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2017 Volume 33 Issue 5
2017, 33(5): 713-737
doi: 10.11862/CJIC.2017.105
Abstract:
The syntheses methods, structure characteristics and various applications of UiO series of metal-organic frameworks (MOFs) including UiO-66, UiO-67 and UiO-68 were reviewed. The syntheses methods of UiO series of MOFs like evaporation, solvothermal method, microwave-assisted synthesis, mechanochemical synthesis, continuous flow method, and electrochemical synthesis were introduced. The detailed reaction conditions, the compositions and structures characteristic of the final products, and the advantages/disadvantages of above-stated syntheses methods were analyzed. UiO-MOFs possessed both ultrahigh thermal stability and chemical stability resulted from their strong Zr-O bond and high coordination number of Zr (Ⅳ). Considering UiO-MOFs exceptional porosity with uniform but tunable pore sizes, incredibly high internal surface areas and the active Zr-O clusters, they had been used extensively in many research fields like catalysis, photocatalysis, gas adsorption, gas separation, adsorptive removal of organic pollutants in wastewater, medical, capacitor and so on. Finally, the research trends of UiO-MOFs are prospected.
The syntheses methods, structure characteristics and various applications of UiO series of metal-organic frameworks (MOFs) including UiO-66, UiO-67 and UiO-68 were reviewed. The syntheses methods of UiO series of MOFs like evaporation, solvothermal method, microwave-assisted synthesis, mechanochemical synthesis, continuous flow method, and electrochemical synthesis were introduced. The detailed reaction conditions, the compositions and structures characteristic of the final products, and the advantages/disadvantages of above-stated syntheses methods were analyzed. UiO-MOFs possessed both ultrahigh thermal stability and chemical stability resulted from their strong Zr-O bond and high coordination number of Zr (Ⅳ). Considering UiO-MOFs exceptional porosity with uniform but tunable pore sizes, incredibly high internal surface areas and the active Zr-O clusters, they had been used extensively in many research fields like catalysis, photocatalysis, gas adsorption, gas separation, adsorptive removal of organic pollutants in wastewater, medical, capacitor and so on. Finally, the research trends of UiO-MOFs are prospected.
2017, 33(5): 738-744
doi: 10.11862/CJIC.2017.098
Abstract:
The Ag2O/TiO2 composite was synthesized via a facile flame thermal method using tetrabutyl orthotitanate and AgNO3 as precursors. The samples were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible diffuse reflectance spectroscope (UV-Vis DRS) and photocatalytic hydrogen evolution under UV-Vis light irradiation. XRD results showed that anatase TiO2 was obtained directly and no obvious effect on the crystal structure was observed with the introduction of desired amount of Ag. SEM images show microspherical morphology for the as-synthesized samples without Ag and irregular morphology for those with higher content of Ag. XPS and chemical precipitation method results indicated that Ag existed in the forms of Ag2O in the resulted samples. UV-Vis DRS showed that the introduction of Ag could enhance light absorption. The highest photocatalytic hydrogen generation rate of sample was about 15 times as high as that of P25. The sample after photocatalytic reaction was chemically analyzed and it is assumed that the Ag2O was partly photoreduced to Ag, which further benefits the photocatalytic hydrogen production from Ag/TiO2 heterostructures.
The Ag2O/TiO2 composite was synthesized via a facile flame thermal method using tetrabutyl orthotitanate and AgNO3 as precursors. The samples were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible diffuse reflectance spectroscope (UV-Vis DRS) and photocatalytic hydrogen evolution under UV-Vis light irradiation. XRD results showed that anatase TiO2 was obtained directly and no obvious effect on the crystal structure was observed with the introduction of desired amount of Ag. SEM images show microspherical morphology for the as-synthesized samples without Ag and irregular morphology for those with higher content of Ag. XPS and chemical precipitation method results indicated that Ag existed in the forms of Ag2O in the resulted samples. UV-Vis DRS showed that the introduction of Ag could enhance light absorption. The highest photocatalytic hydrogen generation rate of sample was about 15 times as high as that of P25. The sample after photocatalytic reaction was chemically analyzed and it is assumed that the Ag2O was partly photoreduced to Ag, which further benefits the photocatalytic hydrogen production from Ag/TiO2 heterostructures.
2017, 33(5): 745-752
doi: 10.11862/CJIC.2017.100
Abstract:
By using the mica (001) lattice plane as the substrate and rat tail type Ⅰ collagen monomers as adsorbates, both 'bottom-up' self-assembly of protein monomers guided by the substrate and 'top-down' manipulation of protein membrane by AFM tip were investigated:(1) both preparation approaches can fabricate collagen nanowire arrays with precisely controllable structures; (2) the 'bottom-up' approach was due to the 'reverse-phase biomineralization' mechanism arising from the cooperative recognition and regulation between the protein and substrate at the interface; (3) the 'top-down' manipulation was based on the 'molecular broom' mechanism of the AFM tip in the Contact Mode.
By using the mica (001) lattice plane as the substrate and rat tail type Ⅰ collagen monomers as adsorbates, both 'bottom-up' self-assembly of protein monomers guided by the substrate and 'top-down' manipulation of protein membrane by AFM tip were investigated:(1) both preparation approaches can fabricate collagen nanowire arrays with precisely controllable structures; (2) the 'bottom-up' approach was due to the 'reverse-phase biomineralization' mechanism arising from the cooperative recognition and regulation between the protein and substrate at the interface; (3) the 'top-down' manipulation was based on the 'molecular broom' mechanism of the AFM tip in the Contact Mode.
2017, 33(5): 753-760
doi: 10.11862/CJIC.2017.103
Abstract:
The Eu3+ doped calcium bismuth borate glasses were prepared by a rapid melt quenching technique. The general physical properties including density, molar volume, refractive index and so on were studied. Furthermore, the structure, optical properties and thermal stability of glasses with different nB/nBi and CaO concentration were also investigated. The experimental results demonstrate that Eu3+ is melted homogeneously in glass samples and acts as a well activator. An intense emission peak at 613 nm appears in the emission spectra under 465 nm excitation. The excited and emitted spectra intensities have no obvious variation as nB/nBi gradually decreasing, but that decrease with CaO concentration increasing. All glass samples present amorphous states and relative low symmetric structure. The tightness and symmetries of glass structure decrease totally as nB/nBi decreasing and increase as CaO concentration increasing. The[BO3], [BO4], [BiO3] and[BiO6] units are identified in glass samples, however, six member rings consisting of[BO3] are not observed. The glass samples possess red light under matching blue light chip, and exhibit many virtues such as well thermal stability, low melting temperature and appropriate refractive index.
The Eu3+ doped calcium bismuth borate glasses were prepared by a rapid melt quenching technique. The general physical properties including density, molar volume, refractive index and so on were studied. Furthermore, the structure, optical properties and thermal stability of glasses with different nB/nBi and CaO concentration were also investigated. The experimental results demonstrate that Eu3+ is melted homogeneously in glass samples and acts as a well activator. An intense emission peak at 613 nm appears in the emission spectra under 465 nm excitation. The excited and emitted spectra intensities have no obvious variation as nB/nBi gradually decreasing, but that decrease with CaO concentration increasing. All glass samples present amorphous states and relative low symmetric structure. The tightness and symmetries of glass structure decrease totally as nB/nBi decreasing and increase as CaO concentration increasing. The[BO3], [BO4], [BiO3] and[BiO6] units are identified in glass samples, however, six member rings consisting of[BO3] are not observed. The glass samples possess red light under matching blue light chip, and exhibit many virtues such as well thermal stability, low melting temperature and appropriate refractive index.
2017, 33(5): 761-768
doi: 10.11862/CJIC.2017.086
Abstract:
La7O6(BO3)(PO4)2:Tb3+ and La7O6(BO3)(PO4)2:Eu3+ phosphors were prepared by a high-temperature solid state reaction, and the phase behavior, crystal structure, luminescence properties and thermal stability were investigated. The La7O6(BO3)(PO4)2:Eu3+ phosphors emitted a red light under the ultraviolet excitation. The emission maximum was at 616 nm, corresponding to the 5D0-7F2 transition of Eu3+. The concentration quenching pheno-menon was observed when the doping concentration of Eu3+ ion was beyond 0.08. The corresponding CIE coordinates were calculated to be (0.610 2, 0.382 3). The La7O6(BO3)(PO4)2:Tb3+ phosphors emitted a green light under the ultraviolet excitation. The emission maximum was at 544 nm, corresponding to the 5D4-7F5 transition of Tb3+. Concentration quenching phenomenon was observed when the concentration of Tb3+ ion was beyond 0.15, and its CIE coordinates are calculated to be (0.317 7, 0.535 2). Based on the analysis of temperature-dependent emission spectra of La7O6(BO3)(PO4)2:Tb3+ and La7O6(BO3)(PO4)2:Eu3+ phosphors, it can be found that both phosphors possess good thermal stability.
La7O6(BO3)(PO4)2:Tb3+ and La7O6(BO3)(PO4)2:Eu3+ phosphors were prepared by a high-temperature solid state reaction, and the phase behavior, crystal structure, luminescence properties and thermal stability were investigated. The La7O6(BO3)(PO4)2:Eu3+ phosphors emitted a red light under the ultraviolet excitation. The emission maximum was at 616 nm, corresponding to the 5D0-7F2 transition of Eu3+. The concentration quenching pheno-menon was observed when the doping concentration of Eu3+ ion was beyond 0.08. The corresponding CIE coordinates were calculated to be (0.610 2, 0.382 3). The La7O6(BO3)(PO4)2:Tb3+ phosphors emitted a green light under the ultraviolet excitation. The emission maximum was at 544 nm, corresponding to the 5D4-7F5 transition of Tb3+. Concentration quenching phenomenon was observed when the concentration of Tb3+ ion was beyond 0.15, and its CIE coordinates are calculated to be (0.317 7, 0.535 2). Based on the analysis of temperature-dependent emission spectra of La7O6(BO3)(PO4)2:Tb3+ and La7O6(BO3)(PO4)2:Eu3+ phosphors, it can be found that both phosphors possess good thermal stability.
2017, 33(5): 787-795
doi: 10.11862/CJIC.2017.102
Abstract:
The Au/Fe3O4 catalyst was successfully prepared by the simple ultrasonic method and in-situ reduction method. Au was immobilized on the surface of Fe3O4 using APTES as an organic bridging bond to obtain monodisperse magnetic Au/Fe3O4. Au0 could not agglomerated in the condition of NH3+, so that it had high catalytic activity and stability. The results of XRD, HRTEM, EDS and XPS showed that Au/Fe3O4 has been prepared successfully. It was used to catalyze the reduction of 4-nitrophenols to 4-aminophenols, which showed high catalytic activity with rate constant of 0.225 6 min-1. The repeatability test showed that the catalyst had good stability. After 9 cycles of reaction, the conversion rate of the reaction was still 94%.
The Au/Fe3O4 catalyst was successfully prepared by the simple ultrasonic method and in-situ reduction method. Au was immobilized on the surface of Fe3O4 using APTES as an organic bridging bond to obtain monodisperse magnetic Au/Fe3O4. Au0 could not agglomerated in the condition of NH3+, so that it had high catalytic activity and stability. The results of XRD, HRTEM, EDS and XPS showed that Au/Fe3O4 has been prepared successfully. It was used to catalyze the reduction of 4-nitrophenols to 4-aminophenols, which showed high catalytic activity with rate constant of 0.225 6 min-1. The repeatability test showed that the catalyst had good stability. After 9 cycles of reaction, the conversion rate of the reaction was still 94%.
2017, 33(5): 796-800
doi: 10.11862/CJIC.2017.111
Abstract:
Molybdenum disulfide, which is composed of a monolayer or few layers, is a new kind of two-dimensional materials following the study of grapheme. It is a kind of direct band-gap semiconductor with excellent photoelectric properties, which has attracted much attention. In this paper, molybdenum disulfide with different particle size was successfully prepared by heat-up method. The MoCl5 was reacted with L-cysteine in the presence of oleylamine at 220℃, and we performed different reaction time from 1 to 5 h to understand the formation mechanism. There are two mechanisms occurred in the formation process of MoS2 nanodots:one is the Ostwald ripening and the other is an epitaxial growth. Until there are no enough nuclei for growth, the size remains unchanged regardless of the growth of the time. The prepared MoS2 nanodots are homogeneous in the aspects of size and height from the large range due to the protection of OLA. In addition, OLA providing a strong reductive environment reduces Mo5+ to Mo4+ and avoids oxidation of the nanoparticles, which integrated with L-cysteine to results in the formation of H2S. The molybdenum disulfide quantum dots prepared for 3 h had monolayer structure. We also investigate the photoluminescence behaviors of the materials to inquire the size effect. The fluorescence spectra and Raman spectra of three kinds of molybdenum disulfides were studied. It was found that when the particle size or the excitation wavelength increased, the peak position of the fluorescence spectrum occurred red shift.
Molybdenum disulfide, which is composed of a monolayer or few layers, is a new kind of two-dimensional materials following the study of grapheme. It is a kind of direct band-gap semiconductor with excellent photoelectric properties, which has attracted much attention. In this paper, molybdenum disulfide with different particle size was successfully prepared by heat-up method. The MoCl5 was reacted with L-cysteine in the presence of oleylamine at 220℃, and we performed different reaction time from 1 to 5 h to understand the formation mechanism. There are two mechanisms occurred in the formation process of MoS2 nanodots:one is the Ostwald ripening and the other is an epitaxial growth. Until there are no enough nuclei for growth, the size remains unchanged regardless of the growth of the time. The prepared MoS2 nanodots are homogeneous in the aspects of size and height from the large range due to the protection of OLA. In addition, OLA providing a strong reductive environment reduces Mo5+ to Mo4+ and avoids oxidation of the nanoparticles, which integrated with L-cysteine to results in the formation of H2S. The molybdenum disulfide quantum dots prepared for 3 h had monolayer structure. We also investigate the photoluminescence behaviors of the materials to inquire the size effect. The fluorescence spectra and Raman spectra of three kinds of molybdenum disulfides were studied. It was found that when the particle size or the excitation wavelength increased, the peak position of the fluorescence spectrum occurred red shift.
2017, 33(5): 801-808
doi: 10.11862/CJIC.2017.106
Abstract:
The Tm3+, Er3+ and Ho3+ co-doped bismuth silicate glasses 50SiO2-40Bi2O3-5AlF3-5BaF2 were prepared by high-temperature melt-quenching method. The spectroscopic properties of Tm3+, Er3+ and Ho3+ co-doped bismuth silicate at 2 060 nm exited by 808 nm Laser Diode were investigated. Thermal stability of the glasses, absorption spectra and fluorescence spectra of the Tm3+, Er3+ and Ho3+ co-doped glass samples were measured. According to the absorption spectrum and Judd-Oflet theory, the Judd-Oflet intensity parameters of Ho3+ Ωt(t=2, 4, 6), absorption cross sections of Tm3+, Er3+ and Ho3+ were calculated, respectively. The measured fluorescence spectra manifest that the maximal emission intensity of Ho3+:5I7→5I8 at 2 060 nm can be achieved at the concentration of 0.75% Tm2O3, 1.0% Er2O3 and 0.5% Ho2O3 in bismuth silicate glasses. Besides the spectroscopic properties of Tm3+, Er3+ and Ho3+ separately and possible energy transfer mechanisms among Tm3+, Er3+ and Ho3+ were analyzed and discussed in detail. The maximal absorption and emission cross sections of Ho3+ are 9.08×10-21 cm2 at 1 953 nm and 1.168×10-20 cm2 at 2 060 nm, respectively, with a lifetime of 2.75 ms, while large σemτ achieved (3.212×10-20 cm2·ms) suggesting its efficient application in 2 μm fiber lasers.
The Tm3+, Er3+ and Ho3+ co-doped bismuth silicate glasses 50SiO2-40Bi2O3-5AlF3-5BaF2 were prepared by high-temperature melt-quenching method. The spectroscopic properties of Tm3+, Er3+ and Ho3+ co-doped bismuth silicate at 2 060 nm exited by 808 nm Laser Diode were investigated. Thermal stability of the glasses, absorption spectra and fluorescence spectra of the Tm3+, Er3+ and Ho3+ co-doped glass samples were measured. According to the absorption spectrum and Judd-Oflet theory, the Judd-Oflet intensity parameters of Ho3+ Ωt(t=2, 4, 6), absorption cross sections of Tm3+, Er3+ and Ho3+ were calculated, respectively. The measured fluorescence spectra manifest that the maximal emission intensity of Ho3+:5I7→5I8 at 2 060 nm can be achieved at the concentration of 0.75% Tm2O3, 1.0% Er2O3 and 0.5% Ho2O3 in bismuth silicate glasses. Besides the spectroscopic properties of Tm3+, Er3+ and Ho3+ separately and possible energy transfer mechanisms among Tm3+, Er3+ and Ho3+ were analyzed and discussed in detail. The maximal absorption and emission cross sections of Ho3+ are 9.08×10-21 cm2 at 1 953 nm and 1.168×10-20 cm2 at 2 060 nm, respectively, with a lifetime of 2.75 ms, while large σemτ achieved (3.212×10-20 cm2·ms) suggesting its efficient application in 2 μm fiber lasers.
2017, 33(5): 809-816
doi: 10.11862/CJIC.2017.087
Abstract:
A series of silver-modified TiO2 flexible film electrodes with hierarchical 3D nano-network structure are facilely synthesized using hydrothermal method followed via the traditional silver mirror reaction. Successful deposition of Ag nanoparticles on to the TiO2 nanowires surface is confirmed by inductively coupled plasma (ICP) technique, X-ray diffraction (XRD), scanning electron microscope (SEM) with energy-dispersive X-ray analysis (EDX) and transmission electron microscopy (TEM). The electrochemical properties of the Ag@TiO2 nanowires were researched in this work. Our results show that the Ag@TiO2 nanowires with 4.0%(w/w) silver exhibits a better rate performance and more excellent reversibility than pristine one. At different current densities of 50, 100, 200, 400, 800 and 1 200 mA·g-1, the discharge capacities of the Ag@TiO2 electrodes are 261.4, 253.7, 239.5, 216.5, 193.1 and 185.1 mAh·g-1, respectively. After 80 cycles at 200 mA·g-1, its discharge capacity retention is 99.8% indicating Ag@TiO2 electrodes are potentially useful for LIBs.
A series of silver-modified TiO2 flexible film electrodes with hierarchical 3D nano-network structure are facilely synthesized using hydrothermal method followed via the traditional silver mirror reaction. Successful deposition of Ag nanoparticles on to the TiO2 nanowires surface is confirmed by inductively coupled plasma (ICP) technique, X-ray diffraction (XRD), scanning electron microscope (SEM) with energy-dispersive X-ray analysis (EDX) and transmission electron microscopy (TEM). The electrochemical properties of the Ag@TiO2 nanowires were researched in this work. Our results show that the Ag@TiO2 nanowires with 4.0%(w/w) silver exhibits a better rate performance and more excellent reversibility than pristine one. At different current densities of 50, 100, 200, 400, 800 and 1 200 mA·g-1, the discharge capacities of the Ag@TiO2 electrodes are 261.4, 253.7, 239.5, 216.5, 193.1 and 185.1 mAh·g-1, respectively. After 80 cycles at 200 mA·g-1, its discharge capacity retention is 99.8% indicating Ag@TiO2 electrodes are potentially useful for LIBs.
2017, 33(5): 817-822
doi: 10.11862/CJIC.2017.095
Abstract:
By postsynthetic modification method (PSM), chiral metal-organic frameworks (MOFs) were designed and synthesized. The L-proline derivative (Boc-L-ProCl) was anchored on the pore of Cr-MIL-101-NH2 by PSM method to gain a chiral MOFs (Cr-MIL-101-PaB2). 1H NMR spectra confirmed the yield up to 64% by twice process of PSM, and solid circular dichroism (CD) result showed that Cr-MIL-101-PaB2 was a chiral compound. Their structures were characterized by infrared spectroscopy (IR), nitrogen desorption-adsorption, thermogravimetry (TGA), powder X-ray diffraction (PXRD). The experimental results confirmed that synthesized chiral MOFs by PSM method for the needed purpose can avoid the self-assembly uncertainty of MOFs.
By postsynthetic modification method (PSM), chiral metal-organic frameworks (MOFs) were designed and synthesized. The L-proline derivative (Boc-L-ProCl) was anchored on the pore of Cr-MIL-101-NH2 by PSM method to gain a chiral MOFs (Cr-MIL-101-PaB2). 1H NMR spectra confirmed the yield up to 64% by twice process of PSM, and solid circular dichroism (CD) result showed that Cr-MIL-101-PaB2 was a chiral compound. Their structures were characterized by infrared spectroscopy (IR), nitrogen desorption-adsorption, thermogravimetry (TGA), powder X-ray diffraction (PXRD). The experimental results confirmed that synthesized chiral MOFs by PSM method for the needed purpose can avoid the self-assembly uncertainty of MOFs.
2017, 33(5): 823-829
doi: 10.11862/CJIC.2017.104
Abstract:
Three novel coordination polymers, formulated as[Cd3(pic)4(H2bmimb)]n (1), [Co3(pic)4(H2bmimb)]n (2), [Cd2(1, 2-mbix)(pic)2(H2O)2]n (3) (H2bmimb=1, 4-bis ((2-methyl-1H-imidazol-1-yl) methyl) benzene, 1, 2-mbix=1, 2-bis ((2-methyl-1H-imidazol-1-yl) methyl) benzene, pic=5-phenylisophthalic acid), were synthesized by self-assembly of mixed ligands with Cd (Ⅱ) and Co (Ⅱ) under solvothermal conditions and characterized by means of single-crystal X-ray diffraction, X-ray powder diffraction, infrared spectra, thermogravimetric analysis and fluorescence spectra. Single-crystal X-ray diffraction analysis revealed that complexes 1 and 2 possess 3D anionic frameworks, in which the protonated bis-imidazole ligands balance the charge of the frameworks. In complex 3, the Cd2+ ions are linked by pic and 1, 2-mbix ligands to generate a 1D chain structure. The adjacent chains are held together to form a 2D layer via π…π stacking and then a 3D supramolecular framework through hydrogen-bonding interactions. In addition, luminescence properties of complexes 1 and 3 in the solid state were characterized.
Three novel coordination polymers, formulated as[Cd3(pic)4(H2bmimb)]n (1), [Co3(pic)4(H2bmimb)]n (2), [Cd2(1, 2-mbix)(pic)2(H2O)2]n (3) (H2bmimb=1, 4-bis ((2-methyl-1H-imidazol-1-yl) methyl) benzene, 1, 2-mbix=1, 2-bis ((2-methyl-1H-imidazol-1-yl) methyl) benzene, pic=5-phenylisophthalic acid), were synthesized by self-assembly of mixed ligands with Cd (Ⅱ) and Co (Ⅱ) under solvothermal conditions and characterized by means of single-crystal X-ray diffraction, X-ray powder diffraction, infrared spectra, thermogravimetric analysis and fluorescence spectra. Single-crystal X-ray diffraction analysis revealed that complexes 1 and 2 possess 3D anionic frameworks, in which the protonated bis-imidazole ligands balance the charge of the frameworks. In complex 3, the Cd2+ ions are linked by pic and 1, 2-mbix ligands to generate a 1D chain structure. The adjacent chains are held together to form a 2D layer via π…π stacking and then a 3D supramolecular framework through hydrogen-bonding interactions. In addition, luminescence properties of complexes 1 and 3 in the solid state were characterized.
2017, 33(5): 830-836
doi: 10.11862/CJIC.2017.107
Abstract:
Two di-n-butyltin carboxylates with a Sn4O4 ladder-like framework, [(μ3-O)(μ2-OMe)(n-Bu2Sn)2(O2CR)]2 (R=4-methylphenyl (1), 4-(dimethylamino) phenyl (2)), were obtained by the microwave-assisted solvothermal reaction of di-n-butyltin oxide precursor with the 4-methylbenzoic acid, 4-dimethylaminobenzoic acid in methanol environments, respectively. The compounds were characterized by elemental analysis, IR, (1H, 13C and 119Sn) NMR spectra and X-ray crystallography diffraction analyses. The compounds have similar structures containing a Sn4O4 ladder-like skeleton, in which two endo-cyclic tin and one exo-tin atoms is bonded to the μ3-O atom, in addition, one endo-cyclic tin and one exo-tin atoms is bonded to the μ2-O atom from the methanol, respectively. The ladder-like molecule has a three-ring fused skeleton, which is almost coplanar. The endo-cyclic and exo-cyclic tin atoms all are five-coordinated with distorted trigonal bipyramid geometry. The antitumor activity shows that compounds 1 and 2 have higher activities than cisplatin in HT-29, HepG2, MCF-7, KB and A549 cell line in vitro.
Two di-n-butyltin carboxylates with a Sn4O4 ladder-like framework, [(μ3-O)(μ2-OMe)(n-Bu2Sn)2(O2CR)]2 (R=4-methylphenyl (1), 4-(dimethylamino) phenyl (2)), were obtained by the microwave-assisted solvothermal reaction of di-n-butyltin oxide precursor with the 4-methylbenzoic acid, 4-dimethylaminobenzoic acid in methanol environments, respectively. The compounds were characterized by elemental analysis, IR, (1H, 13C and 119Sn) NMR spectra and X-ray crystallography diffraction analyses. The compounds have similar structures containing a Sn4O4 ladder-like skeleton, in which two endo-cyclic tin and one exo-tin atoms is bonded to the μ3-O atom, in addition, one endo-cyclic tin and one exo-tin atoms is bonded to the μ2-O atom from the methanol, respectively. The ladder-like molecule has a three-ring fused skeleton, which is almost coplanar. The endo-cyclic and exo-cyclic tin atoms all are five-coordinated with distorted trigonal bipyramid geometry. The antitumor activity shows that compounds 1 and 2 have higher activities than cisplatin in HT-29, HepG2, MCF-7, KB and A549 cell line in vitro.
2017, 33(5): 837-842
doi: 10.11862/CJIC.2017.096
Abstract:
A new water-soluble and more water-stable analogue of lobaplatin, cis-[Pt (Ⅱ)(trans-1, 2-bis (methylamino) cyclobutane)(3-hydroxyl-1, 1-cyclobutanedicarboxylate)], was designed, with an attempt to improve the water-stability of lobaplatin while retaining its excellent anticancer profile, via the structural recombination and optimization of lobaplatin and carboplatin. The analogue was synthesized by the direct reaction between cis-[Pt (Ⅱ)(trans-1, 2-bis (methylamino)) I2] as an intermediate and the silver salt of 3-hydroxyl-1, 1-cyclobutanedicarboxylic acid, and characterized by elemental analysis, ESI-MS, IR and 1H, 13C NMR. The anticancer activity was evaluated by both in vitro cyotoxicity against four human cancer cell lines and in vivo antitumor efficiency in human lung carcinoma NCI-H460 xenografts in nude mice. The biological tests revealed that the analogue produced significant inhibition of the tumor growth, resulting in an inhibitory rate of 54% at the dose of 60 mg·kg-1 and more importantly, it had in vivo anticancer activity comparable to that of lobaplatin.
A new water-soluble and more water-stable analogue of lobaplatin, cis-[Pt (Ⅱ)(trans-1, 2-bis (methylamino) cyclobutane)(3-hydroxyl-1, 1-cyclobutanedicarboxylate)], was designed, with an attempt to improve the water-stability of lobaplatin while retaining its excellent anticancer profile, via the structural recombination and optimization of lobaplatin and carboplatin. The analogue was synthesized by the direct reaction between cis-[Pt (Ⅱ)(trans-1, 2-bis (methylamino)) I2] as an intermediate and the silver salt of 3-hydroxyl-1, 1-cyclobutanedicarboxylic acid, and characterized by elemental analysis, ESI-MS, IR and 1H, 13C NMR. The anticancer activity was evaluated by both in vitro cyotoxicity against four human cancer cell lines and in vivo antitumor efficiency in human lung carcinoma NCI-H460 xenografts in nude mice. The biological tests revealed that the analogue produced significant inhibition of the tumor growth, resulting in an inhibitory rate of 54% at the dose of 60 mg·kg-1 and more importantly, it had in vivo anticancer activity comparable to that of lobaplatin.
2017, 33(5): 843-852
doi: 10.11862/CJIC.2017.108
Abstract:
Magnetic porous composites of Fe3O4@SiO2-PSS@UiO-66 were prepared by hydrothermal method. The microstructure and morphology was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscope (SEM), infrared (IR), thermogravimetric analysis (TG), vibrating sample magnetometer (VSM) and N2 adsorption-desorption. The results show that magnetic UiO-66 composites are a core shell structure with spherical Fe3O4 as core and cubic MOF as shell. The composites show good superparamagnetism. The adsorption performance of 2-nitroresorcinolon Fe3O4@SiO2-PSS@UiO-66 was further studied. And the effects of contact time, adsorbent dose and initial 2-nitroresorcinol concentration on the adsorption process were explored. The results show that the maximum adsorption capacity is 161.36 mg·g-1 in following experimental conditions:contact time is 120 min, adsorbent dose is 5 mg, initial 2-nitroresorcinol concentration is 400 mg·L-1. In addition, the higher adsorption efficiency of 2-nitroresorcinol on magnetic UiO-66 composites may be due to the electrostatic interaction and π-π interaction of phenyl ring between UiO-66 and 2-nitroresorcinol.
Magnetic porous composites of Fe3O4@SiO2-PSS@UiO-66 were prepared by hydrothermal method. The microstructure and morphology was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscope (SEM), infrared (IR), thermogravimetric analysis (TG), vibrating sample magnetometer (VSM) and N2 adsorption-desorption. The results show that magnetic UiO-66 composites are a core shell structure with spherical Fe3O4 as core and cubic MOF as shell. The composites show good superparamagnetism. The adsorption performance of 2-nitroresorcinolon Fe3O4@SiO2-PSS@UiO-66 was further studied. And the effects of contact time, adsorbent dose and initial 2-nitroresorcinol concentration on the adsorption process were explored. The results show that the maximum adsorption capacity is 161.36 mg·g-1 in following experimental conditions:contact time is 120 min, adsorbent dose is 5 mg, initial 2-nitroresorcinol concentration is 400 mg·L-1. In addition, the higher adsorption efficiency of 2-nitroresorcinol on magnetic UiO-66 composites may be due to the electrostatic interaction and π-π interaction of phenyl ring between UiO-66 and 2-nitroresorcinol.
2017, 33(5): 853-859
doi: 10.11862/CJIC.2017.085
Abstract:
Silicon carbide precursors were synthesized by pyrolysis of polycarbosilane (PCS) at higher temperature. Subsequently, silicon carbide-derived carbons (SiC-CDCs) were obtained via chlorination of the SiC precursors at 1 000℃. The microstructure and morphology of the SiC-CDCs were characterized by X-ray diffraction pattern (XRD), Raman spectra, Transmission electron microscope (TEM) and N2 adsorption-desorption method. The effects of pyrolysis temperature on the crystal phase, morphology, pore size and distribution of the SiC-CDCs were investigated and the electrochemical performances as the electrode of supercapacitors were evaluated. The results show that SiC-CDCs with larger specific surface areas and sub-nanometer pores can be successfully prepared by chlorination of SiC precursors. Meanwhile, the SiC-CDCs exhibit better specific capacitances and supercapacitive performances at different current densities.
Silicon carbide precursors were synthesized by pyrolysis of polycarbosilane (PCS) at higher temperature. Subsequently, silicon carbide-derived carbons (SiC-CDCs) were obtained via chlorination of the SiC precursors at 1 000℃. The microstructure and morphology of the SiC-CDCs were characterized by X-ray diffraction pattern (XRD), Raman spectra, Transmission electron microscope (TEM) and N2 adsorption-desorption method. The effects of pyrolysis temperature on the crystal phase, morphology, pore size and distribution of the SiC-CDCs were investigated and the electrochemical performances as the electrode of supercapacitors were evaluated. The results show that SiC-CDCs with larger specific surface areas and sub-nanometer pores can be successfully prepared by chlorination of SiC precursors. Meanwhile, the SiC-CDCs exhibit better specific capacitances and supercapacitive performances at different current densities.
2017, 33(5): 860-866
doi: 10.11862/CJIC.2017.112
Abstract:
Layered LiMnxCoyO2 was prepared by co-precipitation preparation of precursor, and then sintered under 900℃ with different time. The results of X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the crystalline structure of the layered LiMnxCoyO2 is rhombohedron lattice whose space group is R3m, and has a similar lattice constant with LiCoO2. Under different sintering time, samples are spherical under scanning electron microscopy (SEM); as the sintering time extended, spherical morphology is better. With different samples of electrochemical performance test show that the samples with longer sintering time and higher relative content of Mn has better initial charge-discharge capacity and cycle performance.
Layered LiMnxCoyO2 was prepared by co-precipitation preparation of precursor, and then sintered under 900℃ with different time. The results of X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the crystalline structure of the layered LiMnxCoyO2 is rhombohedron lattice whose space group is R3m, and has a similar lattice constant with LiCoO2. Under different sintering time, samples are spherical under scanning electron microscopy (SEM); as the sintering time extended, spherical morphology is better. With different samples of electrochemical performance test show that the samples with longer sintering time and higher relative content of Mn has better initial charge-discharge capacity and cycle performance.
2017, 33(5): 867-873
doi: 10.11862/CJIC.2017.101
Abstract:
A multidentate Schiff base ligand (H3Lds, 1) with[NO3] donor set, derived from the condensation of salicylaldehyde and 2-Amino-2-methyl-1, 3-propanediol, reacted with copper (Ⅱ) chloride or cobalt (Ⅱ) acetate to yield two complexes[CuCl (H2Lds)]·H2O (2) and[Co2(H2O)2(Lds)2]·5H2O (3). The ligand and complexes were characterized by elemental analysis, IR, UV spectra and X-ray diffraction analysis. The results reveal that 1 crystallizes in orthorhombic space group P212121, 2 with Cu (Ⅱ) in distorted square-planar coordination in orthorhombic space group Pbca, 3 with Co (Ⅲ) in distorted coordination octahedron in monoclinic space group P21/c, respectively. The H3Lds is linked by intermolecular H-bonds to form two-dimension supramolecular network, while both complexes are connected by intermolecular hydrogen-bonding interactions to form a supramolecular chains, respectively.
A multidentate Schiff base ligand (H3Lds, 1) with[NO3] donor set, derived from the condensation of salicylaldehyde and 2-Amino-2-methyl-1, 3-propanediol, reacted with copper (Ⅱ) chloride or cobalt (Ⅱ) acetate to yield two complexes[CuCl (H2Lds)]·H2O (2) and[Co2(H2O)2(Lds)2]·5H2O (3). The ligand and complexes were characterized by elemental analysis, IR, UV spectra and X-ray diffraction analysis. The results reveal that 1 crystallizes in orthorhombic space group P212121, 2 with Cu (Ⅱ) in distorted square-planar coordination in orthorhombic space group Pbca, 3 with Co (Ⅲ) in distorted coordination octahedron in monoclinic space group P21/c, respectively. The H3Lds is linked by intermolecular H-bonds to form two-dimension supramolecular network, while both complexes are connected by intermolecular hydrogen-bonding interactions to form a supramolecular chains, respectively.
2017, 33(5): 769-778
doi: 10.11862/CJIC.2017.076
Abstract:
The probe 1 was readily prepared via condensation of 8-formyl-7-hydroxy-coumarin and carbonic dihydrazide in a one-step procedure. Probe 1 exhibited high sensitivity and selectivity towards Zn2+ and F- through a "turn-on" fluorescence response and/or ratiometric colorimetric response with low detection limits of the order of 10-8 mol·L-1. The complex behaviour was fully investigated by spectral titration, isothermal titration calorimetry, 1H NMR spectroscopic titration and mass spectrometry. Interestingly, probe 1 not only recognizes the cation Zn2+ and the anion F-, but can also distinguish between these two ions via the max wavelength in their UV-Vis spectra (360 nm for 1-Zn2+ vs 400 nm for 1-F- complex) or their fluorescent spectra (λex, λem=360, 454 nm for 1-Zn2+ vs λex, λem=400, 475 nm for 1-F- complex) due to their differing red-shifts. Additionally, probe 1 has been further explored in the detection of Zn2+ in living cells.
The probe 1 was readily prepared via condensation of 8-formyl-7-hydroxy-coumarin and carbonic dihydrazide in a one-step procedure. Probe 1 exhibited high sensitivity and selectivity towards Zn2+ and F- through a "turn-on" fluorescence response and/or ratiometric colorimetric response with low detection limits of the order of 10-8 mol·L-1. The complex behaviour was fully investigated by spectral titration, isothermal titration calorimetry, 1H NMR spectroscopic titration and mass spectrometry. Interestingly, probe 1 not only recognizes the cation Zn2+ and the anion F-, but can also distinguish between these two ions via the max wavelength in their UV-Vis spectra (360 nm for 1-Zn2+ vs 400 nm for 1-F- complex) or their fluorescent spectra (λex, λem=360, 454 nm for 1-Zn2+ vs λex, λem=400, 475 nm for 1-F- complex) due to their differing red-shifts. Additionally, probe 1 has been further explored in the detection of Zn2+ in living cells.
2017, 33(5): 779-786
doi: 10.11862/CJIC.2017.089
Abstract:
Fe/Cu nanocomposite was simply self-assembled through the cathodic decomposition of tetragonal spinel CuFe2O4 (t-CuFe2O4) in alkaline solution. The phase transition from t-CuFe2O4 to Cu/Fe3O4, and eventually to Fe/Cu composite was monitored by cyclic voltammetry (CV) and X-ray powder diffraction (XRD). Transmission electron microscope (TEM), selected area electron diffraction (SAED) and scanning TEM-energy dispersive X-ray (STEM-EDX) observations showed that the electro-crystallized copper and iron nanoparticles dispersed homogeneously and contacted intimately. When the Fe/Cu nanocomposite electrode was tested as the anode for nickel-iron (Ni-Fe) rechargeable battery, it exhibited enhanced discharge capacity, charge-acceptance and especially remarkable high-rate and low-temperature performances. Excellent capacity output and potential characteristics were achieved at high discharge current density (4 500 mA·gFe-1) or low operation temperature (-40℃), respectively. Linear scanning voltammetry (LSV) analyses demonstrated that the incorporation of in situ formed copper facilitated the anodic kinetics of active iron, resulting to the markedly enhanced high-rate and low-temperature discharge-ability of electrode.
Fe/Cu nanocomposite was simply self-assembled through the cathodic decomposition of tetragonal spinel CuFe2O4 (t-CuFe2O4) in alkaline solution. The phase transition from t-CuFe2O4 to Cu/Fe3O4, and eventually to Fe/Cu composite was monitored by cyclic voltammetry (CV) and X-ray powder diffraction (XRD). Transmission electron microscope (TEM), selected area electron diffraction (SAED) and scanning TEM-energy dispersive X-ray (STEM-EDX) observations showed that the electro-crystallized copper and iron nanoparticles dispersed homogeneously and contacted intimately. When the Fe/Cu nanocomposite electrode was tested as the anode for nickel-iron (Ni-Fe) rechargeable battery, it exhibited enhanced discharge capacity, charge-acceptance and especially remarkable high-rate and low-temperature performances. Excellent capacity output and potential characteristics were achieved at high discharge current density (4 500 mA·gFe-1) or low operation temperature (-40℃), respectively. Linear scanning voltammetry (LSV) analyses demonstrated that the incorporation of in situ formed copper facilitated the anodic kinetics of active iron, resulting to the markedly enhanced high-rate and low-temperature discharge-ability of electrode.
2017, 33(5): 874-880
doi: 10.11862/CJIC.2017.099
Abstract:
Two lanthanide coordination polymers, La (nbpdc)(phen)(FA) (1), Eu (nbpdc)(phen)(FA) (2) (FA=formic acid ion) based on bridging ligand 2, 2'-dinitro-4, 4'-biphenyldicarboxylic acid (H2nbpdc) and 1, 10-Phenanthroline monohydrate (phen), have been synthesized by the hydrothermal method and characterized by IR, single-crystal X-ray structure analysis, thermogravimetric analysis, luminescent properties, circular dichroism (CD) analysis and dielectric properties. Complexes 1 and 2 exhibited a rare three-interlude 3D structure with the same topology structure of (44·62). In addition, the two complexes exhibit fluorescent emissions in the solid state at room temperature. Fluorescent analysis of complexes 1 and 2 showed an intense emission band at 606 nm (λex=495 nm) and 615.5 nm (λex=395.5 nm), respectively. Moreover, the circular dichroism analysis of complexes 1 and 2 was measured with chirality.
Two lanthanide coordination polymers, La (nbpdc)(phen)(FA) (1), Eu (nbpdc)(phen)(FA) (2) (FA=formic acid ion) based on bridging ligand 2, 2'-dinitro-4, 4'-biphenyldicarboxylic acid (H2nbpdc) and 1, 10-Phenanthroline monohydrate (phen), have been synthesized by the hydrothermal method and characterized by IR, single-crystal X-ray structure analysis, thermogravimetric analysis, luminescent properties, circular dichroism (CD) analysis and dielectric properties. Complexes 1 and 2 exhibited a rare three-interlude 3D structure with the same topology structure of (44·62). In addition, the two complexes exhibit fluorescent emissions in the solid state at room temperature. Fluorescent analysis of complexes 1 and 2 showed an intense emission band at 606 nm (λex=495 nm) and 615.5 nm (λex=395.5 nm), respectively. Moreover, the circular dichroism analysis of complexes 1 and 2 was measured with chirality.
2017, 33(5): 881-889
doi: 10.11862/CJIC.2017.079
Abstract:
Two colorimetric sensors, derived from pentaerythrityltetramine and salicylaldehyde (1) or o-vanillin (2), had been synthesized. Both sensors showed selective colorimetric sensing ability for Fe (Ⅱ) and Fe (Ⅲ) by changing color from light yellow to either orange or purple when immersed in water samples. The sensors coordinated to Fe (Ⅲ) with 1:1 stoichiometry, as has been confirmed from the results of LC-MS spectrometry and UV-Vis spectrum titration. The detection limits of sensors 1 (0.19 μmol·L-1) and 2 (0.21 μmol·L-1) are lower than the WHO guideline (5 μmol·L-1) in drinking water.
Two colorimetric sensors, derived from pentaerythrityltetramine and salicylaldehyde (1) or o-vanillin (2), had been synthesized. Both sensors showed selective colorimetric sensing ability for Fe (Ⅱ) and Fe (Ⅲ) by changing color from light yellow to either orange or purple when immersed in water samples. The sensors coordinated to Fe (Ⅲ) with 1:1 stoichiometry, as has been confirmed from the results of LC-MS spectrometry and UV-Vis spectrum titration. The detection limits of sensors 1 (0.19 μmol·L-1) and 2 (0.21 μmol·L-1) are lower than the WHO guideline (5 μmol·L-1) in drinking water.
2017, 33(5): 890-896
doi: 10.11862/CJIC.2017.109
Abstract:
Two complexes, namely[NiL2]·CH3OH·0.5H2O (1) and[Cd (HL) Cl2)] (2) (HL=1-(3-methylpyrazin-2-yl) ethylidene-4-phenylsemicarbazide) have been synthesized and characterized by single crystal X-ray diffraction, elemental analysis and IR spectroscopy. X-ray diffraction analysis results show that the central Ni (Ⅱ) ion in complex 1 is surrounded by two independent anionic ligands with N2O donor set, thus possesses a distorted octahedral coordination geometry. However, in complex 2, the Cd (Ⅱ) ion with a distorted square pyramidal is coordinated with one neutral tridentate ligand HL and two chloride anions. In addition, the fluorescence spectra indicate that the interactions of the complexes with DNA are stronger than that of the ligand HL. CCDC 1479242:1; 1479243:2.
Two complexes, namely[NiL2]·CH3OH·0.5H2O (1) and[Cd (HL) Cl2)] (2) (HL=1-(3-methylpyrazin-2-yl) ethylidene-4-phenylsemicarbazide) have been synthesized and characterized by single crystal X-ray diffraction, elemental analysis and IR spectroscopy. X-ray diffraction analysis results show that the central Ni (Ⅱ) ion in complex 1 is surrounded by two independent anionic ligands with N2O donor set, thus possesses a distorted octahedral coordination geometry. However, in complex 2, the Cd (Ⅱ) ion with a distorted square pyramidal is coordinated with one neutral tridentate ligand HL and two chloride anions. In addition, the fluorescence spectra indicate that the interactions of the complexes with DNA are stronger than that of the ligand HL. CCDC 1479242:1; 1479243:2.
2017, 33(5): 897-904
doi: 10.11862/CJIC.2017.097
Abstract:
Three coordination complexes, namely[Cd2(ptp)2(SO4)(H2O)2]n (1), [Zn (ptp)2(H2O)2] (2) and[Cd (ptp)2(H2O)2] (3) (Hptp=2-(5-(pyridin-3-yl)-1H-1, 2, 4-triazol-3-yl) pyrazine), have been synthesized and characterized by elemental analyses, infrared spectra and single-crystal X-ray diffraction analyze. In complex 1, corrugated 1D chains constructed by the ptp- and Cd2+ were connected by SO42- to form a 3D structure. In isostructural complexes 2 and 3, intermolecular O-H…N hydrogen bonds link the mononuclear molecules into plane superstructure. The photocatalytic experiment result indicates that in the presence of H2O2, the degradation ratios of methylene blue (MB) reach to 79%, 81% and 88%, respectively, when complexes 1, 2 and 3 act as catalyst.
Three coordination complexes, namely[Cd2(ptp)2(SO4)(H2O)2]n (1), [Zn (ptp)2(H2O)2] (2) and[Cd (ptp)2(H2O)2] (3) (Hptp=2-(5-(pyridin-3-yl)-1H-1, 2, 4-triazol-3-yl) pyrazine), have been synthesized and characterized by elemental analyses, infrared spectra and single-crystal X-ray diffraction analyze. In complex 1, corrugated 1D chains constructed by the ptp- and Cd2+ were connected by SO42- to form a 3D structure. In isostructural complexes 2 and 3, intermolecular O-H…N hydrogen bonds link the mononuclear molecules into plane superstructure. The photocatalytic experiment result indicates that in the presence of H2O2, the degradation ratios of methylene blue (MB) reach to 79%, 81% and 88%, respectively, when complexes 1, 2 and 3 act as catalyst.
2017, 33(5): 905-912
doi: 10.11862/CJIC.2017.094
Abstract:
A new aroylhydrazone compound 4-fluoro-N'-(3-ethoxy-2-hydroxybenzylidene) benzohydrazide (H2L) was prepared. Reaction of H2L and VO (acac)2 with maltol (mat) and ethylmaltol (Emat), respectively, in methanol afforded the complexes[VO (L)(mat)] (1) and[VO (L)(Emat)] (2). Both H2L and the oxovanadium complexes were characterized by elemental analysis, IR, UV-Vis and 1H NMR spectra. The structures of the compounds were further confirmed by single crystal X-ray diffraction. The aroylhydrazone ligand, in its dianionic form, coordinated to the V atoms through the phenolate oxygen, imino nitrogen and enolate oxygen. The maltol and ethylmaltol ligands coordinated to the V atoms through the carbonyl oxygen and deprotonated hydroxyl oxygen. The V atom in each complex is in octahedral coordination. The complexes were administered intragastrically to both normal and alloxan-diabetic mice for two weeks. The biological activity results show that the complexes at doses of 10.0 and 20.0 mgV·kg-1, can significantly decrease the blood glucose level in alloxan-diabetic mice, but the blood glucose level in the treated normal mice was not altered.
A new aroylhydrazone compound 4-fluoro-N'-(3-ethoxy-2-hydroxybenzylidene) benzohydrazide (H2L) was prepared. Reaction of H2L and VO (acac)2 with maltol (mat) and ethylmaltol (Emat), respectively, in methanol afforded the complexes[VO (L)(mat)] (1) and[VO (L)(Emat)] (2). Both H2L and the oxovanadium complexes were characterized by elemental analysis, IR, UV-Vis and 1H NMR spectra. The structures of the compounds were further confirmed by single crystal X-ray diffraction. The aroylhydrazone ligand, in its dianionic form, coordinated to the V atoms through the phenolate oxygen, imino nitrogen and enolate oxygen. The maltol and ethylmaltol ligands coordinated to the V atoms through the carbonyl oxygen and deprotonated hydroxyl oxygen. The V atom in each complex is in octahedral coordination. The complexes were administered intragastrically to both normal and alloxan-diabetic mice for two weeks. The biological activity results show that the complexes at doses of 10.0 and 20.0 mgV·kg-1, can significantly decrease the blood glucose level in alloxan-diabetic mice, but the blood glucose level in the treated normal mice was not altered.
