through hydrogen bonds. While complex 2 is a 1D polymeric chain, which can be packed into a 3D supramolecular through hydrogen bonding interactions. Besides, the variable-temperature susceptibility of 1 as well as the photocatalytic activity of 2 have been investigated.
Two coordination polymers, namely {[Mn2(L)2(H2O)5]·2H2O}n (1) and[Cd(L)(H2O)2]n (2), have been assembled from the π-conjugated ligand of 3, 3'-(1, 3, 6, 8-tetraoxobenzol[lmn][3, 8]-phenanthroline-2, 7(1H, 3H, 6H, 8H)diyl)-di-benzoic acid) (H2L) under hydrothermal condition. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses (EA), IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Structural analysis reveals that complex 1 is a 2D sheet with 1D { Mn3(COO)2} chain, which was further expanded to a 3D supramolecular structure through hydrogen bonds. While complex 2 is a 1D polymeric chain, which can be packed into a 3D supramolecular through hydrogen bonding interactions. Besides, the variable-temperature susceptibility of 1 as well as the photocatalytic activity of 2 have been investigated.
2018, 34(10): 1783-1791
doi: 10.11862/CJIC.2018.217
Abstract:
Four new chromium picolinate derivatives were synthesized and characterized by X-ray crystal diffraction, ESI-MS, analytical element, conductivity and IR analysis. The effect of substituent groups on its redox property and hydroxyl radical (·OH) generation induced by the complex were investigated by cyclic voltammetry and Fenton-like reaction. As a result, three complexes generate less ·OH than Cr(pic)3. Besides, acute toxicity and antihyperglycemic effect indicated that high dose of complex 3 is hypotoxic and exhibited more efficiency than Cr(pic)3 in reducing fasten blood glucose (FBG) and low density lipoprotein by low dose.
Four new chromium picolinate derivatives were synthesized and characterized by X-ray crystal diffraction, ESI-MS, analytical element, conductivity and IR analysis. The effect of substituent groups on its redox property and hydroxyl radical (·OH) generation induced by the complex were investigated by cyclic voltammetry and Fenton-like reaction. As a result, three complexes generate less ·OH than Cr(pic)3. Besides, acute toxicity and antihyperglycemic effect indicated that high dose of complex 3 is hypotoxic and exhibited more efficiency than Cr(pic)3 in reducing fasten blood glucose (FBG) and low density lipoprotein by low dose.
2018, 34(10): 1792-1798
doi: 10.11862/CJIC.2018.232
Abstract:
SnO2 fibers and SnO2-C fibers were synthesized through electrospun technology and calcined under air or Ar atmosphere. Samples were characterized by different methods. The results showed that SnO2 fibers and SnO2-C fibers have a grid-like structure, which can effectively alleviate the disadvantages caused by the huge volume change of SnO2 during charging-discharging process. SnO2-C fibers showed a better electrochemical performance than SnO2 nanoparticles, but worse than that of SnO2 fibers. SnO2 fibers could discharged a much high capacity and had a good rate performance and long cycle life at the same time. After working at the current density of 0.4, 0.8, 1.6, 2.4 A·g-1 and 4 A·g-1 for 10 cycles, SnO2 fibers could still discharge a capacity of 1 372, 832, 685, 642 and 599 mAh·g-1. And when the current density went back to 0.4 A·g-1, its capacity could arrive 1 113 mAh·g-1 again. Furthermore, the SnO2 fibers could also release a high discharge capacity of 613 mAh·g-1 and almost 100% coulomb efficiency after 200 cycles at the current density of 1.6 A·g-1, showing an excellent electrochemistry performance.
SnO2 fibers and SnO2-C fibers were synthesized through electrospun technology and calcined under air or Ar atmosphere. Samples were characterized by different methods. The results showed that SnO2 fibers and SnO2-C fibers have a grid-like structure, which can effectively alleviate the disadvantages caused by the huge volume change of SnO2 during charging-discharging process. SnO2-C fibers showed a better electrochemical performance than SnO2 nanoparticles, but worse than that of SnO2 fibers. SnO2 fibers could discharged a much high capacity and had a good rate performance and long cycle life at the same time. After working at the current density of 0.4, 0.8, 1.6, 2.4 A·g-1 and 4 A·g-1 for 10 cycles, SnO2 fibers could still discharge a capacity of 1 372, 832, 685, 642 and 599 mAh·g-1. And when the current density went back to 0.4 A·g-1, its capacity could arrive 1 113 mAh·g-1 again. Furthermore, the SnO2 fibers could also release a high discharge capacity of 613 mAh·g-1 and almost 100% coulomb efficiency after 200 cycles at the current density of 1.6 A·g-1, showing an excellent electrochemistry performance.
2018, 34(10): 1799-1807
doi: 10.11862/CJIC.2018.231
Abstract:
Poly(3, 4-ethylenedioxythiophene) (PEDOT) microtube electrodes doped with different acids and surfactants were obtained by one-step electrochemical deposition method and could be used for flexible and all-solid-state supercapacitors (SCs). We also investigated the effect of deposition time on the capacitance performance of PEDOT microtubes doped with the same acid medium and surfactant. The structures of the final product were characterized by different characterization techniques including scanning electron microscopy (SEM) and FT-IR spectra. The electrochemical results showed that the capacitance of PEDOT microtubes doped with sulfuric acid (H2SO4) and sodium dodecyl sulfate (SDS) could be improved significantly. The areal capacitance of the prepared supercapacitor with deposition time of 600 s could achieve to 113.5 mF·cm-2 at the scan rate of 10 mV·s-1. The areal capacitances under the different bending angles remained at 93% of initial capacitive value revealing that the supercapacitor had highly mechanical stability. In addition, it remained 95.5% of the initial capacitive value after 2 000 cycles at a current density of 0.6 mA·cm-2 showing its superior cycling stability. The prepared flexible all-solid-state supercapacitor can power a light-emitting-diode (LED) which meets the practical applications of micro-power supplies.
Poly(3, 4-ethylenedioxythiophene) (PEDOT) microtube electrodes doped with different acids and surfactants were obtained by one-step electrochemical deposition method and could be used for flexible and all-solid-state supercapacitors (SCs). We also investigated the effect of deposition time on the capacitance performance of PEDOT microtubes doped with the same acid medium and surfactant. The structures of the final product were characterized by different characterization techniques including scanning electron microscopy (SEM) and FT-IR spectra. The electrochemical results showed that the capacitance of PEDOT microtubes doped with sulfuric acid (H2SO4) and sodium dodecyl sulfate (SDS) could be improved significantly. The areal capacitance of the prepared supercapacitor with deposition time of 600 s could achieve to 113.5 mF·cm-2 at the scan rate of 10 mV·s-1. The areal capacitances under the different bending angles remained at 93% of initial capacitive value revealing that the supercapacitor had highly mechanical stability. In addition, it remained 95.5% of the initial capacitive value after 2 000 cycles at a current density of 0.6 mA·cm-2 showing its superior cycling stability. The prepared flexible all-solid-state supercapacitor can power a light-emitting-diode (LED) which meets the practical applications of micro-power supplies.
2018, 34(10): 1808-1816
doi: 10.11862/CJIC.2018.228
Abstract:
This work developed a novel approach to prepare the CNTs/CNRs mixed nanomaterials by nanocasting method with tuning HNTs/PVA proportion, which employed HNTs as template and PVA as carbon source. We explored the effect of HNTs/PVA proportion on the structure of the mixed carbon nanomaterials. A series of characterizations, such as XRD, FTIR, Raman, N2 adsorption-desorption, TEM, SEM, resistivity and dispersibility, were used to determine the structure of the CNTs/CNRs mixed nanomaterials. The results found that PVA nanocasting content in the hollow nanostructure of HNTs affected the increase of CNRs in the CNTs/CNRs mixed nanomaterials. Upon the mass proportion of PVA/HNTs up to 1:1, the pore volume of the CNTs/CNRs mixed nanomaterials approached to the maximum of 2.142 cm3·g-1 and the specific surface area was up to 583 m2·g-1, and definitely showed a better conductivity and dispersibility, demonstrating that a lower PVA nanocasting content in HNTs could fulfilled a higher CNTs content in the CNTs/CNRs mixed nanomaterials.
This work developed a novel approach to prepare the CNTs/CNRs mixed nanomaterials by nanocasting method with tuning HNTs/PVA proportion, which employed HNTs as template and PVA as carbon source. We explored the effect of HNTs/PVA proportion on the structure of the mixed carbon nanomaterials. A series of characterizations, such as XRD, FTIR, Raman, N2 adsorption-desorption, TEM, SEM, resistivity and dispersibility, were used to determine the structure of the CNTs/CNRs mixed nanomaterials. The results found that PVA nanocasting content in the hollow nanostructure of HNTs affected the increase of CNRs in the CNTs/CNRs mixed nanomaterials. Upon the mass proportion of PVA/HNTs up to 1:1, the pore volume of the CNTs/CNRs mixed nanomaterials approached to the maximum of 2.142 cm3·g-1 and the specific surface area was up to 583 m2·g-1, and definitely showed a better conductivity and dispersibility, demonstrating that a lower PVA nanocasting content in HNTs could fulfilled a higher CNTs content in the CNTs/CNRs mixed nanomaterials.
2018, 34(10): 1817-1825
doi: 10.11862/CJIC.2018.222
Abstract:
The R-Y-Ni based A2B7-type R0.3Y0.7Ni3.25Mn0.15Al0.1 (R=Y, La, Pr, Ce, Nd, Gd, Sm) alloys were prepared by vacuum arc melting and followed by annealing treatment. The effects of rare earth element R on the microstructure, hydrogen storage and electrochemical properties of the alloys were investigated systematically. XRD and SEM-EDS analysis showed that the annealed alloys mainly composed of Ce2Ni7-type main phases, minor PuNi3-type and CaCu5-type phases. The lattice constants a, c and cell volume V of the Ce2Ni7-type main phases decreased in sequence with the decreasing radius of R atoms. The annealed alloys obviously presented a hydrogen absorption/desorption platform, the maximum hydrogen storage capacities and the equilibrium hydrogen absorption pressures (Peq) at room temperature were in the range of 1.17%~1.48% (w/w) and 0.037~0.194 MPa, respectively. Electrochemical analysis showed that the electrochemical activation performance was excellent. The heterogeneity of microstructure and electrochemical oxidation corrosion of rare earth elements were main reason that affected the cycling stability of alloy electrodes. For all the alloys, the R=La alloys exhibited the highest electrochemical discharge capacity of 389.2 mAh·g-1 and the best cyclic stability S100=85.7% (charge/discharge after 100 cycles). The high rate discharge ability HRD900 (current density was 900 mA·g-1) of the alloys was 71.05%~86.94% and the control step of the reaction kinetics was mainly controlled by the diffusion rate of the hydrogen atom in the alloys.
The R-Y-Ni based A2B7-type R0.3Y0.7Ni3.25Mn0.15Al0.1 (R=Y, La, Pr, Ce, Nd, Gd, Sm) alloys were prepared by vacuum arc melting and followed by annealing treatment. The effects of rare earth element R on the microstructure, hydrogen storage and electrochemical properties of the alloys were investigated systematically. XRD and SEM-EDS analysis showed that the annealed alloys mainly composed of Ce2Ni7-type main phases, minor PuNi3-type and CaCu5-type phases. The lattice constants a, c and cell volume V of the Ce2Ni7-type main phases decreased in sequence with the decreasing radius of R atoms. The annealed alloys obviously presented a hydrogen absorption/desorption platform, the maximum hydrogen storage capacities and the equilibrium hydrogen absorption pressures (Peq) at room temperature were in the range of 1.17%~1.48% (w/w) and 0.037~0.194 MPa, respectively. Electrochemical analysis showed that the electrochemical activation performance was excellent. The heterogeneity of microstructure and electrochemical oxidation corrosion of rare earth elements were main reason that affected the cycling stability of alloy electrodes. For all the alloys, the R=La alloys exhibited the highest electrochemical discharge capacity of 389.2 mAh·g-1 and the best cyclic stability S100=85.7% (charge/discharge after 100 cycles). The high rate discharge ability HRD900 (current density was 900 mA·g-1) of the alloys was 71.05%~86.94% and the control step of the reaction kinetics was mainly controlled by the diffusion rate of the hydrogen atom in the alloys.
2018, 34(10): 1826-1832
doi: 10.11862/CJIC.2018.226
Abstract:
The layered yttrium hydroxide (LYH) composite (FN/OS-LYH, where FN is fluorescein, 2-(6-hydroxy-3-oxo-(3H)-xanthen-9-yl)benzoic acid, and OS is the anionic surfactant of 1-octane sulfonic acid sodium) is synthesized. The photoluminescence property of the FN/OS-LYH and the application on detection of Hg(Ⅱ) ions of the delaminated FN/OS-LYH is studied. In solid state, pure FN salt shows no any emission, while the FN/OS-LYH composite displays yellow-green emission at 564 nm, and at delaminated state in formamide (FM), it displays a green emission at 540 nm (with 24 nm blue shift), in contrast to the 572 nm emission of free FN anions with a 32 nm blue shift. The delaminated FN/OS-LYH colloidal suspension exhibits high selectivity for Hg2+ over other ions (Mg2+, Ni2+, Co2+, Cu2+, Zn2+, Pb2+, and Cd2+) with fluorescence quenching. The detection limit of Hg2+ is determined to be 2.73×10-7 mol·L-1 and the quenching constant (Ksv) is 4.82×102 L·mol-1.
The layered yttrium hydroxide (LYH) composite (FN/OS-LYH, where FN is fluorescein, 2-(6-hydroxy-3-oxo-(3H)-xanthen-9-yl)benzoic acid, and OS is the anionic surfactant of 1-octane sulfonic acid sodium) is synthesized. The photoluminescence property of the FN/OS-LYH and the application on detection of Hg(Ⅱ) ions of the delaminated FN/OS-LYH is studied. In solid state, pure FN salt shows no any emission, while the FN/OS-LYH composite displays yellow-green emission at 564 nm, and at delaminated state in formamide (FM), it displays a green emission at 540 nm (with 24 nm blue shift), in contrast to the 572 nm emission of free FN anions with a 32 nm blue shift. The delaminated FN/OS-LYH colloidal suspension exhibits high selectivity for Hg2+ over other ions (Mg2+, Ni2+, Co2+, Cu2+, Zn2+, Pb2+, and Cd2+) with fluorescence quenching. The detection limit of Hg2+ is determined to be 2.73×10-7 mol·L-1 and the quenching constant (Ksv) is 4.82×102 L·mol-1.
2018, 34(10): 1833-1840
doi: 10.11862/CJIC.2018.214
Abstract:
Solvothermal reactions of a p-bitmb ligand (4-bis(1-imidazol-1-ylmethyl)-2, 3, 5, 6-tetramethyl benzene) with[Os(arene)Cl2]2 in dichloromethane were used to yield novel mononuclear osmium complexes 1 and 2 (1, arene=p-cym; 2, arene=bip), which were fully characterized by 1H NMR, ESI-MS, elemental analysis and single-crystal X-ray diffraction analysis. X-ray diffraction revealed that 1 is a mononuclear arene-osmium complex, forming a "bowl-like" structure that belongs to monoclinic system with space P21/c. The center osmium atom is coordinated with two nitrogen atom from ligands (p-bitmb) and Cl anion, whereas other imidazole ring of ligand is connected by a-CH2-group to form a dipositive bis-imidazolium center. Cl- anion can be trapped inside the cavity of this "bowl-like" structure, forming H-bonds with the backbone. 1H NMR study showed that the source of the bridging-CH2-group is the solvent, CH2Cl2. These complexes are stable in the buffer solution confirmed by the stability study with UV-Vis spectra. Furthermore, the results of UV-Vis spectra, circular dichroism and viscosity measurements revealed significant interactions between 1, 2 and calf thymus DNA (CT-DNA) via the intercalation, reduction of the base stacking, and induction of the DNA despiralization.
Solvothermal reactions of a p-bitmb ligand (4-bis(1-imidazol-1-ylmethyl)-2, 3, 5, 6-tetramethyl benzene) with[Os(arene)Cl2]2 in dichloromethane were used to yield novel mononuclear osmium complexes 1 and 2 (1, arene=p-cym; 2, arene=bip), which were fully characterized by 1H NMR, ESI-MS, elemental analysis and single-crystal X-ray diffraction analysis. X-ray diffraction revealed that 1 is a mononuclear arene-osmium complex, forming a "bowl-like" structure that belongs to monoclinic system with space P21/c. The center osmium atom is coordinated with two nitrogen atom from ligands (p-bitmb) and Cl anion, whereas other imidazole ring of ligand is connected by a-CH2-group to form a dipositive bis-imidazolium center. Cl- anion can be trapped inside the cavity of this "bowl-like" structure, forming H-bonds with the backbone. 1H NMR study showed that the source of the bridging-CH2-group is the solvent, CH2Cl2. These complexes are stable in the buffer solution confirmed by the stability study with UV-Vis spectra. Furthermore, the results of UV-Vis spectra, circular dichroism and viscosity measurements revealed significant interactions between 1, 2 and calf thymus DNA (CT-DNA) via the intercalation, reduction of the base stacking, and induction of the DNA despiralization.
2018, 34(10): 1841-1850
doi: 10.11862/CJIC.2018.239
Abstract:
Three water-soluble copper porphyrin complexes (water-soluble bromine-containing copper porphyrin CuP-1 and its bromine substituted derivatives CuP-2 and CuP-3) have been synthesized and characterized by 1H NMR, elementary analysis and MS spectra. The interaction of CuP-1, CuP-2 and CuP-3 with CT-DNA have been investigated by UV spectrum, EB-DNA fluorescence quenching, viscosity method and circular dichroism spectrum. Moreover, the antitumor activities of CuP-1~CuP-3 against Hela (cervical cancer) cell lines and MDA (breast carcinoma) cell lines have been studied by MTT assay. L929 (human fibroblast) cell line was used as a normal cell lines. Various spectroscopic approaches indicates that CuP-1 could effectively bind with CT-DNA through intercalation mode, while CuP-2 and CuP-3 may interact with CT-DNA by outside groove binding mode. And the binding affinity of CuP-1 with CT-DNA is better than its derivatives CuP-2 and CuP-3. In vitro antitumor activity experiments showed that CuP-1~CuP-3 can inhibit the growth of Hela and MDA cell lines, and the inhibition shows concentration and time dependent. In addition, antitumor activity in vitro of CuP-1 is much better than CuP-2 and CuP-3.
Three water-soluble copper porphyrin complexes (water-soluble bromine-containing copper porphyrin CuP-1 and its bromine substituted derivatives CuP-2 and CuP-3) have been synthesized and characterized by 1H NMR, elementary analysis and MS spectra. The interaction of CuP-1, CuP-2 and CuP-3 with CT-DNA have been investigated by UV spectrum, EB-DNA fluorescence quenching, viscosity method and circular dichroism spectrum. Moreover, the antitumor activities of CuP-1~CuP-3 against Hela (cervical cancer) cell lines and MDA (breast carcinoma) cell lines have been studied by MTT assay. L929 (human fibroblast) cell line was used as a normal cell lines. Various spectroscopic approaches indicates that CuP-1 could effectively bind with CT-DNA through intercalation mode, while CuP-2 and CuP-3 may interact with CT-DNA by outside groove binding mode. And the binding affinity of CuP-1 with CT-DNA is better than its derivatives CuP-2 and CuP-3. In vitro antitumor activity experiments showed that CuP-1~CuP-3 can inhibit the growth of Hela and MDA cell lines, and the inhibition shows concentration and time dependent. In addition, antitumor activity in vitro of CuP-1 is much better than CuP-2 and CuP-3.
2018, 34(10): 1851-1856
doi: 10.11862/CJIC.2018.241
Abstract:
WO3/YF3:Eu3+ nanocomposite materials were prepared by direct precipitation method and its composition, structure, morphology and luminescent properties were investigated. XRD analysis showed that the nanocomposite is composed of WO3 and orthorhombic YF3:Eu3+. SEM showed that the nanocomposite is irregular flake structure, and it is obvious that many YF3:Eu3+ particles are uniformly deposited on the surface of WO3 flake. The particle size of YF3:Eu3+ nanoparticles is in the range of 10~50 nm. PL indicated that the strongest emission peak at 593 nm can be assigned to magnetic dipole transition of 5D0→7F1. Compared with the pure YF3:Eu3+, the luminescence intensity of WO3/YF3:Eu3+ is obviously enhanced. It showed that the WO3 with local surface plasmon resonance (LSPR) play a role in enhancing the luminescence properties of the shell YF3:Eu3+.
WO3/YF3:Eu3+ nanocomposite materials were prepared by direct precipitation method and its composition, structure, morphology and luminescent properties were investigated. XRD analysis showed that the nanocomposite is composed of WO3 and orthorhombic YF3:Eu3+. SEM showed that the nanocomposite is irregular flake structure, and it is obvious that many YF3:Eu3+ particles are uniformly deposited on the surface of WO3 flake. The particle size of YF3:Eu3+ nanoparticles is in the range of 10~50 nm. PL indicated that the strongest emission peak at 593 nm can be assigned to magnetic dipole transition of 5D0→7F1. Compared with the pure YF3:Eu3+, the luminescence intensity of WO3/YF3:Eu3+ is obviously enhanced. It showed that the WO3 with local surface plasmon resonance (LSPR) play a role in enhancing the luminescence properties of the shell YF3:Eu3+.
2018, 34(10): 1857-1863
doi: 10.11862/CJIC.2018.216
Abstract:
The 1, 5-asymmetric disubstituted carbohydrazide ligands were prepared by condensation of carbohy-drazide with salicylaldehyde and then with vanillin. The butyltin complex B1 based on the 1, 5-disubstituted carbohydrazide and the complex B2 containing salicylaldehyde azine were obtained by solvothermal reaction of n-BuSnCl3 with the ligand in methanol environments, which have been structurally characterized by elemental analysis, IR and 1H, 13C, 119Sn NMR spectra. The crystal of complex B1 belongs to monoclinic system, space group P21/n, and the crystal of complex B2 belongs to triclinic system, space group P1. The Sn atom is six-coordinated with distorted octahedral geometry by O, N atoms from ligand, C atom of butyl and two Cl atoms. The complex B1 had good fluorescence properties in the DMF-H2O solvents, and the water content in the 0~10%(V/V) range had aggregation induced emission enhancement(AIE). When the water content was more than 10%, the fluorescence intensity decreased with the increase of water volume fraction, and finally was quenched. The ligand and its butyltin complex B1 have the effect of growth on the target plants, such as Portulaca oleracea L., Amaranthus spinosus L., Cassia tora L., Brassica campestris L. ssp. chinensis var. utilis Tsen et Lee and Amaranthus tricolor L. The ligand has a good inhibitory effect on the growth of Portulaca oleracea L. and Amaranthus spinosus L., and the complex has selective inhibition on the growth of Cassia tora L., which can be used as a candidate compound for Cassia tora L. herbicide.
The 1, 5-asymmetric disubstituted carbohydrazide ligands were prepared by condensation of carbohy-drazide with salicylaldehyde and then with vanillin. The butyltin complex B1 based on the 1, 5-disubstituted carbohydrazide and the complex B2 containing salicylaldehyde azine were obtained by solvothermal reaction of n-BuSnCl3 with the ligand in methanol environments, which have been structurally characterized by elemental analysis, IR and 1H, 13C, 119Sn NMR spectra. The crystal of complex B1 belongs to monoclinic system, space group P21/n, and the crystal of complex B2 belongs to triclinic system, space group P1. The Sn atom is six-coordinated with distorted octahedral geometry by O, N atoms from ligand, C atom of butyl and two Cl atoms. The complex B1 had good fluorescence properties in the DMF-H2O solvents, and the water content in the 0~10%(V/V) range had aggregation induced emission enhancement(AIE). When the water content was more than 10%, the fluorescence intensity decreased with the increase of water volume fraction, and finally was quenched. The ligand and its butyltin complex B1 have the effect of growth on the target plants, such as Portulaca oleracea L., Amaranthus spinosus L., Cassia tora L., Brassica campestris L. ssp. chinensis var. utilis Tsen et Lee and Amaranthus tricolor L. The ligand has a good inhibitory effect on the growth of Portulaca oleracea L. and Amaranthus spinosus L., and the complex has selective inhibition on the growth of Cassia tora L., which can be used as a candidate compound for Cassia tora L. herbicide.
